Center for Biologically Inspired Materials and Material Systems Pratt School of Engineering Duke University |
||
HOME > pratt > CBIMMS | Search Help Login |
| Publications of Stefan Zauscher :chronological alphabetical combined listing:%% Papers Published @article{fds369714, Author = {Young, MN and Sindoni, MJ and Lewis, AH and Zauscher, S and Grandl, J}, Title = {The energetics of rapid cellular mechanotransduction.}, Journal = {Proc Natl Acad Sci U S A}, Volume = {120}, Number = {8}, Pages = {e2215747120}, Year = {2023}, Month = {February}, url = {http://dx.doi.org/10.1073/pnas.2215747120}, Abstract = {Cells throughout the human body detect mechanical forces. While it is known that the rapid (millisecond) detection of mechanical forces is mediated by force-gated ion channels, a detailed quantitative understanding of cells as sensors of mechanical energy is still lacking. Here, we combine atomic force microscopy with patch-clamp electrophysiology to determine the physical limits of cells expressing the force-gated ion channels (FGICs) Piezo1, Piezo2, TREK1, and TRAAK. We find that, depending on the ion channel expressed, cells can function either as proportional or nonlinear transducers of mechanical energy and detect mechanical energies as little as ~100 fJ, with a resolution of up to ~1 fJ. These specific energetic values depend on cell size, channel density, and cytoskeletal architecture. We also make the surprising discovery that cells can transduce forces either nearly instantaneously (<1 ms) or with a substantial time delay (~10 ms). Using a chimeric experimental approach and simulations, we show how such delays can emerge from channel-intrinsic properties and the slow diffusion of tension in the membrane. Overall, our experiments reveal the capabilities and limits of cellular mechanosensing and provide insights into molecular mechanisms that different cell types may employ to specialize for their distinct physiological roles.}, Doi = {10.1073/pnas.2215747120}, Key = {fds369714} } @article{fds362173, Author = {Simon, M and Prause, A and Zauscher, S and Gradzielski, M}, Title = {Self-Assembled Single-Stranded DNA Nano-Networks in Solution and at Surfaces.}, Journal = {Biomacromolecules}, Volume = {23}, Number = {3}, Pages = {1242-1250}, Year = {2022}, Month = {March}, url = {http://dx.doi.org/10.1021/acs.biomac.1c01493}, Abstract = {We studied the directed self-assembly of two types of complementary single-stranded DNA (ssDNA) strands [i.e., poly(dA) and poly(dT)] into more complex, organized, and percolating networks in dilute solutions and at surfaces. Understanding ssDNA self-assembly into 2D networks on surfaces is important for the use of such networks in the fabrication of well-defined nanotechnological devices, as, for instance, required in nanoelectronics or for biosensing. To control the formation of 2D networks on surfaces, it is important to know whether DNA assemblies are formed already in dilute solutions or only during the drying/immobilization process at the surface, where the concentration automatically increases. Fluorescence cross-correlation spectroscopy clearly shows the presence of larger DNA complexes in mixed poly(dA) and poly(dT) solutions already at very low DNA concentrations (<1 nM), that is, well below the overlap concentration. Here, we describe for the first time such supramolecular complexes in solution and how their structure depends on the ssDNA length and concentration and ionic strength. Hence, future attempts to control such networks should also focus on network precursors in solution and not only on their immobilization on surfaces.}, Doi = {10.1021/acs.biomac.1c01493}, Key = {fds362173} } @article{fds359628, Author = {Gilpin, A and Zeng, Y and Hoque, J and Ryu, JH and Yang, Y and Zauscher, S and Eward, W and Varghese, S}, Title = {Self-Healing of Hyaluronic Acid to Improve In Vivo Retention and Function.}, Journal = {Adv Healthc Mater}, Volume = {10}, Number = {23}, Pages = {e2100777}, Year = {2021}, Month = {December}, url = {http://dx.doi.org/10.1002/adhm.202100777}, Abstract = {Convergent advances in the field of soft matter, macromolecular chemistry, and engineering have led to the development of biomaterials that possess autonomous, adaptive, and self-healing characteristics similar to living systems. These rationally designed biomaterials can surpass the capabilities of their parent material. Herein, the modification of hyaluronic acid (HA) to exhibit self-healing properties is described, and its physical and biological function both in vitro and in vivo is studied. The in vitro findings showed that self-healing HA designed to undergo self-repair improves lubrication, enhances free radical scavenging, and attenuates enzymatic degradation compared to unmodified HA. Longitudinal imaging following intraarticular injection of self-healing HA shows improved in vivo retention despite its low molecular weight. Concomitant with these functions, intraarticular injection of self-healing HA mitigates anterior cruciate ligament injury-mediated cartilage degeneration in rodents. This proof-of-concept study shows how incorporation of functional properties such as self-healing can be used to surpass the existing capabilities of biolubricants.}, Doi = {10.1002/adhm.202100777}, Key = {fds359628} } @article{fds358984, Author = {Yang, Y and Lu, Q and Huang, C-M and Qian, H and Zhang, Y and Deshpande, S and Arya, G and Ke, Y and Zauscher, S}, Title = {Programmable Site-Specific Functionalization of DNA Origami with Polynucleotide Brushes.}, Journal = {Angewandte Chemie International Edition}, Volume = {60}, Number = {43}, Pages = {23241-23247}, Publisher = {WILEY}, Year = {2021}, Month = {October}, url = {http://dx.doi.org/10.1002/anie.202107829}, Abstract = {Combining surface-initiated, TdT (terminal deoxynucleotidyl transferase) catalyzed enzymatic polymerization (SI-TcEP) with precisely engineered DNA origami nanostructures (DONs) presents an innovative pathway for the generation of stable, polynucleotide brush-functionalized DNA nanostructures. We demonstrate that SI-TcEP can site-specifically pattern DONs with brushes containing both natural and non-natural nucleotides. The brush functionalization can be precisely controlled in terms of the location of initiation sites on the origami core and the brush height and composition. Coarse-grained simulations predict the conformation of the brush-functionalized DONs that agree well with the experimentally observed morphologies. We find that polynucleotide brush-functionalization increases the nuclease resistance of DONs significantly, and that this stability can be spatially programmed through the site-specific growth of polynucleotide brushes. The ability to site-specifically decorate DONs with brushes of natural and non-natural nucleotides provides access to a large range of functionalized DON architectures that would allow for further supramolecular assembly, and for potential applications in smart nanoscale delivery systems.}, Doi = {10.1002/anie.202107829}, Key = {fds358984} } @article{fds358983, Author = {Navarro, LA and Ryan, JJ and Dzuricky, M and Gradzielski, M and Chilkoti, A and Zauscher, S}, Title = {Microphase Separation of Resilin-like and Elastin-like Diblock Copolypeptides in Concentrated Solutions.}, Journal = {Biomacromolecules}, Volume = {22}, Number = {9}, Pages = {3827-3838}, Year = {2021}, Month = {September}, url = {http://dx.doi.org/10.1021/acs.biomac.1c00672}, Abstract = {Diblock copolymers are valued for their ability to form thin films with nanoscale features that typically reflect those of their microphase-separated structures in concentrated solution. Here, we show that such self-assembled structures can be easily formed with diblock copolymers composed of thermally responsive polypeptides, such as resilin-like polypeptides (RLP) and elastin-like polypeptides (ELP), by exploiting the inverse temperature transition behavior of ELPs in aqueous media. Specifically, we examine the self-assembly of a series of RLP-<i>b</i>-ELP diblock copolypeptides in concentrated aqueous solution (30 and 50 wt %) by small-angle X-ray scattering (SAXS). By systematically varying RLP block length and temperature (10-45 °C), we observed microphase separation into hexagonally packed cylinders and lamellae. By analyzing the observed order-order transitions (OOT) and order-disorder transitions (ODT), we determined that self-assembly in this system is primarily driven by polymer-solvent interactions. While these thermally responsive polymers showed clear ODTs and OOTs at certain temperatures, temperature only had a weak effect on the spacing of the resulting nanostructures. In contrast, we found that nanostructure spacing was far more sensitive to RLP block length. Finally, we used atomic force microscopy (AFM) to demonstrate that spin casting RLP-<i>b</i>-ELP diblock copolypeptides also produce nanostructured thin films with spacings that correlate with those in concentrated solution.}, Doi = {10.1021/acs.biomac.1c00672}, Key = {fds358983} } @article{fds354600, Author = {Walkowiak, J and Gradzielski, M and Zauscher, S and Ballauff, M}, Title = {Interaction of Proteins with a Planar Poly(acrylic acid) Brush: Analysis by Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D).}, Journal = {Polymers}, Volume = {13}, Number = {1}, Pages = {E122}, Year = {2020}, Month = {December}, url = {http://dx.doi.org/10.3390/polym13010122}, Abstract = {We describe the preparation of a poly(acrylic acid) (PAA) brush, polymerized by atom transfer radical polymerization (ATRP) of tert-butyl acrylate (tBA) and subsequent acid hydrolysis, on the flat gold surfaces of quartz-crystal microbalance (QCM) crystals. The PAA brushes were characterized by Fourier transform infrared (FT-IR) spectroscopy, ellipsometry and water contact angle analysis. The interaction of the PAA brushes with human serum albumin (HSA) was studied for a range of ionic strengths and pH conditions by quartz-crystal microbalance with dissipation monitoring (QCM-D). The quantitative analysis showed a strong adsorption of protein molecules onto the PAA brush. By increasing the ionic strength, we were able to release a fraction of the initially bound HSA molecules. This finding highlights the importance of counterions in the polyelectrolyte-mediated protein adsorption/desorption. A comparison with recent calorimetric studies related to the binding of HSA to polyelectrolytes allowed us to fully analyze the QCM data based on the results of the thermodynamic analysis of the binding process.}, Doi = {10.3390/polym13010122}, Key = {fds354600} } @article{fds351487, Author = {Fries, CN and Wu, Y and Kelly, SH and Wolf, M and Votaw, NL and Zauscher, S and Collier, JH}, Title = {Controlled Lengthwise Assembly of Helical Peptide Nanofibers to Modulate CD8+ T-Cell Responses.}, Journal = {Advanced Materials (Deerfield Beach, Fla.)}, Volume = {32}, Number = {39}, Pages = {e2003310}, Year = {2020}, Month = {October}, url = {http://dx.doi.org/10.1002/adma.202003310}, Abstract = {Peptide nanofibers are useful for many biological applications, including immunotherapy, tissue engineering, and drug delivery. The robust lengthwise assembly of these peptides into nanofibers is typically difficult to control, resulting in polydisperse fiber lengths and an incomplete understanding of how nanofiber length affects biological responses. Here, rationally designed capping peptides control the length of helical peptide nanofibers with unique precision. These designed peptides bind the tips of elongated nanofibers to shorten and narrow their length distributions. Demonstrating their use as immunotherapies, capped nanofibers are preferentially cross-presented by dendritic cells compared to uncapped nanofibers. Due to increased cross-presentation, these capped nanofibers trigger stronger CD8<sup>+</sup> T-cell responses in mice than uncapped nanofibers. This strategy illustrates a means for controlling the length of supramolecular peptide nanofibers to modulate their immunogenicity in the context of immunotherapies.}, Doi = {10.1002/adma.202003310}, Key = {fds351487} } @article{fds352662, Author = {Noyce, SG and Doherty, JL and Zauscher, S and Franklin, AD}, Title = {Understanding and Mapping Sensitivity in MoS2 Field-Effect-Transistor-Based Sensors.}, Journal = {Acs Nano}, Volume = {14}, Number = {9}, Pages = {11637-11647}, Year = {2020}, Month = {September}, url = {http://dx.doi.org/10.1021/acsnano.0c04192}, Abstract = {Sensors based on two-dimensional (2D) field-effect transistors (FETs) are extremely sensitive and can detect charged analytes with attomolar limits of detection (LOD). Despite some impressive LODs, the operating mechanisms and factors that determine the signal-to-noise ratio in 2D FET-based sensors remain poorly understood. These uncertainties, coupled with an expansive design space for sensor layout and analyte positioning, result in a field with many reported highlights but limited collective progress. Here, we provide insight into sensing mechanisms of 2D molybdenum disulfide (MoS<sub>2</sub>) FETs by realizing precise control over the position and charge of an analyte using a customized atomic force microscope (AFM), with the AFM tip acting as an analyte. The sensitivity of the MoS<sub>2</sub> FET channel is revealed to be nonuniform, manifesting sensitive hotspots with locations that are stable over time. When the charge of the analyte is varied, an asymmetry is observed in the device drain-current response, with analytes acting to turn the device off leading to a 2.5× increase in the signal-to-noise ratio (SNR). We developed a numerical model, applicable to all FET-based charge-detection sensors, that confirms our experimental observation and suggests an underlying mechanism. Further, extensive characterization of a set of different MoS<sub>2</sub> FETs under various analyte conditions, coupled with the numerical model, led to the identification of three distinct SNRs that peak with dependence on the layout and operating conditions used for a sensor. These findings reveal the important role of analyte position and coverage in determining the optimal operating bias conditions for maximal sensitivity in 2D FET-based sensors, which provides key insights for future sensor design and control.}, Doi = {10.1021/acsnano.0c04192}, Key = {fds352662} } @article{fds349645, Author = {Navarro, LA and Shah, TP and Zauscher, S}, Title = {Grafting To of Bottlebrush Polymers: Conformation and Kinetics.}, Journal = {Langmuir : the Acs Journal of Surfaces and Colloids}, Volume = {36}, Number = {17}, Pages = {4745-4756}, Year = {2020}, Month = {May}, url = {http://dx.doi.org/10.1021/acs.langmuir.9b03620}, Abstract = {Specifically adsorbed bottlebrush coatings are found in nature as brush-like glycoproteins that decorate biointerfaces and provide antifouling, lubrication, or wear-protection. Although various synthetic strategies have been developed to mimic glycoprotein structure and function, the use of these mimics is still limited because of the current lack of understanding of their adsorption behavior and surface conformation. In this paper, we examine the adsorption behavior of PEG-based, biotinylated bottlebrushes with different backbone and bristle lengths to streptavidin model surfaces in phosphate-buffered saline. By using quartz crystal microbalance, localized surface plasmon resonance, and atomic force microscopy, we learn how bottlebrush dimensions impact their adsorption kinetics, surface conformation, mechanical properties, and antifouling properties. Our bottlebrushes qualitatively mirror the adsorption behavior of linear polymers and exhibit three kinetic regimes of adsorption: (I) a transport-limited regime, (II) a pause, and (III) a penetration-limited regime. Furthermore, we find that the bristle length more dramatically affects brush properties than the backbone length. Generally, larger bottlebrush dimensions lead to reduced molar adsorption, retarded kinetics, weaker antifouling, and softer brush coatings. Longer bristles also lead to less mass adsorption, while the opposite trend is observed for increasing backbone length. In summary, our findings aid the rational design of new bottlebrush coatings by elucidating how their dimensions impact adsorption, surface conformation, and the properties of the final coating.}, Doi = {10.1021/acs.langmuir.9b03620}, Key = {fds349645} } @article{fds348734, Author = {Zhou, Y and Maleski, K and Anasori, B and Thostenson, JO and Pang, Y and Feng, Y and Zeng, K and Parker, CB and Zauscher, S and Gogotsi, Y and Glass, JT and Cao, C}, Title = {Ti3C2Tx MXene-Reduced Graphene Oxide Composite Electrodes for Stretchable Supercapacitors.}, Journal = {Acs Nano}, Volume = {14}, Number = {3}, Pages = {3576-3586}, Year = {2020}, Month = {March}, url = {http://dx.doi.org/10.1021/acsnano.9b10066}, Abstract = {The development of stretchable electronics requires the invention of compatible high-performance power sources, such as stretchable supercapacitors and batteries. In this work, two-dimensional (2D) titanium carbide (Ti3C2Tx) MXene is being explored for flexible and printed energy storage devices by fabrication of a robust, stretchable high-performance supercapacitor with reduced graphene oxide (RGO) to create a composite electrode. The Ti3C2Tx/RGO composite electrode combines the superior electrochemical and mechanical properties of Ti3C2Tx and the mechanical robustness of RGO resulting from strong nanosheet interactions, larger nanoflake size, and mechanical flexibility. It is found that the Ti3C2Tx/RGO composite electrodes with 50 wt % RGO incorporated prove to mitigate cracks generated under large strains. The composite electrodes exhibit a large capacitance of 49 mF/cm2 (∼490 F/cm3 and ∼140 F/g) and good electrochemical and mechanical stability when subjected to cyclic uniaxial (300%) or biaxial (200% × 200%) strains. The as-assembled symmetric supercapacitor demonstrates a specific capacitance of 18.6 mF/cm2 (∼90 F/cm3 and ∼29 F/g) and a stretchability of up to 300%. The developed approach offers an alternative strategy to fabricate stretchable MXene-based energy storage devices and can be extended to other members of the large MXene family.}, Doi = {10.1021/acsnano.9b10066}, Key = {fds348734} } @article{fds348924, Author = {Roberts, S and Miao, V and Costa, S and Simon, J and Kelly, G and Shah, T and Zauscher, S and Chilkoti, A}, Title = {Complex microparticle architectures from stimuli-responsive intrinsically disordered proteins.}, Journal = {Nature Communications}, Volume = {11}, Number = {1}, Pages = {1342}, Year = {2020}, Month = {March}, url = {http://dx.doi.org/10.1038/s41467-020-15128-9}, Abstract = {The controllable production of microparticles with complex geometries is useful for a variety of applications in materials science and bioengineering. The formation of intricate microarchitectures typically requires sophisticated fabrication techniques such as flow lithography or multiple-emulsion microfluidics. By harnessing the molecular interactions of a set of artificial intrinsically disordered proteins (IDPs), we have created complex microparticle geometries, including porous particles, core-shell and hollow shell structures, and a unique 'fruits-on-a-vine' arrangement, by exploiting the metastable region of the phase diagram of thermally responsive IDPs within microdroplets. Through multi-site unnatural amino acid (UAA) incorporation, these protein microparticles can also be photo-crosslinked and stably extracted to an all-aqueous environment. This work expands the functional utility of artificial IDPs as well as the available microarchitectures of this class of biocompatible IDPs, with potential applications in drug delivery and tissue engineering.}, Doi = {10.1038/s41467-020-15128-9}, Key = {fds348924} } @article{fds358985, Author = {Kim, HS and Brown, NA and Zauscher, S and Yingling, YG}, Title = {Effect of Octadecylamine Surfactant on DNA Interactions with Graphene Surfaces.}, Journal = {Langmuir : the Acs Journal of Surfaces and Colloids}, Volume = {36}, Number = {4}, Pages = {931-938}, Year = {2020}, Month = {February}, url = {http://dx.doi.org/10.1021/acs.langmuir.9b02926}, Abstract = {Understanding of how to integrate DNA molecules with graphene materials is important for the development of biosensors and biomolecular logic circuits. For some of these applications, controlling DNA structural conformation on the graphene substrate is critically important and can be achieved through the use of self-assembled monolayers. Here, we performed all-atom molecular dynamics simulations to understand how various 1-octadecylamine (ODA) coatings of the graphene surface affect the conformation of double-stranded DNA (dsDNA) on the surface. The simulation results demonstrated that dsDNA structures become more stable as ODA concentration increases due to the formation of DNA-ODA hydrogen bonds and reduction of DNA-surface interactions, which aid in retaining internal DNA interactions. Specifically, the interaction of ODA molecules with DNA prevents nucleobases from forming π-π stacking interactions with the surface. Some dsDNA conformations, such as sharp kinks or unwinding, can occur more frequently in DNA with A-T sequences due to weaker pairing interactions than with G-C sequences. Furthermore, our results conclude that both DNA sequence and ODA concentration play an essential role in experimentally observed conformational changes of DNA on the graphene surface.}, Doi = {10.1021/acs.langmuir.9b02926}, Key = {fds358985} } @article{fds347038, Author = {Walkowiak, J and Lu, Y and Gradzielski, M and Zauscher, S and Ballauff, M}, Title = {Thermodynamic Analysis of the Uptake of a Protein in a Spherical Polyelectrolyte Brush.}, Journal = {Macromolecular Rapid Communications}, Volume = {41}, Number = {1}, Pages = {e1900421}, Year = {2020}, Month = {January}, url = {http://dx.doi.org/10.1002/marc.201900421}, Abstract = {A thermodynamic study of the adsorption of Human Serum Albumin (HSA) onto spherical polyelectrolyte brushes (SPBs) by isothermal titration calorimetry (ITC) is presented. The SPBs are composed of a solid polystyrene core bearing long chains of poly(acrylic acid). ITC measurements done at different temperatures and ionic strengths lead to a full set of thermodynamicbinding constants together with the enthalpies and entropies of binding. The adsorption of HSA onto SPBs is described with a two-step model. The free energy of binding ΔGb depends only weakly on temperature because of a marked compensation of enthalpy by entropy. Studies of the adsorbed HSA by Fourier transform infrared spectroscopy (FT-IR) demonstrate no significant disturbance in the secondary structure of the protein. The quantitative analysis demonstrates that counterion release is the major driving force for adsorption in a process where proteins become multivalent counterions of the polyelectrolyte chains upon adsorption. A comparison with the analysis of other sets of data related to the binding of HSA to polyelectrolytes demonstrates that the cancellation of enthalpy and entropy is a general phenomenon that always accompanies the binding of proteins to polyelectrolytes dominated by counterion release.}, Doi = {10.1002/marc.201900421}, Key = {fds347038} } @article{fds345459, Author = {Eldridge, WJ and Ceballos, S and Shah, T and Park, HS and Steelman, ZA and Zauscher, S and Wax, A}, Title = {Shear Modulus Measurement by Quantitative Phase Imaging and Correlation with Atomic Force Microscopy.}, Journal = {Biophysical Journal}, Volume = {117}, Number = {4}, Pages = {696-705}, Year = {2019}, Month = {August}, url = {http://dx.doi.org/10.1016/j.bpj.2019.07.008}, Abstract = {Many approaches have been developed to characterize cell elasticity. Among these, atomic force microscopy (AFM) combined with modeling has been widely used to characterize cellular compliance. However, such approaches are often limited by the difficulties associated with using a specific instrument and by the complexity of analyzing the measured data. More recently, quantitative phase imaging (QPI) has been applied to characterize cellular stiffness by using an effective spring constant. This metric was further correlated to mass distribution (disorder strength) within the cell. However, these measurements are difficult to compare to AFM-derived measurements of Young's modulus. Here, we describe, to our knowledge, a new way of analyzing QPI data to directly retrieve the shear modulus. Our approach enables label-free measurement of cellular mechanical properties that can be directly compared to values obtained from other rheological methods. To demonstrate the technique, we measured shear modulus and phase disorder strength using QPI, as well as Young's modulus using AFM, across two breast cancer cell-line populations dosed with three different concentrations of cytochalasin D, an actin-depolymerizing toxin. Comparison of QPI-derived and AFM moduli shows good agreement between the two measures and further agrees with theory. Our results suggest that QPI is a powerful tool for cellular biophysics because it allows for optical quantitative measurements of cell mechanical properties.}, Doi = {10.1016/j.bpj.2019.07.008}, Key = {fds345459} } @article{fds358986, Author = {Sokolowski, M and Parlak, Z and Bartsch, C and Zauscher, S and Gradzielski, M}, Title = {Interaction between Soft Nanoparticles and Phospholipid Membranes: Effect of the Polymer-Grafting Density on Nanoparticle Adsorption}, Journal = {Acs Applied Nano Materials}, Volume = {2}, Number = {4}, Pages = {1808-1819}, Year = {2019}, Month = {April}, url = {http://dx.doi.org/10.1021/acsanm.8b01868}, Abstract = {Nanoparticles (NPs) have large potential for biological applications as typically they exhibit strongly size-dependent properties. Specifically, the interaction of NPs with phospholipid membranes is of significant relevance to nanomedicine and the related field of nanotoxicology. Therefore, the investigation of NP interactions with model membranes is not only of fundamental importance but also of practical value to understand NP interactions with more complex cell membranes. Supported lipid bilayers (SLBs) provide a powerful platform to study such interactions. Here, we report on the interaction of SiO2-NPs, covered with cationic polymer (PDMAEMA) of different grafting density but approximately constant polymer layer thickness, with SLBs of differing charge density. We studied binding of the NPs to the SLBs by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). A key result of the study is that at low solution pH and in the presence of electrostatic attraction, the amount of adsorbed NPs drastically decreases with increasing polymer brush grafting density beyond a critical value. However, upon increasing the solution pH (thereby lowering the apparent electrostatic attraction) even NPs with high polymer grafting density adsorb. In this transitional range, NP adsorption depends strongly on NP concentration becoming reduced at higher concentration. The experimental observations were interpreted by simple models taking into account electrostatic and van der Waals interactions that allow to gain some insights into the prevailing conditions.}, Doi = {10.1021/acsanm.8b01868}, Key = {fds358986} } @article{fds341550, Author = {Navarro, LA and Enciso, AE and Matyjaszewski, K and Zauscher, S}, Title = {Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring.}, Journal = {Journal of the American Chemical Society}, Volume = {141}, Number = {7}, Pages = {3100-3109}, Year = {2019}, Month = {February}, url = {http://dx.doi.org/10.1021/jacs.8b12072}, Abstract = {Polymer brush coatings are frequently prepared by radical polymerization, a notoriously oxygen sensitive process. Glucose oxidase (GOx) can inexpensively enable radical polymerization in solution by enzymatically consuming oxygen as it oxidizes glucose. Here, we report the growth of polymeric brushes using GOx-assisted atom transfer radical polymerization (ATRP) from a surface while open to air. Specifically, we grew a set of biomedically relevant polymer brushes, including poly(oligo(ethylene glycol) methacrylate) (POEGMA), poly(2-dimethylaminoethyl methacrylate) (PDMAEMA), poly(sulfobetaine methacrylate) (PSBMA), and poly(2-(methylsulfinyl)ethyl acrylate (PMSEA). For each of these polymers, we monitored GOx-assisted and GOx-free ATRP reaction kinetics in real time using quartz crystal microbalance (QCM) and verified findings with localized surface plasmon resonance (LSPR). We modeled brush growth kinetics considering bimolecular termination. This model fit our data well ( r<sup>2</sup> > 0.987 for all samples) and shows the addition of GOx increased effective kinetic chain lengths, propagation rates, and reproducibility. We tested the antifouling properties of the polymer brush coatings against human blood plasma and were surprised to find that coatings prepared with GOx repelled more plasma proteins in all cases than their GOx-free counterparts.}, Doi = {10.1021/jacs.8b12072}, Key = {fds341550} } @article{fds339660, Author = {Navarro, LA and French, DL and Zauscher, S}, Title = {Advances in mucin mimic synthesis and applications in surface science}, Journal = {Current Opinion in Colloid & Interface Science}, Volume = {38}, Pages = {122-134}, Publisher = {Elsevier BV}, Year = {2018}, Month = {November}, url = {http://dx.doi.org/10.1016/j.cocis.2018.09.004}, Abstract = {Mucins are a class of glycoproteins that serve key roles in tissue protection, hydration, and lubrication. However, their study and application are complicated by their post-translational modifications, heterogeneity, and their propensity to deteriorate upon isolation. As a result, several groups have made strides in synthesizing mucin-mimicking compounds for systematic study and therapeutic applications. In this paper, we review general mucin structure, recent trends in the design and synthesis of mucin mimics, and the ways mucin analogues can outperform native mucins. Specifically, we highlight the structures of lubricin and aggrecan, which are the subject of many biomimetic approaches. Furthermore, we showcase the structural features that allow analogues to mimic mucin functions and categorize them based on their roles as monolayer coatings, gel formers, or adhesion promoters. Lastly, we examine the chemical composition of mucin analogues, emphasizing how modular approaches provide flexibility to repurpose mucin mimics for different applications.}, Doi = {10.1016/j.cocis.2018.09.004}, Key = {fds339660} } @article{fds340146, Author = {Feng, Y and Marusak, KE and You, L and Zauscher, S}, Title = {Biosynthetic transition metal chalcogenide semiconductor nanoparticles: Progress in synthesis, property control and applications}, Journal = {Current Opinion in Colloid & Interface Science}, Volume = {38}, Pages = {190-203}, Publisher = {Elsevier BV}, Year = {2018}, Month = {November}, url = {http://dx.doi.org/10.1016/j.cocis.2018.11.002}, Abstract = {Transition metal (TM) chalcogenides are a group of semiconductor materials with applications that range from antibacterial particles to thin films in energy conversion devices. Significant progress in synthetic biology combined with the benefits of low energy consumption and low toxic waste burden of “green synthesis,” have directed considerable research attention to the biosynthesis of these inorganic materials. TM chalcogenide nanoparticles (NP) can be produced by a variety of microorganisms including bacteria, fungi, algae, and yeast, as well as cell-free approaches using enzymes. Recent research shows that the size, crystal structure, and bandgap of these TM NPs can be well controlled, which has led to prototypical applications of these biosynthetic NPs in the areas of bio-remediation, bio-imaging, photocatalysis, and energy conversion. This review is the first to combine recent progress in the biosynthesis, property control, and applications of TM chalcogenide NPs.}, Doi = {10.1016/j.cocis.2018.11.002}, Key = {fds340146} } @article{fds340147, Author = {Malmsten, M and Zauscher, S}, Title = {Editorial overview: Colloids and surfaces in biology}, Journal = {Current Opinion in Colloid & Interface Science}, Volume = {38}, Pages = {A1-A3}, Publisher = {Elsevier BV}, Year = {2018}, Month = {November}, url = {http://dx.doi.org/10.1016/j.cocis.2018.11.006}, Doi = {10.1016/j.cocis.2018.11.006}, Key = {fds340147} } @article{fds327223, Author = {Rastogi, SK and Anderson, HE and Lamas, J and Barret, S and Cantu, T and Zauscher, S and Brittain, WJ and Betancourt, T}, Title = {Enhanced Release of Molecules upon Ultraviolet (UV) Light Irradiation from Photoresponsive Hydrogels Prepared from Bifunctional Azobenzene and Four-Arm Poly(ethylene glycol).}, Journal = {Acs Applied Materials & Interfaces}, Volume = {10}, Number = {36}, Pages = {30071-30080}, Year = {2018}, Month = {September}, url = {http://dx.doi.org/10.1021/acsami.6b16183}, Abstract = {Advances in biosensors and drug delivery are dependent on hydrogels that respond to external stimuli. In this work, we describe the preparation and characterization of photoresponsive hydrogels prepared by cross-linking of di-NHS ester of azobenzoic acid and four-armed, amine-terminated poly(ethylene glycol). The porous structure and composition of the hydrogels were confirmed by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. The reversible photoisomerization of the azobenzene-containing hydrogel cross-linkers in the gels was confirmed by absorption spectroscopy. Specifically, the photoisomerization of the cross-linkers between their trans and cis configurations was observed by monitoring the absorbance of the hydrogels at the two characteristic peaks of azobenzene (π-π* at 330 nm and n-π* at 435 nm). The effect of photoisomerization on the hydrogel structure was investigated by microscopy. Ultraviolet (UV) irradiation-induced reduction in hydrogel size was observed, which may be a result of the inherently smaller footprint of the cis azobenzene conformation, as well as dipole-dipole interactions between the polar cis azobenzene and the polymer network. The UV-triggered reduction in hydrogel size was accompanied by enhanced release of the near-infrared fluorescent dye Alexa Fluor 750 (AF<sub>750</sub>). Enhanced release of AF<sub>750</sub> was observed in samples irradiated with UV versus dark control. Together, these data demonstrate the potential of these systems as reversible photoresponsive biomaterials.}, Doi = {10.1021/acsami.6b16183}, Key = {fds327223} } @article{fds335903, Author = {Navarro, LA and French, DL and Zauscher, S}, Title = {Synthesis of Modular Brush Polymer-Protein Hybrids Using Diazotransfer and Copper Click Chemistry.}, Journal = {Bioconjugate Chemistry}, Volume = {29}, Number = {8}, Pages = {2594-2605}, Year = {2018}, Month = {August}, url = {http://dx.doi.org/10.1021/acs.bioconjchem.8b00309}, Abstract = {Proteoglycans are important brush-like biomacromolecules, which serve a variety of functions in the human body. While protein-bottlebrush hybrids are promising proteoglycan mimics, many challenges still exist to robustly produce such polymers. In this paper, we report the modular synthesis of protein-brush hybrids containing elastin-like polypeptides (ELP) as model proteins by copper-catalyzed azide-alkyne cycloaddition. We exploit the recently discovered imidazole-1-sulfonyl azide (ISA) in a diazotransfer reaction to introduce an N-terminal azide onto an ELP. Next, we use a click reaction to couple the azido-ELP to an alkyne-terminated amine-rich polymer followed by a second diazotransfer step to produce an azide-rich backbone that serves as a scaffold. Finally, we used a second click reaction to graft alkyne-terminated poly(oligoethylene glycol methacrylate) (POEGMA) bristles to the azide-rich backbone to produce the final protein-bottlebrush hybrid. We demonstrate the effectiveness of this synthetic path at each step through careful characterization with <sup>1</sup>H NMR, FTIR, GPC, and diagnostic test reactions on SDS-PAGE. Final reaction products could be consistently obtained for a variety of different molecular weight backbones with final total grafting efficiencies around 70%. The high-yielding reactions employed in this highly modular approach allow for the synthesis of protein-bottlebrush hybrids with different proteins and brush polymers. Additionally, the mild reaction conditions used have the potential to avoid damage to proteins during synthesis.}, Doi = {10.1021/acs.bioconjchem.8b00309}, Key = {fds335903} } @article{fds335904, Author = {Gu, R and Oweida, T and Yingling, YG and Chilkoti, A and Zauscher, S}, Title = {Enzymatic Synthesis of Nucleobase-Modified Single-Stranded DNA Offers Tunable Resistance to Nuclease Degradation.}, Journal = {Biomacromolecules}, Volume = {19}, Number = {8}, Pages = {3525-3535}, Publisher = {American Chemical Society (ACS)}, Year = {2018}, Month = {August}, url = {http://dx.doi.org/10.1021/acs.biomac.8b00816}, Abstract = {We synthesized long, nucleobase-modified, single-stranded DNA (ssDNA) using terminal deoxynucleotidyl transferase (TdT) enzymatic polymerization. Specifically, we investigated the effect of unnatural nucleobase size and incorporation density on ssDNA resistance to exo- and endonuclease degradation. We discovered that increasing the size and density of unnatural nucleobases enhances ssDNA resistance to degradation in the presence of exonuclease I, DNase I, and human serum. We also studied the mechanism of this resistance enhancement using molecular dynamics simulations. Our results show that the presence of unnatural nucleobases in ssDNA decreases local chain flexibility and hampers nuclease access to the ssDNA backbone, which hinders nuclease binding to ssDNA and slows its degradation. Our discoveries suggest that incorporating nucleobase-modified nucleotides into ssDNA, using enzymatic polymerization, is an easy and efficient strategy to prolong and tune the half-life of DNA-based materials in nucleases-containing environments.}, Doi = {10.1021/acs.biomac.8b00816}, Key = {fds335904} } @article{fds335905, Author = {Maskarinec, SA and Parlak, Z and Tu, Q and Levering, V and Zauscher, S and López, GP and Fowler, VG and Perfect, JR}, Title = {On-demand release of Candida albicans biofilms from urinary catheters by mechanical surface deformation.}, Journal = {Biofouling}, Volume = {34}, Number = {6}, Pages = {595-604}, Year = {2018}, Month = {July}, url = {http://dx.doi.org/10.1080/08927014.2018.1474461}, Abstract = {Candida albicans is a leading cause of catheter-associated urinary tract infections and elimination of these biofilm-based infections without antifungal agents would constitute a significant medical advance. A novel urinary catheter prototype that utilizes on-demand surface deformation is effective at eliminating bacterial biofilms and here the broader applicability of this prototype to remove fungal biofilms has been demonstrated. C. albicans biofilms were debonded from prototypes by selectively inflating four additional intralumens surrounding the main lumen of the catheters to provide the necessary surface strain to remove the adhered biofilm. Deformable catheters eliminated significantly more biofilm than the controls (>90% eliminated vs 10% control; p < 0.001). Mechanical testing revealed that fungal biofilms have an elastic modulus of 45 ± 6.7 kPa with a fracture energy of 0.4-2 J m-2. This study underscores the potential of mechanical disruption as a materials design strategy to combat fungal device-associated infections.}, Doi = {10.1080/08927014.2018.1474461}, Key = {fds335905} } @article{fds333788, Author = {Shields, CW and White, JP and Osta, EG and Patel, J and Rajkumar, S and Kirby, N and Therrien, J-P and Zauscher, S}, Title = {Encapsulation and controlled release of retinol from silicone particles for topical delivery.}, Journal = {Journal of Controlled Release : Official Journal of the Controlled Release Society}, Volume = {278}, Pages = {37-48}, Year = {2018}, Month = {May}, url = {http://dx.doi.org/10.1016/j.jconrel.2018.03.023}, Abstract = {Retinol, a derivative of vitamin A, is a ubiquitous compound used to treat acne, reduce wrinkles and protect against conditions like psoriasis and ichthyosis. While retinol is used as the primary active ingredient (AI) in many skin care formulations, its efficacy is often limited by an extreme sensitivity to degrade and toxicity at high concentrations. While microencapsulation is an appealing method to help overcome these issues, few microencapsulation strategies have made a major translational impact due to challenges with complexity, cost, limited protection of the AI and poor control of the release of the AI. We have developed a class of silicone particles that addresses these challenges for the encapsulation, protection and controlled release of retinol and other hydrophobic compounds. The particles are prepared by the sol-gel polymerization of silane monomers, which enables their rapid and facile synthesis at scale while maintaining a narrow size distribution (i.e., CV < 20%). We show that our particles can: (i) encapsulate retinol with high efficiency (>85%), (ii) protect retinol from degradation (yielding a half-life 9× greater than unencapsulated retinol) and (iii) slowly release retinol over several hours (at rates from 0.14 to 0.67 μg cm-2 s-1/2). To demonstrate that the controlled release of retinol from the particles can reduce irritation, we performed a double blind study on human subjects and found that formulations containing our particles were 12-23% less irritating than identical formulations containing Microsponge® particles (an industry standard by Amcol, Inc.). To show that the silicone particles can elicit a favorable biological response, similar to the Microsponge® particles, we applied both formulations to reconstructed human epidermal tissues and found an upregulation of keratin 19 (K19) and a downregulation of K10, indicating that the reduced irritation observed in the human study was not caused by reduced activity. We also found a decrease in the production of interleukin-1α (IL-1α) compared to formulations containing the Microsponge particles, suggesting lower irritation levels and supporting the findings from the human study. Finally, we show that the silicone particles can encapsulate other AIs, including betamethasone, N, N-diethyl-meta-toluamide (DEET), homosalate and ingenol mebutate, establishing these particles as a true platform technology.}, Doi = {10.1016/j.jconrel.2018.03.023}, Key = {fds333788} } @article{fds331313, Author = {Costa, SA and Simon, JR and Amiram, M and Tang, L and Zauscher, S and Brustad, EM and Isaacs, FJ and Chilkoti, A}, Title = {Photo-Crosslinkable Unnatural Amino Acids Enable Facile Synthesis of Thermoresponsive Nano- to Microgels of Intrinsically Disordered Polypeptides.}, Journal = {Advanced Materials (Deerfield Beach, Fla.)}, Volume = {30}, Number = {5}, Year = {2018}, Month = {February}, url = {http://dx.doi.org/10.1002/adma.201704878}, Abstract = {Hydrogel particles are versatile materials that provide exquisite, tunable control over the sequestration and delivery of materials in pharmaceutics, tissue engineering, and photonics. The favorable properties of hydrogel particles depend largely on their size, and particles ranging from nanometers to micrometers are used in different applications. Previous studies have only successfully fabricated these particles in one specific size regime and required a variety of materials and fabrication methods. A simple yet powerful system is developed to easily tune the size of polypeptide-based, thermoresponsive hydrogel particles, from the nano- to microscale, using a single starting material. Particle size is controlled by the self-assembly and unique phase transition behavior of elastin-like polypeptides in bulk and within microfluidic-generated droplets. These particles are then stabilized through ultraviolet irradiation of a photo-crosslinkable unnatural amino acid (UAA) cotranslationally incorporated into the parent polypeptide. The thermoresponsive property of these particles provides an active mechanism for actuation and a dynamic responsive to the environment. This work represents a fundamental advance in the generation of crosslinked biomaterials, especially in the form of soft matter colloids, and is one of the first demonstrations of successful use of UAAs in generating a novel material.}, Doi = {10.1002/adma.201704878}, Key = {fds331313} } @article{fds333231, Author = {Marusak, KE and Krug, JR and Feng, Y and Cao, Y and You, L and Zauscher, S}, Title = {Bacterially driven cadmium sulfide precipitation on porous membranes: Toward platforms for photocatalytic applications.}, Journal = {Biointerphases}, Volume = {13}, Number = {1}, Pages = {011006}, Year = {2018}, Month = {February}, url = {http://dx.doi.org/10.1116/1.5008393}, Abstract = {The emerging field of biofabrication capitalizes on nature's ability to create materials with a wide range of well-defined physical and electronic properties. Particularly, there is a current push to utilize programmed, self-organization of living cells for material fabrication. However, much research is still necessary at the interface of synthetic biology and materials engineering to make biofabrication a viable technique to develop functional devices. Here, the authors exploit the ability of Escherichia coli to contribute to material fabrication by designing and optimizing growth platforms to direct inorganic nanoparticle (NP) synthesis, specifically cadmium sulfide (CdS) NPs, onto porous polycarbonate membranes. Additionally, current, nonbiological, chemical synthesis methods for CdS NPs are typically energy intensive and use high concentrations of hazardous cadmium precursors. Using biosynthesis methods through microorganisms could potentially alleviate these issues by precipitating NPs with less energy and lower concentrations of toxic precursors. The authors adopted extracellular precipitation strategies to form CdS NPs on the membranes as bacterial/membrane composites and characterized them by spectroscopic and imaging methods, including energy dispersive spectroscopy, and scanning and transmission electron microscopy. This method allowed us to control the localization of NP precipitation throughout the layered bacterial/membrane composite, by varying the timing of the cadmium precursor addition. Additionally, the authors demonstrated the photodegradation of methyl orange using the CdS functionalized porous membranes, thus confirming the photocatalytic properties of these composites for eventual translation to device development. If combined with the genetically programmed self-organization of cells, this approach promises to directly pattern CdS nanostructures on solid supports.}, Doi = {10.1116/1.5008393}, Key = {fds333231} } @article{fds332900, Author = {Li, L and Li, NK and Tu, Q and Im, O and Mo, C-K and Han, W and Fuss, WH and Carroll, NJ and Chilkoti, A and Yingling, YG and Zauscher, S and López, GP}, Title = {Functional Modification of Silica through Enhanced Adsorption of Elastin-Like Polypeptide Block Copolymers.}, Journal = {Biomacromolecules}, Volume = {19}, Number = {2}, Pages = {298-306}, Year = {2018}, Month = {February}, url = {http://dx.doi.org/10.1021/acs.biomac.7b01307}, Abstract = {A powerful tool for controlling interfacial properties and molecular architecture relies on the tailored adsorption of stimuli-responsive block copolymers onto surfaces. Here, we use computational and experimental approaches to investigate the adsorption behavior of thermally responsive polypeptide block copolymers (elastin-like polypeptides, ELPs) onto silica surfaces, and to explore the effects of surface affinity and micellization on the adsorption kinetics and the resultant polypeptide layers. We demonstrate that genetic incorporation of a silica-binding peptide (silaffin R5) results in enhanced adsorption of these block copolymers onto silica surfaces as measured by quartz crystal microbalance and ellipsometry. We find that the silaffin peptide can also direct micelle adsorption, leading to close-packed micellar arrangements that are distinct from the sparse, patchy arrangements observed for ELP micelles lacking a silaffin tag, as evidenced by atomic force microscopy measurements. These experimental findings are consistent with results of dissipative particle dynamics simulations. Wettability measurements suggest that surface immobilization hampers the temperature-dependent conformational change of ELP micelles, while adsorbed ELP unimers (i.e., unmicellized block copolymers) retain their thermally responsive property at interfaces. These observations provide guidance on the use of ELP block copolymers as building blocks for fabricating smart surfaces and interfaces with programmable architecture and functionality.}, Doi = {10.1021/acs.biomac.7b01307}, Key = {fds332900} } @article{fds339853, Author = {Yildiz, T and Gu, R and Zauscher, S and Betancourt, T}, Title = {Doxorubicin-loaded protease-activated near-infrared fluorescent polymeric nanoparticles for imaging and therapy of cancer.}, Journal = {International Journal of Nanomedicine}, Volume = {13}, Pages = {6961-6986}, Year = {2018}, Month = {January}, url = {http://dx.doi.org/10.2147/ijn.s174068}, Abstract = {<h4>Introduction</h4>Despite significant progress in the field of oncology, cancer remains one of the leading causes of death. Chemotherapy is one of the most common treatment options for cancer patients but is well known to result in off-target toxicity. Theranostic nanomedicines that integrate diagnostic and therapeutic functions within an all-in-one platform can increase tumor selectivity for more effective chemotherapy and aid in diagnosis and monitoring of therapeutic responses.<h4>Material and methods</h4>In this work, theranostic nanoparticles were synthesized with commonly used biocompatible and biodegradable polymers and used as cancer contrast and therapeutic agents for optical imaging and treatment of breast cancer. These core-shell nanoparticles were prepared by nanoprecipitation of blends of the biodegradable and biocompatible amphiphilic copolymers poly(lactic-<i>co</i>-glycolic acid)-<i>b</i>-poly-l-lysine and poly(lactic acid)-<i>b</i>-poly(ethylene glycol). Poly-l-lysine in the first copolymer was covalently decorated with near-infrared fluorescent Alexa Fluor 750 molecules.<h4>Results</h4>The spherical nanoparticles had an average size of 60-80 nm. The chemotherapeutic drug doxorubicin was encapsulated in the core of nanoparticles at a loading of 3% (w:w) and controllably released over a period of 30 days. A 33-fold increase in near-infrared fluorescence, mediated by protease-mediated cleavage of the Alexa Fluor 750-labeled poly-l-lysine on the surface of the nanoparticles, was observed upon interaction with the model protease trypsin. The cytocompatibility of drug-free nanoparticles and growth inhibition of drug-loaded nanoparticles on MDA-MB-231 breast cancer cells were investigated with a luminescence cell-viability assay. Drug-free nanoparticles were found to cause minimal toxicity, even at high concentrations (0.2-2,000 µg/mL), while doxorubicin-loaded nanoparticles significantly reduced cell viability at drug concentrations >10 µM. Finally, the interaction of the nanoparticles with breast cancer cells was studied utilizing fluorescence microscopy, demonstrating the potential of the nanoparticles to act as near-infrared fluorescence optical imaging agents and drug-delivery carriers.<h4>Conclusion</h4>Doxorubicin-loaded, enzymatically activatable nanoparticles of less than 100 nm were prepared successfully by nanoprecipitation of copolymer blends. These nanoparticles were found to be suitable as controlled drug delivery systems and contrast agents for imaging of cancer cells.}, Doi = {10.2147/ijn.s174068}, Key = {fds339853} } @article{fds357336, Author = {Maniura-Weber, K and Zauscher, S and McArthur, S}, Title = {Some changes, but still communicating exciting key insights from the biointerface.}, Journal = {Biointerphases}, Volume = {12}, Number = {5}, Pages = {050201}, Year = {2018}, Month = {January}, url = {http://dx.doi.org/10.1116/1.5018515}, Doi = {10.1116/1.5018515}, Key = {fds357336} } @article{fds330454, Author = {Cao, Y and Feng, Y and Ryser, MD and Zhu, K and Herschlag, G and Cao, C and Marusak, K and Zauscher, S and You, L}, Title = {Programmable assembly of pressure sensors using pattern-forming bacteria.}, Journal = {Nat Biotechnol}, Volume = {35}, Number = {11}, Pages = {1087-1093}, Year = {2017}, Month = {November}, url = {http://dx.doi.org/10.1038/nbt.3978}, Abstract = {Biological systems can generate microstructured materials that combine organic and inorganic components and possess diverse physical and chemical properties. However, these natural processes in materials fabrication are not readily programmable. Here, we use a synthetic-biology approach to assemble patterned materials. We demonstrate programmable fabrication of three-dimensional (3D) materials by printing engineered self-patterning bacteria on permeable membranes that serve as a structural scaffold. Application of gold nanoparticles to the colonies creates hybrid organic-inorganic dome structures. The dynamics of the dome structures' response to pressure is determined by their geometry (colony size, dome height, and pattern), which is easily modified by varying the properties of the membrane (e.g., pore size and hydrophobicity). We generate resettable pressure sensors that process signals in response to varying pressure intensity and duration.}, Doi = {10.1038/nbt.3978}, Key = {fds330454} } @article{fds329514, Author = {Li, NK and Kuang, H and Fuss, WH and Zauscher, S and Kokkoli, E and Yingling, YG}, Title = {Salt Responsive Morphologies of ssDNA-Based Triblock Polyelectrolytes in Semi-Dilute Regime: Effect of Volume Fractions and Polyelectrolyte Length.}, Journal = {Macromolecular Rapid Communications}, Volume = {38}, Number = {20}, Year = {2017}, Month = {October}, url = {http://dx.doi.org/10.1002/marc.201700422}, Abstract = {A comprehensive study is reported on the effect of salt concentration, polyelectrolyte block length, and polymer concentration on the morphology and structural properties of nanoaggregates self-assembled from BAB single-strand DNA (ssDNA) triblock polynucleotides in which A represents polyelectrolyte blocks and B represents hydrophobic neutral blocks. A morphological phase diagram above the gelation point is developed as a function of solvent ionic strength and polyelectrolyte block length utilizing an implicit solvent ionic strength method for dissipative particle dynamics simulations. As the solvent ionic strength increases, the self-assembled DNA network structures shrinks considerably, leading to a morphological transition from a micellar network to worm-like or hamburger-shape aggregates. This study provides insight into the network morphology and its changes by calculating the aggregation number, number of hydrophobic cores, and percentage of bridge chains in the network. The simulation results are corroborated through cryogenic transmission electron microscopy on the example of the self-assembly of ssDNA triblocks.}, Doi = {10.1002/marc.201700422}, Key = {fds329514} } @article{fds328288, Author = {Du, K-Z and Tu, Q and Zhang, X and Han, Q and Liu, J and Zauscher, S and Mitzi, DB}, Title = {Two-Dimensional Lead(II) Halide-Based Hybrid Perovskites Templated by Acene Alkylamines: Crystal Structures, Optical Properties, and Piezoelectricity.}, Journal = {Inorganic Chemistry}, Volume = {56}, Number = {15}, Pages = {9291-9302}, Year = {2017}, Month = {August}, url = {http://dx.doi.org/10.1021/acs.inorgchem.7b01094}, Abstract = {A series of two-dimensional (2D) hybrid organic-inorganic perovskite (HOIP) crystals, based on acene alkylamine cations (i.e., phenylmethylammonium (PMA), 2-phenylethylammonium (PEA), 1-(2-naphthyl)methanammonium (NMA), and 2-(2-naphthyl)ethanammonium (NEA)) and lead(II) halide (i.e., PbX<sub>4</sub><sup>2-</sup>, X = Cl, Br, and I) frameworks, and their corresponding thin films were fabricated and examined for structure-property relationship. Several new or redetermined crystal structures are reported, including those for (NEA)<sub>2</sub>PbI<sub>4</sub>, (NEA)<sub>2</sub>PbBr<sub>4</sub>, (NMA)<sub>2</sub>PbBr<sub>4</sub>, (PMA)<sub>2</sub>PbBr<sub>4</sub>, and (PEA)<sub>2</sub>PbI<sub>4</sub>. Non-centrosymmetric structures from among these 2D HOIPs were confirmed by piezoresponse force microscopy-especially noteworthy is the structure of (PMA)<sub>2</sub>PbBr<sub>4</sub>, which was previously reported as centrosymmetric. Examination of the impact of organic cation and inorganic layer choice on the exciton absorption/emission properties, among the set of compounds considered, reveals that perovskite layer distortion (i.e., Pb-I-Pb bond angle between adjacent PbI<sub>6</sub> octahedra) has a more global effect on the exciton properties than octahedral distortion (i.e., variation of I-Pb-I bond angles and discrepancy among Pb-I bond lengths within each PbI<sub>6</sub> octahedron). In addition to the characteristic sharp exciton emission for each perovskite, (PMA)<sub>2</sub>PbCl<sub>4</sub>, (PEA)<sub>2</sub>PbCl<sub>4</sub>, (NMA)<sub>2</sub>PbCl<sub>4</sub>, and (PMA)<sub>2</sub>PbBr<sub>4</sub> exhibit separate, broad "white" emission in the long wavelength range. Piezoelectric compounds identified from these 2D HOIPs may be considered for future piezoresponse-type energy or electronic applications.}, Doi = {10.1021/acs.inorgchem.7b01094}, Key = {fds328288} } @article{fds326497, Author = {Tang, L and Navarro, LA and Chilkoti, A and Zauscher, S}, Title = {High-Molecular-Weight Polynucleotides by Transferase-Catalyzed Living Chain-Growth Polycondensation.}, Journal = {Angewandte Chemie International Edition}, Volume = {56}, Number = {24}, Pages = {6778-6782}, Publisher = {WILEY}, Year = {2017}, Month = {June}, url = {http://dx.doi.org/10.1002/anie.201700991}, Abstract = {We present terminal deoxynucleotidyl transferase-catalyzed enzymatic polymerization (TcEP) for the template-free synthesis of high-molecular-weight, single-stranded DNA (ssDNA) and demonstrate that it proceeds by a living chain-growth polycondensation mechanism. We show that the molecular weight of the reaction products is nearly monodisperse, and can be manipulated by the feed ratio of nucleotide (monomer) to oligonucleotide (initiator), as typically observed for living polymerization reactions. Understanding the synthesis mechanism and the reaction kinetics enables the rational, template-free synthesis of ssDNA that can be used for a range of biomedical and nanotechnology applications.}, Doi = {10.1002/anie.201700991}, Key = {fds326497} } @article{fds325857, Author = {Tu, Q and Kim, HS and Oweida, TJ and Parlak, Z and Yingling, YG and Zauscher, S}, Title = {Interfacial Mechanical Properties of Graphene on Self-Assembled Monolayers: Experiments and Simulations.}, Journal = {Acs Applied Materials & Interfaces}, Volume = {9}, Number = {11}, Pages = {10203-10213}, Year = {2017}, Month = {March}, url = {http://dx.doi.org/10.1021/acsami.6b16593}, Abstract = {Self-assembled monolayers (SAMs) have been widely used to engineer the electronic properties of substrate-supported graphene devices. However, little is known about how the surface chemistry of SAMs affects the interfacial mechanical properties of graphene supported on SAMs. Fluctuations and changes in these properties affect the stress transfer between substrate and the supported graphene and thus the performance of graphene-based devices. The changes in interfacial mechanical properties can be characterized by measuring the out-of-plane elastic properties. Combining contact resonance atomic force microcopy experiments with molecular dynamics simulations, we show that the head group chemistry of a SAM, which affects the interfacial interactions, can have a significant effect on the out-of-plane elastic modulus of the graphene-SAM heterostructure. Graphene supported on hydrophobic SAMs leads to heterostructures stiffer than those of graphene supported on hydrophilic SAMs, which is largely due to fewer water molecules present at the graphene-SAM interface. Our results provide an important, and often overlooked, insight into the mechanical properties of substrate-supported graphene electronics.}, Doi = {10.1021/acsami.6b16593}, Key = {fds325857} } @article{fds325392, Author = {Feng, Y and Ngaboyamahina, E and Marusak, KE and Cao, Y and You, L and Glass, JT and Zauscher, S}, Title = {Hybrid (Organic/Inorganic) Electrodes from Bacterially Precipitated CdS for PEC/Storage Applications}, Journal = {The Journal of Physical Chemistry C}, Volume = {121}, Number = {7}, Pages = {3734-3743}, Publisher = {American Chemical Society (ACS)}, Year = {2017}, Month = {February}, url = {http://dx.doi.org/10.1021/acs.jpcc.6b11387}, Abstract = {Hybrid organic-inorganic compounds are receiving increasing attention for photoelectrochemical (PEC) devices due to their high electron transport efficiency and facile synthesis. Biosynthesis is a potentially low-cost and eco-friendly method to precipitate transition-metal-based semiconductor nanoparticles (NPs) in an organic matrix. In this work, we examine the structure and composition of bacterially precipitated (BAC) cadmium sulfide (CdS) NPs using electron microscopy, and we determine their PEC properties and the energy band structure by electrochemical measurements. In addition, by taking advantage of the organic matrix, which is residual from the biosynthesis process, we fabricate a prototype photocharged capacitor electrode by incorporating the bacterially precipitated CdS with a reduced graphene oxide (RGO) sheet. Our results show that the hydrophilic groups associated with the organic matrix make BAC CdS NPs a potentially useful component of PEC devices with applications for energy conversion and storage. (Graph Presented).}, Doi = {10.1021/acs.jpcc.6b11387}, Key = {fds325392} } @article{fds319122, Author = {Tu, Q and Lange, B and Parlak, Z and Lopes, JMJ and Blum, V and Zauscher, S}, Title = {Quantitative Subsurface Atomic Structure Fingerprint for 2D Materials and Heterostructures by First-Principles-Calibrated Contact-Resonance Atomic Force Microscopy.}, Journal = {Acs Nano}, Volume = {10}, Number = {7}, Pages = {6491-6500}, Year = {2016}, Month = {July}, url = {http://dx.doi.org/10.1021/acsnano.6b02402}, Abstract = {Interfaces and subsurface layers are critical for the performance of devices made of 2D materials and heterostructures. Facile, nondestructive, and quantitative ways to characterize the structure of atomically thin, layered materials are thus essential to ensure control of the resultant properties. Here, we show that contact-resonance atomic force microscopy-which is exquisitely sensitive to stiffness changes that arise from even a single atomic layer of a van der Waals-adhered material-is a powerful experimental tool to address this challenge. A combined density functional theory and continuum modeling approach is introduced that yields sub-surface-sensitive, nanomechanical fingerprints associated with specific, well-defined structure models of individual surface domains. Where such models are known, this information can be correlated with experimentally obtained contact-resonance frequency maps to reveal the (sub)surface structure of different domains on the sample.}, Doi = {10.1021/acsnano.6b02402}, Key = {fds319122} } @article{fds319125, Author = {Marusak, KE and Feng, Y and Eben, CF and Payne, ST and Cao, Y and You, L and Zauscher, S}, Title = {Cadmium sulphide quantum dots with tunable electronic properties by bacterial precipitation.}, Journal = {Rsc Adv.}, Volume = {6}, Number = {80}, Pages = {76158-76166}, Year = {2016}, Month = {January}, url = {http://dx.doi.org/10.1039/c6ra13835g}, Abstract = {We present a new method to fabricate semiconducting, transition metal nanoparticles (NPs) with tunable bandgap energies using engineered <i>Escherichia coli</i>. These bacteria overexpress the <i>Treponema denticola</i> cysteine desulfhydrase gene to facilitate precipitation of cadmium sulphide (CdS) NPs. Analysis with transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy reveal that the bacterially precipitated NPs are agglomerates of mostly quantum dots, with diameters that can range from 3 to 15 nm, embedded in a carbon-rich matrix. Additionally, conditions for bacterial CdS precipitation can be tuned to produce NPs with bandgap energies that range from quantum-confined to bulk CdS. Furthermore, inducing precipitation at different stages of bacterial growth allows for control over whether the precipitation occurs intra- or extracellularly. This control can be critically important in utilizing bacterial precipitation for the environmentally-friendly fabrication of functional, electronic and catalytic materials. Notably, the measured photoelectrochemical current generated by these NPs is comparable to values reported in the literature and higher than that of synthesized chemical bath deposited CdS NPs. This suggests that bacterially precipitated CdS NPs have potential for applications ranging from photovoltaics to photocatalysis in hydrogen evolution.}, Doi = {10.1039/c6ra13835g}, Key = {fds319125} } @article{fds319123, Author = {Yu, Q and Ista, LK and Gu, R and Zauscher, S and López, GP}, Title = {Nanopatterned polymer brushes: conformation, fabrication and applications.}, Journal = {Nanoscale}, Volume = {8}, Number = {2}, Pages = {680-700}, Year = {2016}, Month = {January}, url = {http://dx.doi.org/10.1039/c5nr07107k}, Abstract = {Surfaces with end-grafted, nanopatterned polymer brushes that exhibit well-defined feature dimensions and controlled chemical and physical properties provide versatile platforms not only for investigation of nanoscale phenomena at biointerfaces, but also for the development of advanced devices relevant to biotechnology and electronics applications. In this review, we first give a brief introduction of scaling behavior of nanopatterned polymer brushes and then summarize recent progress in fabrication and application of nanopatterned polymer brushes. Specifically, we highlight applications of nanopatterned stimuli-responsive polymer brushes in the areas of biomedicine and biotechnology.}, Doi = {10.1039/c5nr07107k}, Key = {fds319123} } @article{fds319124, Author = {Tkatchenko, AV and Luo, X and Tkatchenko, TV and Vaz, C and Tanavde, VM and Maurer-Stroh, S and Zauscher, S and Gonzalez, P and Young, TL}, Title = {Large-Scale microRNA Expression Profiling Identifies Putative Retinal miRNA-mRNA Signaling Pathways Underlying Form-Deprivation Myopia in Mice.}, Journal = {Plos One}, Volume = {11}, Number = {9}, Pages = {e0162541}, Year = {2016}, url = {http://dx.doi.org/10.1371/journal.pone.0162541}, Abstract = {Development of myopia is associated with large-scale changes in ocular tissue gene expression. Although differential expression of coding genes underlying development of myopia has been a subject of intense investigation, the role of non-coding genes such as microRNAs in the development of myopia is largely unknown. In this study, we explored myopia-associated miRNA expression profiles in the retina and sclera of C57Bl/6J mice with experimentally induced myopia using microarray technology. We found a total of 53 differentially expressed miRNAs in the retina and no differences in miRNA expression in the sclera of C57BL/6J mice after 10 days of visual form deprivation, which induced -6.93 ± 2.44 D (p < 0.000001, n = 12) of myopia. We also identified their putative mRNA targets among mRNAs found to be differentially expressed in myopic retina and potential signaling pathways involved in the development of form-deprivation myopia using miRNA-mRNA interaction network analysis. Analysis of myopia-associated signaling pathways revealed that myopic response to visual form deprivation in the retina is regulated by a small number of highly integrated signaling pathways. Our findings highlighted that changes in microRNA expression are involved in the regulation of refractive eye development and predicted how they may be involved in the development of myopia by regulating retinal gene expression.}, Doi = {10.1371/journal.pone.0162541}, Key = {fds319124} } @article{fds263324, Author = {Gu, R and Lamas, J and Rastogi, SK and Li, X and Brittain, W and Zauscher, S}, Title = {Photocontrolled micellar aggregation of amphiphilic DNA-azobenzene conjugates.}, Journal = {Colloids and Surfaces. B, Biointerfaces}, Volume = {135}, Pages = {126-132}, Year = {2015}, Month = {November}, ISSN = {0927-7765}, url = {http://dx.doi.org/10.1016/j.colsurfb.2015.07.010}, Abstract = {We demonstrate the reversible micellar aggregation of a DNA-azobenzene conjugate in aqueous conditions, in which the photoisomerization of the initially apolar trans-azobenzene moiety to the polar cis isomer causes disassembly of the aggregates. The molecular basis for this phenomena is a change in the hydrophobic/hydrophilic balance of the conjugate as the more polar cis azobenzene isomer is formed upon exposure to 365 nm irradiation. The conjugates were prepared by copper-free Click chemistry between an azide-modified, 53-base ssDNA and a cyclooctyne derivative of azobenzene. The photocontrolled aggregation of the conjugate was studied by dynamic light scattering and atomic force microscopy. The reversible micellar aggregation for a DNA-azobenzene conjugate has not been previously reported and holds promise for photocontrolled drug delivery applications.}, Doi = {10.1016/j.colsurfb.2015.07.010}, Key = {fds263324} } @article{fds319126, Author = {Li, NK and Fuss, WH and Tang, L and Gu, R and Chilkoti, A and Zauscher, S and Yingling, YG}, Title = {Prediction of solvent-induced morphological changes of polyelectrolyte diblock copolymer micelles.}, Journal = {Soft Matter}, Volume = {11}, Number = {42}, Pages = {8236-8245}, Year = {2015}, Month = {November}, url = {http://dx.doi.org/10.1039/c5sm01742d}, Abstract = {Self-assembly processes of polyelectrolyte block copolymers are ubiquitous in industrial and biological processes; understanding their physical properties can also provide insights into the design of polyelectrolyte materials with novel and tailored properties. Here, we report systematic analysis on how the ionic strength of the solvent and the length of the polyelectrolyte block affect the self-assembly and morphology of the polyelectrolyte block copolymer materials by constructing a salt-dependent morphological phase diagram using an implicit solvent ionic strength (ISIS) method for dissipative particle dynamics (DPD) simulations. This diagram permits the determination of the conditions for the morphological transition into a specific shape, namely vesicles or lamellar aggregates, wormlike/cylindrical micelles, and spherical micelles. The scaling behavior for the size of spherical micelles is predicted, in terms of radius of gyration (R(g,m)) and thickness of corona (Hcorona), as a function of solvent ionic strength (c(s)) and polyelectrolyte length (NA), which are R(g,m) ∼ c(s)(-0.06)N(A)(0.54) and Hcorona ∼ c(s)(-0.11)N(A)(0.75). The simulation results were corroborated through AFM and static light scattering measurements on the example of the self-assembly of monodisperse, single-stranded DNA block-copolynucleotides (polyT50-b-F-dUTP). Overall, we were able to predict the salt-responsive morphology of polyelectrolyte materials in aqueous solution and show that a spherical-cylindrical-lamellar change in morphology can be obtained through an increase in solvent ionic strength or a decrease of polyelectrolyte length.}, Doi = {10.1039/c5sm01742d}, Key = {fds319126} } @article{fds263325, Author = {Lee, W and Leddy, HA and Chen, Y and Lee, SH and Zelenski, NA and McNulty, AL and Wu, J and Beicker, KN and Coles, J and Zauscher, S and Grandl, J and Sachs, F and Guilak, F and Liedtke, WB}, Title = {Synergy between Piezo1 and Piezo2 channels confers high-strain mechanosensitivity to articular cartilage.}, Journal = {Proc Natl Acad Sci U S A}, Volume = {111}, Number = {47}, Pages = {E5114-E5122}, Year = {2014}, Month = {November}, ISSN = {0027-8424}, url = {http://dx.doi.org/10.1073/pnas.1414298111}, Abstract = {Diarthrodial joints are essential for load bearing and locomotion. Physiologically, articular cartilage sustains millions of cycles of mechanical loading. Chondrocytes, the cells in cartilage, regulate their metabolic activities in response to mechanical loading. Pathological mechanical stress can lead to maladaptive cellular responses and subsequent cartilage degeneration. We sought to deconstruct chondrocyte mechanotransduction by identifying mechanosensitive ion channels functioning at injurious levels of strain. We detected robust expression of the recently identified mechanosensitive channels, PIEZO1 and PIEZO2. Combined directed expression of Piezo1 and -2 sustained potentiated mechanically induced Ca(2+) signals and electrical currents compared with single-Piezo expression. In primary articular chondrocytes, mechanically evoked Ca(2+) transients produced by atomic force microscopy were inhibited by GsMTx4, a PIEZO-blocking peptide, and by Piezo1- or Piezo2-specific siRNA. We complemented the cellular approach with an explant-cartilage injury model. GsMTx4 reduced chondrocyte death after mechanical injury, suggesting a possible therapy for reducing cartilage injury and posttraumatic osteoarthritis by attenuating Piezo-mediated cartilage mechanotransduction of injurious strains.}, Doi = {10.1073/pnas.1414298111}, Key = {fds263325} } @article{fds263326, Author = {Parlak, Z and Tu, Q and Zauscher, S}, Title = {Liquid contact resonance AFM: analytical models, experiments, and limitations.}, Journal = {Nanotechnology}, Volume = {25}, Number = {44}, Pages = {445703}, Year = {2014}, Month = {November}, ISSN = {0957-4484}, url = {http://dx.doi.org/10.1088/0957-4484/25/44/445703}, Abstract = {Contact resonance AFM (CR-AFM) is a scanning probe microscopy technique that utilizes the contact resonances of the AFM cantilever for concurrent imaging of topography and surface stiffness. The technique has not been used in liquid until recently due to analytical and experimental difficulties, associated with viscous damping of cantilever vibrations and fluid loading effects. To address these difficulties, (i) an analytical approach for contact resonances in liquid is developed, and (ii) direct excitation of the contact resonances is demonstrated by actuating the cantilever directly in a magnetic field. By implementing the analytical approach and the direct actuation through magnetic particles, quantitative stiffness imaging on surfaces with a wide range of stiffness can be achieved in liquid with soft cantilevers and low contact forces.}, Doi = {10.1088/0957-4484/25/44/445703}, Key = {fds263326} } @article{fds263327, Author = {Hardy, GJ and Wong, GC and Nayak, R and Anasti, K and Hirtz, M and Shapter, JG and Alam, SM and Zauscher, S}, Title = {HIV-1 antibodies and vaccine antigen selectively interact with lipid domains.}, Journal = {Biochimica Et Biophysica Acta}, Volume = {1838}, Number = {10}, Pages = {2662-2669}, Year = {2014}, Month = {October}, ISSN = {0006-3002}, url = {http://dx.doi.org/10.1016/j.bbamem.2014.07.007}, Abstract = {The rare, broadly neutralizing antibodies, 4E10 and 2F5, that target the HIV-1 membrane proximal external region also associate with HIV-1 membrane lipids as part of a required first-step in HIV-1 neutralization. HIV-1 virions have high concentration of cholesterol and sphingomyelin, which are able to organize into liquid-ordered domains (i.e., lipid rafts), and could influence the interaction of neutralizing antibodies with epitopes proximal to the membrane. The objective of this research is to understand how these lipid domains contribute to 2F5/4E10 membrane interactions and to antigen presentation in liposomal form of HIV-1 vaccines. To this end we have engineered biomimetic supported lipid bilayers and are able to use atomic force microscopy to visualize membrane domains, antigen clustering, and antibody-membrane interactions. Our results demonstrate that 2F5/4E10 do not interact with highly ordered gel and liquid-ordered domains and exclusively bind to a liquid-disordered lipid phase. This suggests that vaccine liposomes that contain key viral membrane components, such as high cholesterol content, may not be advantageous for 2F5/4E10 vaccine strategies. Rather, vaccine liposomes that primarily contain a liquid-disordered phase may be more likely to elicit production of lipid reactive, 2F5- and 4E10-like antibodies.}, Doi = {10.1016/j.bbamem.2014.07.007}, Key = {fds263327} } @article{fds263329, Author = {Tang, L and Tjong, V and Li, N and Yingling, YG and Chilkoti, A and Zauscher, S}, Title = {Enzymatic polymerization of high molecular weight DNA amphiphiles that self-assemble into star-like micelles.}, Journal = {Advanced Materials (Deerfield Beach, Fla.)}, Volume = {26}, Number = {19}, Pages = {3050-3054}, Year = {2014}, Month = {May}, ISSN = {0935-9648}, url = {http://dx.doi.org/10.1002/adma.201306049}, Abstract = {High molecular weight ssDNA amphiphiles are synthesized by enzymatic polymerization. These highly asymmetric diblock DNA copolymers self-assemble into "hairy", star-like micelles, shown in the AFM image and the DPD snapshot.}, Doi = {10.1002/adma.201306049}, Key = {fds263329} } @article{fds263331, Author = {Tjong, V and Tang, L and Zauscher, S and Chilkoti, A}, Title = {"Smart" DNA interfaces.}, Journal = {Chem. Soc. Rev.}, Volume = {43}, Number = {5}, Pages = {1612-1626}, Year = {2014}, Month = {March}, url = {http://www.ncbi.nlm.nih.gov/pubmed/24352168}, Abstract = {This review focuses on surface-grafted DNA, and its use as a molecular building block that exploits its unique properties as a directional (poly)anion that exhibits molecular recognition. The selected examples highlight innovative applications of DNA at surfaces and interfaces ranging from molecular diagnostics and sequencing to biosensing.}, Doi = {10.1039/c3cs60331h}, Key = {fds263331} } @article{fds263330, Author = {Chang, DP and Guilak, F and Jay, GD and Zauscher, S}, Title = {Interaction of lubricin with type II collagen surfaces: adsorption, friction, and normal forces.}, Journal = {Journal of Biomechanics}, Volume = {47}, Number = {3}, Pages = {659-666}, Year = {2014}, Month = {February}, url = {http://www.ncbi.nlm.nih.gov/pubmed/24406099}, Abstract = {One of the major constituents of the synovial fluid that is thought to be responsible for chondroprotection and boundary lubrication is the glycoprotein lubricin (PRG4); however, the molecular mechanisms by which lubricin carries out its critical functions still remain largely unknown. We hypothesized that the interaction of lubricin with type II collagen, the main component of the cartilage extracellular matrix, results in enhanced tribological and wear properties. In this study, we examined: (i) the molecular details by which lubricin interacts with type II collagen and how binding is related to boundary lubrication and adhesive interactions; and (ii) whether collagen structure can affect lubricin adsorption and its chondroprotective properties. We found that lubricin adsorbs strongly onto denatured, amorphous, and fibrillar collagen surfaces. Furthermore, we found large repulsive interactions between the collagen surfaces in presence of lubricin, which increased with increasing lubricin concentration. Lubricin attenuated the large friction and also the long-range adhesion between fibrillar collagen surfaces. Interestingly, lubricin adsorbed onto and mediated the frictional response between the denatured and native amorphous collagen surfaces equally and showed no preference on the supramolecular architecture of collagen. However, the coefficient of friction was lowest on fibrillar collagen in the presence of lubricin. We speculate that an important role of lubricin in mediating interactions at the cartilage surface is to attach to the cartilage surface and provide a protective coating that maintains the contacting surfaces in a sterically repulsive state.}, Doi = {10.1016/j.jbiomech.2013.11.048}, Key = {fds263330} } @article{fds263337, Author = {Wilusz, RE and Zauscher, S and Guilak, F}, Title = {Micromechanical mapping of early osteoarthritic changes in the pericellular matrix of human articular cartilage.}, Journal = {Osteoarthritis and Cartilage}, Volume = {21}, Number = {12}, Pages = {1895-1903}, Year = {2013}, Month = {December}, url = {http://www.ncbi.nlm.nih.gov/pubmed/24025318}, Abstract = {<h4>Objective</h4>Osteoarthritis (OA) is a degenerative joint disease characterized by the progressive loss of articular cartilage. While macroscale degradation of the cartilage extracellular matrix (ECM) has been extensively studied, microscale changes in the chondrocyte pericellular matrix (PCM) and immediate microenvironment with OA are not fully understood. The objective of this study was to quantify osteoarthritic changes in the micromechanical properties of the ECM and PCM of human articular cartilage in situ using atomic force microscopy (AFM).<h4>Method</h4>AFM elastic mapping was performed on cryosections of human cartilage harvested from both condyles of macroscopically normal and osteoarthritic knee joints. This method was used to test the hypotheses that both ECM and PCM regions exhibit a loss of mechanical properties with OA and that the size of the PCM is enlarged in OA cartilage as compared to normal tissue.<h4>Results</h4>Significant decreases were observed in both ECM and PCM moduli of 45% and 30%, respectively, on the medial condyle of OA knee joints as compared to cartilage from macroscopically normal joints. Enlargement of the PCM, as measured biomechanically, was also observed in medial condyle OA cartilage, reflecting the underlying distribution of type VI collagen in the region. No significant differences were observed in elastic moduli or their spatial distribution on the lateral condyle between normal and OA joints.<h4>Conclusion</h4>Our findings provide new evidence of significant site-specific degenerative changes in the chondrocyte micromechanical environment with OA.}, Doi = {10.1016/j.joca.2013.08.026}, Key = {fds263337} } @article{fds263338, Author = {Malmsten, M and Zauscher, S}, Title = {Colloids and surfaces in biology}, Journal = {Current Opinion in Colloid & Interface Science}, Volume = {18}, Number = {5}, Pages = {379-380}, Publisher = {Elsevier BV}, Year = {2013}, Month = {October}, ISSN = {1359-0294}, url = {http://dx.doi.org/10.1016/j.cocis.2013.07.003}, Doi = {10.1016/j.cocis.2013.07.003}, Key = {fds263338} } @article{fds263340, Author = {Hardy, GJ and Nayak, R and Zauscher, S}, Title = {Model cell membranes: Techniques to form complex biomimetic supported lipid bilayers via vesicle fusion.}, Journal = {Current Opinion in Colloid & Interface Science}, Volume = {18}, Number = {5}, Pages = {448-458}, Year = {2013}, Month = {October}, ISSN = {1359-0294}, url = {http://dx.doi.org/10.1016/j.cocis.2013.06.004}, Abstract = {Vesicle fusion has long provided an easy and reliable method to form supported lipid bilayers (SLBs) from simple, zwitterionic vesicles on siliceous substrates. However, for complex compositions, such as vesicles with high cholesterol content and multiple lipid types, the energy barrier for the vesicle-to-bilayer transition is increased or the required vesicle-vesicle and vesicle-substrate interactions are insufficient for vesicle fusion. Thus, for vesicle compositions that more accurately mimic native membranes, vesicle fusion often fails to form SLBs. In this paper, we review three approaches to overcome these barriers to form complex, biomimetic SLBs via vesicle fusion: (i) optimization of experimental conditions (e.g., temperature, buffer ionic strength, osmotic stress, cation valency, and buffer pH), (ii) α-helical (AH) peptide-induced vesicle fusion, and (iii) bilayer edge-induced vesicle fusion. AH peptide-induced vesicle fusion can form complex SLBs on multiple substrate types without the use of additional equipment. Bilayer edge-induced vesicle fusion uses microfluidics to form SLBs from vesicles with complex composition, including vesicles derived from native cell membranes. Collectively, this review introduces vesicle fusion techniques that can be generalized for many biomimetic vesicle compositions and many substrate types, and thus will aid efforts to reliably create complex SLB platforms on a range of substrates.}, Doi = {10.1016/j.cocis.2013.06.004}, Key = {fds263340} } @article{fds263341, Author = {Ferris, RJ and Lin, S and Therezien, M and Yellen, BB and Zauscher, S}, Title = {Electric double layer formed by polarized ferroelectric thin films.}, Journal = {Acs Applied Materials & Interfaces}, Volume = {5}, Number = {7}, Pages = {2610-2617}, Year = {2013}, Month = {April}, url = {http://www.ncbi.nlm.nih.gov/pubmed/23484485}, Abstract = {Ferroelectric surfaces can have very high surface charge densities that can be harnessed for manipulation of charged colloidal particles and soft matter in aqueous environments. Here, we report on the electrical double layer (EDL) formed by polarized ultrasmooth lead zirconium titanate (US-PZT) thin films in dilute electrolyte solutions. Using colloidal probe force microscopy (CPFM) measurements, we show that the ion distribution within the double layer can be changed by reversing the ferroelectric polarization state of US-PZT. The interaction force in dilute 1:1 electrolyte solution between the negatively charged probe and a positive surface charge (upward polarized) US-PZT thin film is attractive, while the interaction force is repulsive for a negative surface charge (downward polarized) film. We modeled these interactions with a constant-potential EDL model between dissimilar surfaces with the inclusion of a Stern layer. We report the surface potentials at the inner and outer-Helmholtz planes both for polarization states and for a range of ionic strength solutions. Effects of free-charge carriers, limitations of the analytical model, and effects of surface roughness are discussed.}, Doi = {10.1021/am3031954}, Key = {fds263341} } @article{fds319132, Author = {Schulz, BS and Zauscher, S and Ammer, H and Sauter-Louis, C and Hartmann, K}, Title = {Side effects suspected to be related to doxycycline use in cats.}, Journal = {The Veterinary Record}, Volume = {172}, Number = {7}, Pages = {184}, Year = {2013}, Month = {February}, url = {http://dx.doi.org/10.1136/vr.101031}, Doi = {10.1136/vr.101031}, Key = {fds319132} } @article{fds263339, Author = {Parlak, Z and Biet, C and Zauscher, S}, Title = {Decoupling mass adsorption from fluid viscosity and density in quartz crystal microbalance measurements using normalized conductance modeling}, Journal = {Measurement Science and Technology}, Volume = {24}, Number = {8}, Pages = {085301-085301}, Publisher = {IOP Publishing}, Year = {2013}, Month = {January}, ISSN = {0957-0233}, url = {http://dx.doi.org/10.1088/0957-0233/24/8/085301}, Abstract = {We describe the physical understanding of a method which differentiates between the frequency shift caused by fluid viscosity and density from that caused by mass adsorption in the resonance of a quartz crystal resonator. This method uses the normalized conductance of the crystal to determine a critical frequency at which the fluid mass and fluid loss compensate each other. Tracking the shift in this critical frequency allows us to determine purely mass adsorption on the crystal. We extended this method to Maxwellian fluids for understanding the mass adsorption in non-Newtonian fluids. We validate our approach by real-time mass adsorption measurements using glycerol and albumin solutions. © 2013 IOP Publishing Ltd.}, Doi = {10.1088/0957-0233/24/8/085301}, Key = {fds263339} } @article{fds263355, Author = {Hardy, GJ and Nayak, R and Alam, SM and Shapter, JG and Heinrich, F and Zauscher, S}, Title = {Biomimetic supported lipid bilayers with high cholesterol content formed by α-helical peptide-induced vesicle fusion.}, Journal = {Journal of Materials Chemistry}, Volume = {22}, Number = {37}, Pages = {19506-19513}, Year = {2012}, Month = {August}, ISSN = {0959-9428}, url = {http://dx.doi.org/10.1039/c2jm32016a}, Abstract = {In this study, we present a technique to create a complex, high cholesterol-containing supported lipid bilayers (SLBs) using α-helical (AH) peptide-induced vesicle fusion. Vesicles consisting of POPC : POPE : POPS : SM : Chol (9.35 : 19.25 : 8.25 : 18.15 : 45.00) were used to form a SLB that models the native composition of the human immunodeficiency virus-1 (HIV-1) lipid envelope. In the absence of AH peptides, these biomimetic vesicles fail to form a complete SLB. We verified and characterized AH peptide-induced vesicle fusion by quartz crystal microbalance with dissipation monitoring, neutron reflectivity, and atomic force microscopy. Successful SLB formation entailed a characteristic frequency shift of -35.4 ± 2.0 Hz and a change in dissipation energy of 1.91 ± 0.52 × 10<sup>-6</sup>. Neutron reflectivity measurements determined the SLB thickness to be 49.9 <sup>+1.9</sup><sub>-1.5</sub> Å, and showed the SLB to be 100 <sup>+0.0</sup><sub>-0.1</sub>% complete and void of residual AH peptide after washing. Atomic force microscopy imaging confirmed complete SLB formation and revealed three distinct domains with no visible defects. This vesicle fusion technique gives researchers access to a complex SLB composition with high cholesterol content and thus the ability to better recapitulate the native HIV-1 lipid membrane.}, Doi = {10.1039/c2jm32016a}, Key = {fds263355} } @article{fds263368, Author = {Hardy, GJ and Lam, Y and Stewart, SM and Anasti, K and Alam, SM and Zauscher, S}, Title = {Screening the interactions between HIV-1 neutralizing antibodies and model lipid surfaces.}, Journal = {J Immunol Methods}, Volume = {376}, Number = {1-2}, Pages = {13-19}, Year = {2012}, Month = {February}, url = {http://www.ncbi.nlm.nih.gov/pubmed/22033342}, Abstract = {Our work is motivated by the observation that rare, broadly neutralizing antibodies (NAbs), 4E10 and 2F5, associate with HIV-1 lipids as part of a required first step in neutralization before binding to membrane-proximal antigens. Subsequently, induction of these types of NAbs may be limited by immunologic tolerance due to autoreactivity with host cell membranes. Despite the significance of this lipid reactivity there is little experimental evidence detailing NAb-membrane interactions. Simple and efficient screening assays are needed to select antibodies that have similar lipid reactivity as known NAbs. To this end we have developed a surface plasmon resonance (SPR) spectroscopy based assay that monitors antibody binding to thiol self-assembled monolayers (SAMs) that replicate salient lipid surface chemistries and NAb binding to lipid surfaces. Specifically, we probed the relative importance of charge and hydrophobicity on antibody-surface interactions. We found that NAb binding to hydrophobic thiol surfaces was significantly greater than that of control monoclonal antibodies (mAbs). Furthermore, we confirmed the importance of charge-mediated antibody surface interactions, originally suggested by results from mAb interactions with conventional lipid vesicle/bilayer surfaces. Our approach, using self-assembled thiol monolayers that replicate the binding behavior of NAbs on lipid surfaces, thus provides an efficient and useful tool to screen interactions of mAbs and lipid-reactive NAbs.}, Doi = {10.1016/j.jim.2011.10.005}, Key = {fds263368} } @article{fds263333, Author = {Tjong, V and Zhang, J and Chilkoti, A and Zauscher, S}, Title = {Stimulus-Responsive Polymers as Intelligent Coatings for Biosensors: Architectures, Response Mechanisms, and Applications}, Pages = {1-30}, Booktitle = {Intelligent Surfaces in Biotechnology}, Publisher = {JOHN WILEY & SONS INC}, Address = {New York}, Editor = {Textor M. and Grandin M}, Year = {2012}, Month = {February}, url = {http://dx.doi.org/10.1002/9781118181249.ch1}, Doi = {10.1002/9781118181249.ch1}, Key = {fds263333} } @article{fds263354, Author = {Chen, T and Chang, DP and Zhang, J and Jordan, R and Zauscher, S}, Title = {Manipulating the motion of gold aggregates using stimulus-responsive patterned polymer brushes as a motor}, Journal = {Advanced Functional Materials}, Volume = {22}, Number = {2}, Pages = {429-434}, Publisher = {WILEY}, Year = {2012}, Month = {January}, ISSN = {1616-301X}, url = {http://dx.doi.org/10.1002/adfm.201101795}, Abstract = {An important goal and major challenge of material science and nanotechnology is building nanomotors for manipulating the motion of nanoparticles (NPs). Here, it is demonstrated that patterned, stimulus-responsive polymer brush microstructures can be used as motor arrays to manipulate the movement of gold NP aggregates in response to external stimuli that induce a conformational change in the brushes as the driving force. The motion of NP aggregates in the out-of-plane direction is achieved with displacements ranging from nanometers to sub-micrometers. These patterned polymer-brush microstructures can find applications as efficient motor arrays and nanosensors, and benefit the design of more complex nanodevices. Patterned, stimulus-responsive, "egg-cup"-shaped polymer brush microstructures can be used as motor arrays to manipulate the movement of gold nanoparticle (NP) aggregates in response to external stimuli that induce a conformational change in the brushes as the driving force. The motion of NP aggregates in the out-of-plane direction was achieved with displacements ranging from nanometers to sub-micrometers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.}, Doi = {10.1002/adfm.201101795}, Key = {fds263354} } @article{fds263353, Author = {Chen, T and Chang, DP and Jordan, R and Zauscher, S}, Title = {Colloidal lithography for fabricating patterned polymer-brush microstructures.}, Journal = {Beilstein Journal of Nanotechnology}, Volume = {3}, Pages = {397-403}, Year = {2012}, Month = {January}, url = {http://www.ncbi.nlm.nih.gov/pubmed/23016144}, Abstract = {We exploit a series of robust, but simple and convenient colloidal lithography (CL) approaches, using a microsphere array as a mask or as a guiding template, and combine this with surface-initiated atom-transfer radical polymerization (SI-ATRP) to fabricate patterned polymer-brush microstructures. The advantages of the CL technique over other lithographic approaches for the fabrication of patterned polymer brushes are (i) that it can be carried out with commercially available colloidal particles at a relatively low cost, (ii) that no complex equipment is required to create the patterned templates with micro- and nanoscale features, and (iii) that polymer brush features are controlled simply by changing the size or chemical functionality of the microspheres or the substrate.}, Doi = {10.3762/bjnano.3.46}, Key = {fds263353} } @article{fds263356, Author = {Ferris, R and Yellen, B and Zauscher, S}, Title = {Ferroelectric thin films in fluidic environments: a new interface for sensing and manipulation of matter.}, Journal = {Small (Weinheim an Der Bergstrasse, Germany)}, Volume = {8}, Number = {1}, Pages = {28-35}, Year = {2012}, Month = {January}, url = {http://www.ncbi.nlm.nih.gov/pubmed/22102532}, Abstract = {For decades ferroelectric thin films (FETFs) have been the focus of research and development for next-generation memory and semiconductor devices. FETFs are attractive because their polarization states are highly localized, stable, and switchable. These unique properties are also attractive for (bio)molecular sensing and separation applications. Polarization of both polymer and ceramic FETF results in the expression of a sustained high, non-Faradaic, surface charge density. If these surface charges are maintained in aqueous environments, then the resulting electrostatic forces should induce the formation of electrolyte gradients and aid in the localization of charged species to the surface. Recently, there has been a growing interest in the interfacial properties of FETFs, specifically how they interact with liquid or gaseous phases. Recent work has shown that the FETF polarization state affects adsorption from the gaseous phase, surface catalysis, and cell growth. Encouraged by these findings, the use of FETFs in aqueous environments is explored. After an introduction to FETFs, the growing body of literature on the FETF interface is reviewed, along with the limited number of studies demonstrating FETF function in gas and liquid environments. Finally, the exciting possibilities that FETFs could bring to interfacial engineering and lab-on-chip (LOC) device design is reviewed.}, Doi = {10.1002/smll.201101173}, Key = {fds263356} } @article{fds263361, Author = {Christensen, SE and Coles, JM and Zelenski, NA and Furman, BD and Leddy, HA and Zauscher, S and Bonaldo, P and Guilak, F}, Title = {Altered trabecular bone structure and delayed cartilage degeneration in the knees of collagen VI null mice.}, Journal = {Plos One}, Volume = {7}, Number = {3}, Pages = {e33397}, Year = {2012}, Month = {January}, url = {http://www.ncbi.nlm.nih.gov/pubmed/22448243}, Abstract = {Mutation or loss of collagen VI has been linked to a variety of musculoskeletal abnormalities, particularly muscular dystrophies, tissue ossification and/or fibrosis, and hip osteoarthritis. However, the role of collagen VI in bone and cartilage structure and function in the knee is unknown. In this study, we examined the role of collagen VI in the morphology and physical properties of bone and cartilage in the knee joint of Col6a1(-/-) mice by micro-computed tomography (microCT), histology, atomic force microscopy (AFM), and scanning microphotolysis (SCAMP). Col6a1(-/-) mice showed significant differences in trabecular bone structure, with lower bone volume, connectivity density, trabecular number, and trabecular thickness but higher structure model index and trabecular separation compared to Col6a1(+/+) mice. Subchondral bone thickness and mineral content increased significantly with age in Col6a1(+/+) mice, but not in Col6a1(-/-) mice. Col6a1(-/-) mice had lower cartilage degradation scores, but developed early, severe osteophytes compared to Col6a1(+/+) mice. In both groups, cartilage roughness increased with age, but neither the frictional coefficient nor compressive modulus of the cartilage changed with age or genotype, as measured by AFM. Cartilage diffusivity, measured via SCAMP, varied minimally with age or genotype. The absence of type VI collagen has profound effects on knee joint structure and morphometry, yet minimal influences on the physical properties of the cartilage. Together with previous studies showing accelerated hip osteoarthritis in Col6a1(-/-) mice, these findings suggest different roles for collagen VI at different sites in the body, consistent with clinical data.}, Doi = {10.1371/journal.pone.0033397}, Key = {fds263361} } @article{fds319136, Author = {Hardy, GJ and Alam, M and Shapter, J and Zauscher, S}, Title = {Visualizing Lipid Reactivity of HIV-1 Antigen and Neutralizing Antibodies using Atomic Force Microscopy}, Journal = {Biophysical Journal}, Volume = {102}, Number = {3}, Pages = {303a-303a}, Publisher = {Elsevier BV}, Year = {2012}, Month = {January}, url = {http://dx.doi.org/10.1016/j.bpj.2011.11.1673}, Doi = {10.1016/j.bpj.2011.11.1673}, Key = {fds319136} } @article{fds263357, Author = {Zhang, J and Parlak, Z and Bowers, CM and Oas, T and Zauscher, S}, Title = {Mapping mechanical properties of organic thin films by force-modulation microscopy in aqueous media.}, Journal = {Beilstein Journal of Nanotechnology}, Volume = {3}, Pages = {464-474}, Year = {2012}, url = {http://www.ncbi.nlm.nih.gov/pubmed/23019540}, Abstract = {The mechanical properties of organic and biomolecular thin films on surfaces play an important role in a broad range of applications. Although force-modulation microscopy (FMM) is used to map the apparent elastic properties of such films with high lateral resolution in air, it has rarely been applied in aqueous media. In this letter we describe the use of FMM to map the apparent elastic properties of self-assembled monolayers and end-tethered protein thin films in aqueous media. Furthermore, we describe a simple analysis of the contact mechanics that enables the selection of FMM imaging parameters and thus yields a reliable interpretation of the FMM image contrast.}, Doi = {10.3762/bjnano.3.53}, Key = {fds263357} } @article{fds263371, Author = {Ferris, R and Hucknall, A and Kwon, BS and Chen, T and Chilkoti, A and Zauscher, S}, Title = {Field-induced nanolithography for patterning of non-fouling polymer brush surfaces.}, Journal = {Small (Weinheim an Der Bergstrasse, Germany)}, Volume = {7}, Number = {21}, Pages = {3032-3037}, Year = {2011}, Month = {November}, url = {http://www.ncbi.nlm.nih.gov/pubmed/21901825}, Doi = {10.1002/smll.201100923}, Key = {fds263371} } @article{fds263370, Author = {Chen, T and Jordan, R and Zauscher, S}, Title = {Dynamic microcontact printing for patterning polymer-brush microstructures.}, Journal = {Small (Weinheim an Der Bergstrasse, Germany)}, Volume = {7}, Number = {15}, Pages = {2148-2152}, Year = {2011}, Month = {August}, url = {http://www.ncbi.nlm.nih.gov/pubmed/21598381}, Doi = {10.1002/smll.201100354}, Key = {fds263370} } @article{ISI:000291354200009, Author = {Chen, T and Jordan, R and Zauscher, S}, Title = {Polymer brush patterning using self-assembled microsphere monolayers as microcontact printing stamps}, Journal = {Soft Matter}, Volume = {7}, Number = {12}, Pages = {5532-5535}, Publisher = {Royal Society of Chemistry (RSC)}, Year = {2011}, Month = {June}, ISSN = {1744-683X}, url = {http://dx.doi.org/10.1039/c1sm05474k}, Abstract = {Self-assembled microsphere monolayers (SMMs) hold significant promise for micro- and nanopatterning. Here we exploit, for the first time, SMMs as stamps for microcontact printing (μCP) and demonstrate this to fabricate patterned initiator templates that can subsequently be amplified into polymer brushes by surface initiated atom transfer radical polymerization (SI-ATRP). SMM stamps avoid the need for expensive and sophisticated instrumentation in pattern generation, and provide a broad range of accessible surface chemistries and pitch size control. © 2011 The Royal Society of Chemistry.}, Doi = {10.1039/c1sm05474k}, Key = {ISI:000291354200009} } @article{fds263334, Author = {Chen, T and Zhang, J and Garcia, A and Ducker, R and Zauscher, S}, Title = {Nanopatterning of Polymer Brush Thin Films by Electron-Beam Lithography and Scanning Probe Lithography}, Volume = {1}, Pages = {501-518}, Booktitle = {Functional Polymer Films}, Publisher = {Wiley-VCH Verlag GmbH & Co. KGaA}, Address = {New York}, Editor = {Advincula, R. and Knoll, W.}, Year = {2011}, Month = {June}, url = {http://dx.doi.org/10.1002/9783527638482.ch14}, Doi = {10.1002/9783527638482.ch14}, Key = {fds263334} } @article{ISI:000291133400001, Author = {Chen, T and Jordan, R and Zauscher, S}, Title = {Extending micro-contact printing for patterning complex polymer brush microstructures}, Journal = {Polymer}, Volume = {52}, Number = {12}, Pages = {2461-2467}, Publisher = {Elsevier BV}, Year = {2011}, Month = {May}, ISSN = {0032-3861}, url = {http://dx.doi.org/10.1016/j.polymer.2011.04.008}, Abstract = {As a fast developing soft lithographic technique, the development of micro-contact printing (μCP) has exceeded the original aim of replicating poly(dimethylsiloxane) (PDMS) stamp patterns. Here we exploited several extended μCP strategies with various printing conditions (over-force or swelling induced physical deformation, and UV-Ozone treated chemical surface modification to a PDMS stamp), combining with surface initiated atom transfer radical polymerization (SI-ATRP), to pattern complex poly(N-isopropylacrylamide) (PNIPAAM) brush microstructures. These series of μCP strategies avoid the need for expensive and sophisticated instrumentation in patterning complex polymer brush microstructures that do not exist on the original PDMS stamp. © 2011 Elsevier Ltd. All rights reserved.}, Doi = {10.1016/j.polymer.2011.04.008}, Key = {ISI:000291133400001} } @article{ISI:000289341500050, Author = {Yang, Y and Erb, RM and Wiley, BJ and Zauscher, S and Yellen, BB}, Title = {Imaginary magnetic tweezers for massively parallel surface adhesion spectroscopy.}, Journal = {Nano Letters}, Volume = {11}, Number = {4}, Pages = {1681-1684}, Year = {2011}, Month = {April}, ISSN = {1530-6984}, url = {http://www.ncbi.nlm.nih.gov/pubmed/21417363}, Abstract = {A massively parallel magnetic tweezer system has been constructed that utilizes the self-repulsion of colloidal beads from a planar interface via a magnetic dipole image force. Self-repulsion enables the application of a uniform magnetic force to thousands of beads simultaneously, which permits the measurement of unbinding histograms at the lowest loading rates ever tested. The adhesion of 9.8 μm polystyrene beads to a fluorocarbon, PEG, and UV-irradiated PEG surfaces were measured between 10(-3)-10(0) pN/s force loading rates, revealing the presence of both kinetic and quasi-equilibrium unbinding regimes.}, Doi = {10.1021/nl200189w}, Key = {ISI:000289341500050} } @article{fds194119, Author = {Parlak, Z. and Zhang, J. and Franch, B. and Morris, C. and Oas, T. and Zauscher, S.}, Title = {Imaging Dynamic Mechanical Properties of Biomolecules by Force Modulation Microscopy}, Journal = {Proceedings of the 1st International Conference on Smart Polymer Systems}, Year = {2011}, Key = {fds194119} } @article{fds263369, Author = {Malmsten, M and Zauscher, S}, Title = {Colloids and surfaces in biology}, Journal = {Current Opinion in Colloid & Interface Science}, Volume = {15}, Number = {6}, Pages = {393-394}, Publisher = {Elsevier BV}, Year = {2010}, Month = {December}, ISSN = {1359-0294}, url = {http://dx.doi.org/10.1016/j.cocis.2010.08.001}, Doi = {10.1016/j.cocis.2010.08.001}, Key = {fds263369} } @article{ISI:000284520000003, Author = {Coles, JM and Chang, DP and Zauscher, S}, Title = {Molecular mechanisms of aqueous boundary lubrication by mucinous glycoproteins}, Journal = {Current Opinion in Colloid & Interface Science}, Volume = {15}, Number = {6}, Pages = {406-416}, Publisher = {Elsevier BV}, Year = {2010}, Month = {December}, ISSN = {1359-0294}, url = {http://dx.doi.org/10.1016/j.cocis.2010.07.002}, Abstract = {Mucins have long been recognized as instrumental to biolubrication but the molecular details of their lubrication mechanisms have only been explored relatively recently. The glycoprotein PRG4, also known as lubricin, shares many features with mucins and appears to lubricate through similar mechanisms. A number of studies have contributed to a more in-depth understanding of mucin adsorption and layer formation on surfaces and the mechanisms by which these layers lubricate. Although mucinous glycoproteins differ in their aggregation properties, their adsorption behaviors on surfaces, and in their ability to reduce friction, they share important similarities favorable for lubrication. They are highly hydrated, they adsorb strongly to a broad range of surfaces, and the layers they form are both sterically and electrostatically repulsive, all attributes thought to contribute to boundary lubrication. They also hydrophilize hydrophobic surfaces, promoting the formation of aqueous fluid films that can lower friction at already relatively low sliding speeds. In this paper we briefly review current knowledge of mucin adsorption and lubrication, with a focus on recent advances. © 2010 Elsevier Ltd.}, Doi = {10.1016/j.cocis.2010.07.002}, Key = {ISI:000284520000003} } @article{ISI:000284343700036, Author = {Coles, JM and Blum, JJ and Jay, GD and Darling, EM and Guilak, F and Zauscher, S}, Title = {Corrigendum to In situ friction measurement on murine cartilage by atomic force microscopy [J. Biomech. 41, 3, (2008) 541-548]}, Journal = {Journal of Biomechanics}, Volume = {43}, Number = {14}, Pages = {2866}, Publisher = {Elsevier BV}, Year = {2010}, Month = {October}, ISSN = {0021-9290}, url = {http://dx.doi.org/10.1016/j.jbiomech.2010.09.020}, Doi = {10.1016/j.jbiomech.2010.09.020}, Key = {ISI:000284343700036} } @inproceedings{ISI:000290920600056, Author = {Zhao, Y and Chen, T and Zhang, X and Zauscher, S and Chen, CH}, Title = {Development of an adaptive vapor chamber with thermoresponsive polymer coating}, Journal = {Proceedings of the Asme Micro/Nanoscale Heat and Mass Transfer International Conference 2009, Mnhmt2009}, Volume = {3}, Pages = {395-398}, Booktitle = {PROCEEDINGS OF THE ASME MICRO/NANOSCALE HEAT AND MASS TRANSFER INTERNATIONAL CONFERENCE, VOL 3}, Publisher = {ASME}, Organization = {ASME Nanotechnol Inst}, Institution = {ASME Nanotechnol Inst}, Year = {2010}, Month = {July}, ISBN = {978-0-7918-4391-8}, url = {http://dx.doi.org/10.1115/MNHMT2009-18276}, Abstract = {We propose a novel concept for an adaptive vapor chamber using a thermoresponsive polymer coating to enhance heat transfer and reduce local thermal gradients. By coating the wick structures with stimulus-responsive polymer brushes with an upper critical solution temperature (UCST), i the hotter surface becomes more wettable than the colder surface. The smaller contact angle at higher temperature generates larger capillary forces and promotes stronger return flow toward the hotspots. In this paper, we present our ; progress toward developing the adaptive vapor chamber. We have grafted poly(2-(meth-acryloyloxy)ethyl(dimethyl(3-sulfopropyl) ammonium hydroxide) (PMEDSAH) brushes on silica wafers, and the PMEDSAH polymer coating exhibits UCST properties with stable and tunable wettability. We have captured infrared images of the evaporator with steady and transient heating, and developed a thermographic technique that can be used to test the adaptive wick functionality in a vapor chamber. Copyright © 2009 by ASME.}, Doi = {10.1115/MNHMT2009-18276}, Key = {ISI:000290920600056} } @article{fds319137, Author = {Chen, T and Chang, DP and Zauscher, S}, Title = {Polymer brushes: Fabrication of Patterned Polymer Brushes on Chemically Active Surfaces by in situ Hydrogen-Bond-Mediated Attachment of an Initiator (Small 14/2010).}, Journal = {Small}, Volume = {6}, Number = {14}, Year = {2010}, Month = {July}, url = {http://dx.doi.org/10.1002/smll.201090044}, Doi = {10.1002/smll.201090044}, Key = {fds319137} } @article{ISI:000280633900008, Author = {Chen, T and Chang, DP and Zauscher, S}, Title = {Fabrication of patterned polymer brushes on chemically active surfaces by in situ hydrogen-bond-mediated attachment of an initiator.}, Journal = {Small (Weinheim an Der Bergstrasse, Germany)}, Volume = {6}, Number = {14}, Pages = {1504-1508}, Year = {2010}, Month = {July}, ISSN = {1613-6810}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20572261}, Doi = {10.1002/smll.200902119}, Key = {ISI:000280633900008} } @article{ISI:000278913500013, Author = {Darling, EM and Wilusz, RE and Bolognesi, MP and Zauscher, S and Guilak, F}, Title = {Spatial mapping of the biomechanical properties of the pericellular matrix of articular cartilage measured in situ via atomic force microscopy.}, Journal = {Biophysical Journal}, Volume = {98}, Number = {12}, Pages = {2848-2856}, Year = {2010}, Month = {June}, ISSN = {0006-3495}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20550897}, Abstract = {In articular cartilage, chondrocytes are surrounded by a narrow region called the pericellular matrix (PCM), which is biochemically, structurally, and mechanically distinct from the bulk extracellular matrix (ECM). Although multiple techniques have been used to measure the mechanical properties of the PCM using isolated chondrons (the PCM with enclosed cells), few studies have measured the biomechanical properties of the PCM in situ. The objective of this study was to quantify the in situ mechanical properties of the PCM and ECM of human, porcine, and murine articular cartilage using atomic force microscopy (AFM). Microscale elastic moduli were quantitatively measured for a region of interest using stiffness mapping, or force-volume mapping, via AFM. This technique was first validated by means of elastomeric models (polyacrylamide or polydimethylsiloxane) of a soft inclusion surrounded by a stiff medium. The elastic properties of the PCM were evaluated for regions surrounding cell voids in the middle/deep zone of sectioned articular cartilage samples. ECM elastic properties were evaluated in regions visually devoid of PCM. Stiffness mapping successfully depicted the spatial arrangement of moduli in both model and cartilage surfaces. The modulus of the PCM was significantly lower than that of the ECM in human, porcine, and murine articular cartilage, with a ratio of PCM to ECM properties of approximately 0.35 for all species. These findings are consistent with previous studies of mechanically isolated chondrons, and suggest that stiffness mapping via AFM can provide a means of determining microscale inhomogeneities in the mechanical properties of articular cartilage in situ.}, Doi = {10.1016/j.bpj.2010.03.037}, Key = {ISI:000278913500013} } @article{ISI:000276553300007, Author = {Chen, T and Chang, DP and Liu, T and Desikan, R and Datar, R and Thundat, T and Berger, R and Zauscher, S}, Title = {Glucose-responsive polymer brushes for microcantilever sensing}, Journal = {Journal of Materials Chemistry}, Volume = {20}, Number = {17}, Pages = {3391-3395}, Publisher = {Royal Society of Chemistry (RSC)}, Year = {2010}, Month = {June}, ISSN = {0959-9428}, url = {http://hdl.handle.net/10161/4121 Duke open access}, Abstract = {Glucose responsive polymer brushes were synthesized on gold substrates and microcantilever arrays. The response properties of these brushes were evaluated by exposing them to different glucose concentrations for a range of pH values. This work demonstrates the potential for polymer brush-functionalized micromechanical cantilevers as glucose detectors. Furthermore, the work demonstrates that stimulus-responsive polymer brushes on micromechanical cantilevers have a significantly larger bending response due to glucose binding compared with self-assembled monolayers. © The Royal Society of Chemistry 2010.}, Doi = {10.1039/b925583d}, Key = {ISI:000276553300007} } @article{ISI:000279432500015, Author = {Coles, JM and Zhang, L and Blum, JJ and Warman, ML and Jay, GD and Guilak, F and Zauscher, S}, Title = {Loss of cartilage structure, stiffness, and frictional properties in mice lacking PRG4.}, Journal = {Arthritis and Rheumatism}, Volume = {62}, Number = {6}, Pages = {1666-1674}, Year = {2010}, Month = {June}, ISSN = {0004-3591}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20191580}, Abstract = {<h4>Objective</h4>To assess the role of the glycoprotein PRG4 in joint lubrication and chondroprotection by measuring friction, stiffness, surface topography, and subsurface histology of the hip joints of Prg4(-/-) and wild-type (WT) mice.<h4>Methods</h4>Friction and elastic modulus were measured in cartilage from the femoral heads of Prg4(-/-) and WT mice ages 2, 4, 10, and 16 weeks using atomic force microscopy, and the surface microstructure was imaged. Histologic sections of each femoral head were stained and graded.<h4>Results</h4>Histologic analysis of the joints of Prg4(-/-) mice showed an enlarged, fragmented surface layer of variable thickness with Safranin O-positive formations sometimes present, a roughened underlying articular cartilage surface, and a progressive loss of pericellular proteoglycans. Friction was significantly higher on cartilage of Prg4(-/-) mice at age 16 weeks, but statistically significant differences in friction were not detected at younger ages. The elastic modulus of the cartilage was similar between cartilage surfaces of Prg4(-/-) and WT mice at young ages, but cartilage of WT mice showed increasing stiffness with age, with significantly higher moduli than cartilage of Prg4(-/-) mice at older ages.<h4>Conclusion</h4>Deletion of the gene Prg4 results in significant structural and biomechanical changes in the articular cartilage with age, some of which are consistent with osteoarthritic degeneration. These findings suggest that PRG4 plays a significant role in preserving normal joint structure and function.}, Doi = {10.1002/art.27436}, Key = {ISI:000279432500015} } @article{ISI:000277710700004, Author = {Huang, X and Zauscher, S and Klitzman, B and Truskey, GA and Reichert, WM and Kenan, DJ and Grinstaff, MW}, Title = {Peptide interfacial biomaterials improve endothelial cell adhesion and spreading on synthetic polyglycolic acid materials.}, Journal = {Ann Biomed Eng}, Volume = {38}, Number = {6}, Pages = {1965-1976}, Year = {2010}, Month = {June}, ISSN = {0090-6964}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20300848}, Abstract = {Resorbable scaffolds such as polyglycolic acid (PGA) are employed in a number of clinical and tissue engineering applications owing to their desirable property of allowing remodeling to form native tissue over time. However, native PGA does not promote endothelial cell adhesion. Here we describe a novel treatment with hetero-bifunctional peptide linkers, termed "interfacial biomaterials" (IFBMs), which are used to alter the surface of PGA to provide appropriate biological cues. IFBMs couple an affinity peptide for the material with a biologically active peptide that promotes desired cellular responses. One such PGA affinity peptide was coupled to the integrin binding domain, Arg-Gly-Asp (RGD), to build a chemically synthesized bimodular 27 amino acid peptide that mediated interactions between PGA and integrin receptors on endothelial cells. Quartz crystal microbalance with dissipation monitoring (QCMD) was used to determine the association constant (K (A) 1 x 10(7) M(-1)) and surface thickness (~3.5 nm). Cell binding studies indicated that IFBM efficiently mediated adhesion, spreading, and cytoskeletal organization of endothelial cells on PGA in an integrin-dependent manner. We show that the IFBM peptide promotes a 200% increase in endothelial cell binding to PGA as well as 70-120% increase in cell spreading from 30 to 60 minutes after plating.}, Doi = {10.1007/s10439-010-9986-5}, Key = {ISI:000277710700004} } @article{ISI:000273810600012, Author = {Stuart, MAC and Huck, WTS and Genzer, J and Müller, M and Ober, C and Stamm, M and Sukhorukov, GB and Szleifer, I and Tsukruk, VV and Urban, M and Winnik, F and Zauscher, S and Luzinov, I and Minko, S}, Title = {Emerging applications of stimuli-responsive polymer materials.}, Journal = {Nature Materials}, Volume = {9}, Number = {2}, Pages = {101-113}, Year = {2010}, Month = {February}, ISSN = {1476-1122}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20094081}, Abstract = {Responsive polymer materials can adapt to surrounding environments, regulate transport of ions and molecules, change wettability and adhesion of different species on external stimuli, or convert chemical and biochemical signals into optical, electrical, thermal and mechanical signals, and vice versa. These materials are playing an increasingly important part in a diverse range of applications, such as drug delivery, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings and textiles. We review recent advances and challenges in the developments towards applications of stimuli-responsive polymeric materials that are self-assembled from nanostructured building blocks. We also provide a critical outline of emerging developments.}, Doi = {10.1038/nmat2614}, Key = {ISI:000273810600012} } @article{ISI:000274776300005, Author = {Chen, T and Ferris, R and Zhang, J and Ducker, R and Zauscher, S}, Title = {Stimulus-responsive polymer brushes on surfaces: Transduction mechanisms and applications}, Journal = {Progress in Polymer Science}, Volume = {35}, Number = {1-2, SI}, Pages = {94-112}, Publisher = {Elsevier BV}, Year = {2010}, Month = {January}, ISSN = {0079-6700}, url = {http://dx.doi.org/10.1016/j.progpolymsci.2009.11.004}, Abstract = {Stimulus-responsive polymer brushes (SRPBs) exhibit a change in conformation and structure, often accompanied by a noticeable change in surface energy, due to an external stimulus such as a change in solvent composition, temperature, pH, ionic strength, light, or mechanical stress. SRPBs offer exciting and new possibilities to fabricate adaptive or responsive smart materials. This review summarizes selected, recent progress in SRPB applications in the field of surface wettability switching, mechanical actuation, and environmental sensing. Furthermore, we review selected papers from an emerging area in which SRPBs are used for nano- and microfabrication. (C) 2009 Elsevier Ltd. All rights reserved.}, Doi = {10.1016/j.progpolymsci.2009.11.004}, Key = {ISI:000274776300005} } @article{fds194118, Author = {Chen, T. and Zauscher, S.}, Title = {Nanopatterning of Functional Polymer Brush Thin Films}, Journal = {Proceedings of the 1st International Conference on Smart Polymer Systems}, Year = {2010}, Key = {fds194118} } @inproceedings{ISI:000280089000533, Author = {Wilusz, RE and Darling, EM and Bolognesi, MP and Zauscher, S and Guilak, F}, Title = {The inhomogeneous mechanical properties of the pericellular matrix of articular cartilage measured in situ by atomic force microscopy}, Journal = {Proceedings of the Asme Summer Bioengineering Conference 2009, Sbc2009}, Number = {PART B}, Pages = {1065-1066}, Booktitle = {PROCEEDINGS OF THE ASME SUMMER BIOENGINEERING CONFERENCE - 2009, PT A AND B}, Publisher = {ASME}, Organization = {ASME Bioengn Div}, Institution = {ASME Bioengn Div}, Year = {2009}, Month = {December}, ISBN = {978-0-7918-4891-3}, url = {http://dx.doi.org/10.1115/SBC2009-206403}, Doi = {10.1115/SBC2009-206403}, Key = {ISI:000280089000533} } @article{ISI:000269493300009, Author = {Chang, DP and Abu-Lail, NI and Coles, JM and Guilak, F and Jay, GD and Zauscher, S}, Title = {Friction Force Microscopy of Lubricin and Hyaluronic Acid between Hydrophobic and Hydrophilic Surfaces.}, Journal = {Soft Matter}, Volume = {5}, Number = {18}, Pages = {3438-3445}, Year = {2009}, Month = {September}, ISSN = {1744-683X}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20936046}, Abstract = {Lubricin and hyaluronic acid (HA), molecular constituents of synovial fluid, have long been theorized to play a role in joint lubrication and wear protection. While lubricin has been shown to function as a boundary lubricant, conflicting evidence exists as to the boundary lubricating ability of hyaluronic acid. Here, we use colloidal force microscopy to explore the friction behavior of these two molecules on the microscale between chemically uniform hydrophilic (hydroxyl-terminated) and hydrophobic (methyl-terminated) surfaces in physiological buffer solution. Behaviors on both surfaces are physiologically relevant since the heterogeneous articular cartilage surface contains both hydrophilic and hydrophobic elements. Friction between hydrophobic surfaces was initially high (μ=1.1, at 100nN of applied normal load) and was significantly reduced by lubricin addition while friction between hydrophilic surfaces was initially low (μ=0.1) and was slightly increased by lubricin addition. At lubricin concentrations above 200 µg/ml, friction behavior on the two surfaces was similar (μ=0.2) indicating that nearly all interaction between the two surfaces was between adsorbed lubricin molecules rather than between the surfaces themselves. In contrast, addition of HA did not appreciably alter the frictional behavior between the model surfaces. No synergistic effect on friction behavior was seen in a physiological mixture of lubricin and HA. Lubricin can equally mediate the frictional response between both hydrophilic and hydrophobic surfaces, likely fully preventing direct surface-to-surface contact at sufficient concentrations, whereas HA provides considerably less boundary lubrication.}, Doi = {10.1039/b907155e}, Key = {ISI:000269493300009} } @article{ISI:000270168900013, Author = {Darling, EM and Pritchett, PE and Evans, BA and Superfine, R and Zauscher, S and Guilak, F}, Title = {Mechanical properties and gene expression of chondrocytes on micropatterned substrates following dedifferentiation in monolayer.}, Journal = {Cellular and Molecular Bioengineering}, Volume = {2}, Number = {3}, Pages = {395-404}, Year = {2009}, Month = {August}, ISSN = {1865-5025}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20625462}, Abstract = {Chondrocytes in articular cartilage normally exhibit high expression of collagen II and aggrecan but rapidly dedifferentiate to a fibroblastic phenotype if passaged in culture. Previous studies have suggested that the loss of chondrocyte phenotype is associated with changes in the structure of the F-actin cytoskeleton, which also controls cell mechanical properties. In this study, we examined how dedifferentiation in monolayer influences the mechanical properties of chondrocytes isolated from different zones of articular cartilage. Atomic force microscopy was used to measure the mechanical properties of superficial and middle/deep zone chondrocytes as they underwent serial passaging and subsequent growth on fibronectin-coated, micropatterned self-assembled monolayers (MSAMs) that restored a rounded cell shape in 2D culture. Chondrocytes exhibited significant increases in elastic and viscoelastic moduli with dedifferentiation in culture. These changes were only partially ameliorated by the restoration of a rounded shape on micropatterned surfaces. Furthermore, intrinsic zonal differences in cell mechanical properties were rapidly lost with passage. These findings indicate that cell mechanical properties may provide additional measures of phenotypic expression of chondrocytes as they undergo dedifferentiation and possibly redifferentiation in culture.}, Doi = {10.1007/s12195-009-0077-3}, Key = {ISI:000270168900013} } @article{ISI:000266976300007, Author = {Hucknall, Angus and Simnick, Andrew J. and Hill, Ryan T. and Chilkoti, Ashutosh and Garcia, Andres and Johannes, Matthew S. and Clark, Robert L. and Zauscher, Stefan and Ratner, Buddy D.}, Title = {Versatile synthesis and micropatterning of nonfouling polymer brushes on the wafer scale}, Journal = {BIOINTERPHASES}, Volume = {4}, Number = {2}, Pages = {FA50-FA57}, Year = {2009}, Month = {June}, ISSN = {1559-4106}, url = {http://dx.doi.org/10.1116/1.3151968}, Abstract = {In this article, the authors describe new approaches to synthesize and pattern surfaces with poly{[}oligo(ethylene glycol) methyl methacrylate] (POEGMA) polymer brushes synthesized by surface-initiated atom transfer radical polymerization. These patterned coatings confer ``nonfouling{''} properties protein and cell resistance-to the surface in a biological milieu. The versatile routes for the synthesis of POEGMA demonstrated here offer clear advantages over other techniques previously used in terms of their simplicity, reliability, and ability to pattern large-area substrates. They also demonstrate that POEGMA polymer brushes can be patterned directly by photolithography, plasma ashing, and reactive ion etching to create patterns at the micro- and nanoscale over large areas with high throughput and repeatability, while preserving the protein and cell resistance of the POEGMA brush.}, Doi = {10.1116/1.3151968}, Key = {ISI:000266976300007} } @article{ISI:000266976300001, Author = {Zauscher, Stefan and Chilkoti, Ashutosh}, Title = {Biological Applications of Polymer Brushes}, Journal = {BIOINTERPHASES}, Volume = {4}, Number = {2}, Pages = {FA1-FA2}, Year = {2009}, Month = {June}, ISSN = {1559-4106}, url = {http://dx.doi.org/10.1116/1.3149787}, Doi = {10.1116/1.3149787}, Key = {ISI:000266976300001} } @booklet{Hucknall09, Author = {Hucknall, A and Simnick, AJ and Hill, RT and Chilkoti, A and Garcia, A and Johannes, MS and Clark, RL and Zauscher, S and Ratner, BD}, Title = {Versatile synthesis and micropatterning of nonfouling polymer brushes on the wafer scale.}, Journal = {Biointerphases}, Volume = {4}, Number = {2}, Pages = {FA50-FA57}, Year = {2009}, Month = {June}, ISSN = {1559-4106}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20408717}, Abstract = {In this article, the authors describe new approaches to synthesize and pattern surfaces with poly[oligo(ethylene glycol) methyl methacrylate] (POEGMA) polymer brushes synthesized by surface-initiated atom transfer radical polymerization. These patterned coatings confer "nonfouling" properties protein and cell resistance-to the surface in a biological milieu. The versatile routes for the synthesis of POEGMA demonstrated here offer clear advantages over other techniques previously used in terms of their simplicity, reliability, and ability to pattern large-area substrates. They also demonstrate that POEGMA polymer brushes can be patterned directly by photolithography, plasma ashing, and reactive ion etching to create patterns at the micro- and nanoscale over large areas with high throughput and repeatability, while preserving the protein and cell resistance of the POEGMA brush.}, Doi = {10.1116/1.3151968}, Key = {Hucknall09} } @booklet{Zauscher09, Author = {Zauscher, S and Chilkoti, A}, Title = {Biological applications of polymer brushes. Preface.}, Journal = {Biointerphases}, Volume = {4}, Number = {2}, Pages = {FA1-FA2}, Year = {2009}, Month = {June}, ISSN = {1559-4106}, url = {http://www.ncbi.nlm.nih.gov/pubmed/20408712}, Doi = {10.1116/1.3149787}, Key = {Zauscher09} } @article{ISI:000266287600007, Author = {Chen, Tao and Zhong, Jianming and Chang, Debby P. and Carcia, Andres and Zauscher, Stefan}, Title = {Fabrication of Micropatterned Stimulus-Responsive Polymer-Brush `Anemone'}, Journal = {ADVANCED MATERIALS}, Volume = {21}, Number = {18}, Pages = {1825+}, Year = {2009}, Month = {May}, ISSN = {0935-9648}, url = {http://dx.doi.org/10.1002/adma.200802484}, Abstract = {A simple strategy to fabricate stimulus-responsive patterned PNIPAAM-brush microstructures ('anemones') is presented. The size of the microstructures can be adjusted by setting the composition of thiol and the contact pressure. We demonstrate that the patterned PNIPAAM-brush microstructures have a triggerable and reversible conformation transition, and can potentially be used as microcontainers to reversibly dock and release microparticles.}, Doi = {10.1002/adma.200802484}, Key = {ISI:000266287600007} } @booklet{Chen09, Author = {Chen, T and Zhong, JM and Chang, DP and Carcia, A and Zauscher, S}, Title = {Fabrication of Micropatterned Stimulus-Responsive Polymer-Brush 'Anemone'}, Journal = {Advanced Materials (Deerfield Beach, Fla.)}, Volume = {21}, Number = {18}, Pages = {1825-+}, Publisher = {WILEY}, Year = {2009}, Month = {May}, ISSN = {0935-9648}, url = {http://dx.doi.org/10.1002/adma.200802484}, Abstract = {A simple strategy to fabricate stimulus-responsive patterned PNIPAAM-brush microstructures ('anemones') is presented. The size of the microstructures can be adjusted by setting the composition of thiol and the contact pressure. We demonstrate that the patterned PNIPAAM-brush microstructures have a triggerable and reversible conformation transition, and can potentially be used as microcontainers to reversibly dock and release microparticles.}, Doi = {10.1002/adma.200802484}, Key = {Chen09} } @article{ISI:000207857807610, Author = {Chen, T and Zauscher, S}, Title = {Fabrication of novel polymer brush microstructures using microcontact printing as a tool}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {237}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2009}, Month = {March}, ISSN = {0065-7727}, url = {http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000207857807610&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=47d3190e77e5a3a53558812f597b0b92}, Key = {ISI:000207857807610} } @article{ISI:000207857803154, Author = {Dyer, DJ and Wong, VN and Mitrovic, B and Kinsel, GR and Zauscher, S}, Title = {Responsive polymer brush nanosponges}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {237}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2009}, Month = {March}, ISSN = {0065-7727}, url = {http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000207857803154&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=47d3190e77e5a3a53558812f597b0b92}, Key = {ISI:000207857803154} } @article{ISI:000264047700006, Author = {Standulescu, Ilinca and Dolbow, John E. and Zauscher, Stefan}, Title = {Computational modeling of surface phenomena in soft-wet materials}, Journal = {INTERNATIONAL JOURNAL OF SOLIDS AND STRUCTURES}, Volume = {46}, Number = {6}, Pages = {1334-1344}, Year = {2009}, Month = {March}, ISSN = {0020-7683}, url = {http://dx.doi.org/10.1016/j.ijsolstr.2008.11.007}, Abstract = {We consider the problem of extracting tribological information from experimental observations of contact with soft-wet materials. Particular attention is placed on simulating the response of two rotating cylinders of soft specimens placed in frictional contact, with a variable coefficient of friction dependent on the relative sliding velocity. The bulk behavior is modeled by means of a finite deformation viscoelasticity formulation, with constitutive parameters taken to be representative of hydrogels. We focus on the modeling of the surface behavior and employ a mortar-finite element contact formulation. Through a series of numerical studies, we demonstrate the strong sensitivity of the results to the choice of interfacial constitutive parameters. The difficulties of extracting such parameters using only experimental data and approximate analytical expressions are also examined. (C) 2008 Elsevier Ltd. All rights reserved.}, Doi = {10.1016/j.ijsolstr.2008.11.007}, Key = {ISI:000264047700006} } @booklet{Standulescu09, Author = {Stanciulescu, I and Dolbow, JE and Zauscher, S}, Title = {Computational modeling of surface phenomena in soft-wet materials}, Journal = {International Journal of Solids and Structures}, Volume = {46}, Number = {6}, Pages = {1334-1344}, Publisher = {Elsevier BV}, Year = {2009}, Month = {March}, ISSN = {0020-7683}, url = {http://dx.doi.org/10.1016/j.ijsolstr.2008.11.007}, Abstract = {We consider the problem of extracting tribological information from experimental observations of contact with soft-wet materials. Particular attention is placed on simulating the response of two rotating cylinders of soft specimens placed in frictional contact, with a variable coefficient of friction dependent on the relative sliding velocity. The bulk behavior is modeled by means of a finite deformation viscoelasticity formulation, with constitutive parameters taken to be representative of hydrogels. We focus on the modeling of the surface behavior and employ a mortar-finite element contact formulation. Through a series of numerical studies, we demonstrate the strong sensitivity of the results to the choice of interfacial constitutive parameters. The difficulties of extracting such parameters using only experimental data and approximate analytical expressions are also examined. © 2008 Elsevier Ltd. All rights reserved.}, Doi = {10.1016/j.ijsolstr.2008.11.007}, Key = {Standulescu09} } @article{ISI:000262827400030, Author = {Wong, Ven Ney and Fernando, Ganga and Wagner, Audrey R. and Zhang, Jianming and Kinsel, Gary R. and Zauscher, Stefan and Dyer, Daniel J.}, Title = {Separation of Peptides with Polyionic Nanosponges for MALDI-MS Analysis}, Journal = {LANGMUIR}, Volume = {25}, Number = {3}, Pages = {1459-1465}, Year = {2009}, Month = {February}, ISSN = {0743-7463}, url = {http://dx.doi.org/10.1021/la802723r}, Abstract = {A polymer brush consisting of 70\% poly(N-isopropylacrylamide) (PNIPAAM) and 30\% polymethacrylic acid (PMAA) was synthesized from gold substrates with a ``grafting from{''} AIBN-type free-radical initiator. Fractionation of two peptides, bradykinin and buccalin, was accomplished in less than 120 s by placing a 30 pM (pH similar to 6.2) droplet onto the polymer brush substrate. The eluant containing the anionic buccalin is pipetted away for MALDI analysis while the cationic bradykinin adsorbed to the swollen anionic brush and was subsequently released by adding a droplet of formic acid to the substrate. This caused the brush to collapse and release the bradykinin, much like squeezing a sponge; these nanosponge substrates exhibited very high loading capacity (>2.0 mg/mL compared to plasma-polymer-modified MALDI substrates. Ellipsometric measurements showed that complementary peptides adsorb rapidly while those of the same charge do not, and MALDI-MS analysis of the two fractions showed separation of both peptides. The adsorption of bradykinin was monitored over time, and 85\% of the peptide had been adsorbed to the nanosponge in 1 min from a 0.5 mg/mL aqueous solution.}, Doi = {10.1021/la802723r}, Key = {ISI:000262827400030} } @booklet{Wong09, Author = {Wong, VN and Fernando, G and Wagner, AR and Zhang, J and Kinsel, GR and Zauscher, S and Dyer, DJ}, Title = {Separation of Peptides with Polyionic Nanosponges for MALDI-MS Analysis}, Journal = {Langmuir : the Acs Journal of Surfaces and Colloids}, Volume = {25}, Number = {3}, Pages = {1459-1465}, Year = {2009}, Month = {February}, ISSN = {0743-7463}, url = {http://www.ncbi.nlm.nih.gov/pubmed/19123797}, Abstract = {A polymer brush consisting of 70\% poly(N-isopropylacrylamide) (PNIPAAM) and 30\% polymethacrylic acid (PMAA) was synthesized from gold substrates with a "grafting from" AIBN-type free-radical initiator. Fractionation of two peptides, bradykinin and buccalin, was accomplished in less than 120 s by placing a 30 pM (pH similar to 6.2) droplet onto the polymer brush substrate. The eluant containing the anionic buccalin is pipetted away for MALDI analysis while the cationic bradykinin adsorbed to the swollen anionic brush and was subsequently released by adding a droplet of formic acid to the substrate. This caused the brush to collapse and release the bradykinin, much like squeezing a sponge; these nanosponge substrates exhibited very high loading capacity ($>$2.0 mg/mL compared to plasma-polymer-modified MALDI substrates. Ellipsometric measurements showed that complementary peptides adsorb rapidly while those of the same charge do not, and MALDI-MS analysis of the two fractions showed separation of both peptides. The adsorption of bradykinin was monitored over time, and 85\% of the peptide had been adsorbed to the nanosponge in 1 min from a 0.5 mg/mL aqueous solution.}, Doi = {10.1021/la802723r}, Key = {Wong09} } @article{fds263360, Author = {Barthel, J and Konkar, S and Sankin, G and Darling, E and Guilak, F and Zhong, P and LaMattina, B and Zauscher, S}, Title = {Effect of shockwaves on the biomechanical and biochemical function of cells}, Journal = {Society for Experimental Mechanics 11th International Congress and Exhibition on Experimental and Applied Mechanics 2008}, Volume = {3}, Pages = {1315-1319}, Year = {2008}, Month = {December}, Abstract = {The number of non-lethal cases of soldiers being exposed to blasts from improvised explosive devices (IED) has increased significantly over the last few years. Concurrently, the number of soft tissue injuries, including traumatic brain injuries (TBI) and heterotopic ossification (HO, i.e., abnormal formation of bone in soft tissue) have increased. Little is known, however, about the molecular and cellular level effects of high strain-rate loading of soft tissues. Here we report on the instrumentation and procedures we have developed to apply high strain-rate loading to cell-sheets in vitro and we will discuss the biomechanical and biochemical properties of cells that have been exposed to high strain rate loading conditions. © 2008 Society for Experimental Mechanics Inc.}, Key = {fds263360} } @booklet{Hook08, Author = {Höök, F and Kasemo, B and Grunze, M and Zauscher, S}, Title = {Quantitative biological surface science: challenges and recent advances.}, Journal = {Acs Nano}, Volume = {2}, Number = {12}, Pages = {2428-2436}, Year = {2008}, Month = {December}, ISSN = {1936-0851}, url = {http://www.ncbi.nlm.nih.gov/pubmed/19206275}, Abstract = {Biological surface science is a broad, interdisciplinary subfield of surface science, where properties and processes at biological and synthetic surfaces and interfaces are investigated, and where biofunctional surfaces are fabricated. The need to study and to understand biological surfaces and interfaces in liquid environments provides sizable challenges as well as fascinating opportunities. Here, we report on recent progress in biological surface science that was described within the program assembled by the Biomaterial Interface Division of the Science and Technology of Materials, Interfaces and Processes (www.avs.org) during their 55th International Symposium and Exhibition held in Boston, October 19-24, 2008. The selected examples show that the rapid progress in nanoscience and nanotechnology, hand-in-hand with theory and simulation, provides increasingly sophisticated methods and tools to unravel the mechanisms and details of complex processes at biological surfaces and in-depth understanding of biomolecular surface interactions.}, Doi = {10.1021/nn800800v}, Key = {Hook08} } @booklet{Mock08, Author = {Mock, JJ and Hill, RT and Degiron, A and Zauscher, S and Chilkoti, A and Smith, DR}, Title = {Distance-dependent plasmon resonant coupling between a gold nanoparticle and gold film.}, Journal = {Nano Letters}, Volume = {8}, Number = {8}, Pages = {2245-2252}, Year = {2008}, Month = {August}, ISSN = {1530-6984}, url = {http://www.ncbi.nlm.nih.gov/pubmed/18590340}, Abstract = {We present an experimental analysis of the plasmonic scattering properties of gold nanoparticles controllably placed nanometers away from a gold metal film. We show that the spectral response of this system results from the interplay between the localized plasmon resonance of the nanoparticle and the surface plasmon polaritons of the gold film, as previously predicted by theoretical studies. In addition, we report that the metal film induces a polarization to the single nanoparticle light scattering, resulting in a doughnut-shaped point spread function when imaged in the far-field. Both the spectral response and the polarization effects are highly sensitive to the nanoparticle-film separation distance. Such a system shows promise in potential biometrology and diagnostic devices.}, Doi = {10.1021/nl080872f}, Key = {Mock08} } @booklet{Valiaev08, Author = {Valiaev, A and Lim, DW and Schmidler, S and Clark, RL and Chilkoti, A and Zauscher, S}, Title = {Hydration and conformational mechanics of single, end-tethered elastin-like polypeptides.}, Journal = {Journal of the American Chemical Society}, Volume = {130}, Number = {33}, Pages = {10939-10946}, Year = {2008}, Month = {August}, ISSN = {0002-7863}, url = {http://www.ncbi.nlm.nih.gov/pubmed/18646848}, Abstract = {We investigated the effect of temperature, ionic strength, solvent polarity, and type of guest residue on the force-extension behavior of single, end-tethered elastin-like polypeptides (ELPs), using single molecule force spectroscopy (SMFS). ELPs are stimulus-responsive polypeptides that contain repeats of the five amino acids Val-Pro-Gly-Xaa-Gly (VPGXG), where Xaa is a guest residue that can be any amino acid with the exception of proline. We fitted the force-extension data with a freely jointed chain (FJC) model which allowed us to resolve small differences in the effective Kuhn segment length distributions that largely arise from differences in the hydrophobic hydration behavior of ELP. Our results agree qualitatively with predictions from recent molecular dynamics simulations and demonstrate that hydrophobic hydration modulates the molecular elasticity for ELPs. Furthermore, our results show that SMFS, when combined with our approach for data analysis, can be used to study the subtleties of polypeptide-water interactions and thus provides a basis for the study of hydrophobic hydration in intrinsically unstructured biomacromolecules.}, Doi = {10.1021/ja800502h}, Key = {Valiaev08} } @booklet{Singamaneni08, Author = {Singamaneni, S and LeMieux, MC and Lang, HP and Gerber, C and Lam, Y and Zauscher, S and Datskos, PG and Lavrik, NV and Jiang, H and Naik, RR and Bunning, TJ and Tsukruk, VV}, Title = {Bimaterial microcantilevers as a hybrid sensing platform}, Journal = {Advanced Materials (Deerfield Beach, Fla.)}, Volume = {20}, Number = {4}, Pages = {653-680}, Publisher = {WILEY}, Year = {2008}, Month = {February}, ISSN = {0935-9648}, url = {http://dx.doi.org/10.1002/adma.200701667}, Abstract = {Microcantilevers, one of the most common MEMS structures, have been introduced as a novel sensing paradigm nearly a decade ago. Ever since, the technology has emerged to find important applications in chemical, biological and physical sensing areas. Today the technology stands at the verge of providing the next generation of sophisticated sensors (such as artificial nose, artificial tongue) with extremely high sensitivity and miniature size. The article provides an overview of the modes of detection, theory behind the transduction mechanisms, materials employed as active layers, and some of the important applications. Emphasizing the material design aspects, the review underscores the most important findings, current trends, key challenges and future directions of the microcantilever based sensor technology. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.}, Doi = {10.1002/adma.200701667}, Key = {Singamaneni08} } @booklet{Chang08, Author = {Chang, DP and Abu-Lail, NI and Guilak, F and Jay, GD and Zauscher, S}, Title = {Conformational mechanics, adsorption, and normal force interactions of lubricin and hyaluronic acid on model surfaces.}, Journal = {Langmuir : the Acs Journal of Surfaces and Colloids}, Volume = {24}, Number = {4}, Pages = {1183-1193}, Year = {2008}, Month = {February}, ISSN = {0743-7463}, url = {http://www.ncbi.nlm.nih.gov/pubmed/18181652}, Abstract = {Glycoproteins, such as lubricin, and hyaluronic acid (HA) play a prominent role in the boundary lubrication mechanism in diarthrodial joints. Although many studies have tried to elucidate the lubrication mechanisms of articular cartilage, the molecular details of how lubricin and HA interact with cartilage surfaces and mediate their interaction still remain poorly understood. Here we used model substrates, functionalized with self-assembled monolayers terminating in hydroxyl or methyl groups, (1) to determine the effect of surface chemistry on lubricin and HA adsorption using surface plasmon resonance (SPR) and (2) to study normal force interactions between these surfaces as a function of lubricin and HA concentration using colloidal probe microscopy. We found that lubricin is amphiphilic and adsorbed strongly onto both methyl- and hydroxyl-terminated surfaces. On hydrophobic surfaces, lubricin likely adopts a compact, looplike conformation in which its hydrophobic domains at the N and C termini serve as surface anchors. On hydrophilic surfaces, lubricin likely adsorbs anywhere along its hydrophilic central domain and adopts, with increasing solution concentration, an extended tail-like conformation. Overall, lubricin develops strong repulsive interactions when compressing two surfaces into contact. Furthermore, upon surface separation, adhesion occurs between the surfaces as a result of molecular bridging and chain disentanglement. This behavior is in contrast to that of HA, which does not adsorb appreciably on either of the model surfaces and does not develop significant repulsive interactions. Adhesive forces, particularly between the hydrophobic surfaces, are large and not appreciably affected by HA. For a mixture of lubricin and HA, we observed slightly larger adsorptions and repulsions than those found for lubricin alone. Our experiments suggest that this interaction depends on unspecific physical rather than chemical interactions between lubricin and HA. We speculate that in mediating interactions at the cartilage surface, an important role of lubricin, possibly in conjunction with HA, is one of providing a protective coating on cartilage surfaces that maintains the contacting surfaces in a sterically repulsive state.}, Doi = {10.1021/la702366t}, Key = {Chang08} } @booklet{Coles08, Author = {Coles, JM and Blum, JJ and Jay, GD and Darling, EM and Guilak, F and Zauscher, S}, Title = {In situ friction measurement on murine cartilage by atomic force microscopy.}, Journal = {Journal of Biomechanics}, Volume = {41}, Number = {3}, Pages = {541-548}, Year = {2008}, Month = {January}, ISSN = {0021-9290}, url = {http://www.ncbi.nlm.nih.gov/pubmed/18054362}, Abstract = {Articular cartilage provides a low-friction, wear-resistant surface for the motion of diarthrodial joints. The objective of this study was to develop a method for in situ friction measurement of murine cartilage using a colloidal probe attached to the cantilever of an atomic force microscope. Sliding friction was measured between a chemically functionalized microsphere and the cartilage of the murine femoral head. Friction was measured at normal loads ranging incrementally from 20 to 100 nN with a sliding speed of 40 microm/s and sliding distance of 64 microm. Under these test conditions, hydrostatic pressurization and biphasic load support in the cartilage were minimized, providing frictional measurements that predominantly reflect boundary lubrication properties. Friction coefficients measured on murine tissue (0.25+/-0.11) were similar to those measured on porcine tissue (0.23+/-0.09) and were in general agreement with measurements of boundary friction on cartilage by other researchers. Using the colloidal probe as an indenter, the elastic mechanical properties and surface roughness were measured in the same configuration. Interfacial shear was found to be the principal mechanism of friction generation, with little to no friction resulting from plowing forces, collision forces, or energy losses due to normal deformation. This measurement technique can be applied to future studies of cartilage friction and mechanical properties on genetically altered mice or other small animals.}, Doi = {10.1016/j.jbiomech.2007.10.013}, Key = {Coles08} } @booklet{Darling08, Author = {Darling, EM and Topel, M and Zauscher, S and Vail, TP and Guilak, F}, Title = {Viscoelastic properties of human mesenchymally-derived stem cells and primary osteoblasts, chondrocytes, and adipocytes.}, Journal = {Journal of Biomechanics}, Volume = {41}, Number = {2}, Pages = {454-464}, Year = {2008}, Month = {January}, ISSN = {0021-9290}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17825308}, Abstract = {The mechanical properties of single cells play important roles in regulating cell-matrix interactions, potentially influencing the process of mechanotransduction. Recent studies also suggest that cellular mechanical properties may provide novel biological markers, or "biomarkers," of cell phenotype, reflecting specific changes that occur with disease, differentiation, or cellular transformation. Of particular interest in recent years has been the identification of such biomarkers that can be used to determine specific phenotypic characteristics of stem cells that separate them from primary, differentiated cells. The goal of this study was to determine the elastic and viscoelastic properties of three primary cell types of mesenchymal lineage (chondrocytes, osteoblasts, and adipocytes) and to test the hypothesis that primary differentiated cells exhibit distinct mechanical properties compared to adult stem cells (adipose-derived or bone marrow-derived mesenchymal stem cells). In an adherent, spread configuration, chondrocytes, osteoblasts, and adipocytes all exhibited significantly different mechanical properties, with osteoblasts being stiffer than chondrocytes and both being stiffer than adipocytes. Adipose-derived and mesenchymal stem cells exhibited similar properties to each other, but were mechanically distinct from primary cells, particularly when comparing a ratio of elastic to relaxed moduli. These findings will help more accurately model the cellular mechanical environment in mesenchymal tissues, which could assist in describing injury thresholds and disease progression or even determining the influence of mechanical loading for tissue engineering efforts. Furthermore, the identification of mechanical properties distinct to stem cells could result in more successful sorting procedures to enrich multipotent progenitor cell populations.}, Doi = {10.1016/j.jbiomech.2007.06.019}, Key = {Darling08} } @booklet{Ducker08, Author = {Ducker, R and Garcia, A and Zhang, JM and Chen, T and Zauscher, S}, Title = {Polymeric and biomacromolecular brush nanostructures: progress in synthesis, patterning and characterization}, Journal = {Soft Matter}, Volume = {4}, Number = {9}, Pages = {1774-1786}, Publisher = {Royal Society of Chemistry (RSC)}, Year = {2008}, ISSN = {1744-683X}, url = {http://dx.doi.org/10.1039/b804861b}, Abstract = {A significant scientific and engineering challenge of recent years has been the fabrication of patterned polymeric and biomacromolecular brush nanostructures on surfaces. These structures provide researchers with a rich platform on which to exploit and observe nanoscale phenomena. In this review we present an overview of the field and highlight, through selected examples, recent advances in the nanostructuring of polymer and biomacromolecular brushes. This includes a brief overview of polymer brush synthesis techniques and how these are integrated with nanolithographic and templating approaches. We discuss the characterization of polymeric nanostructures and its associated difficulties, and we provide some perspective of how we see the future direction of the field evolving.}, Doi = {10.1039/b804861b}, Key = {Ducker08} } @booklet{Zhang08, Author = {Zhang, JM and Nylander, T and Campbell, RA and Rennie, AR and Zauscher, S and Linse, P}, Title = {Novel evaluation method of neutron reflectivity data applied to stimulus-responsive polymer brushes}, Journal = {Soft Matter}, Volume = {4}, Number = {3}, Pages = {500-509}, Publisher = {Royal Society of Chemistry (RSC)}, Year = {2008}, ISSN = {1744-683X}, url = {http://dx.doi.org/10.1039/b714911e}, Abstract = {Neutron reflectivity (NR) measurements have been performed on stimulus-responsive polymer brushes containing N-isopropylacrylamide (NIPAAM) at different temperatures and contrasts using two different brush samples of roughly the same grafting density and layer thickness. The NR data were analyzed using a novel method employing polymer density profiles predicted from lattice mean-field theory augmented with a polymer model to describe polymer solubility that decreases with increasing temperature. The predicted density profiles at the different temperatures were self-consistent with the experimentally observed profiles; hence the experimental data lend credibility to the theory. We found that the brush thickness decreased from 220 to 160 nm and the polymer volume fraction increased from 55 to 75\% when increasing temperature from 293 to 328 K. The new evaluation approach involved significantly fewer independent fitting parameters than methods involving layers of uniform densities. Furthermore, the approach can straightforwardly be extended to analyze neutron reflectivity data of grafted, weakly charged polymers that display pH-sensitive behaviour and also to block copolymers and to surfaces with adsorbed polymers. We propose that such accurate model calculations provide a tool to interpret results from NR experiments more effectively and design neutron reflectivity experiments for optimal outcome.}, Doi = {10.1039/b714911e}, Key = {Zhang08} } @article{fds263367, Author = {Lam, Y and Valiaev, A and Lim, DW and Chilkoti, A and Alam, SM and Zauscher, S}, Title = {Single molecule nanomechanics of HIV-1 envelope glycoproteins and elastin-like polypeptides}, Journal = {Proceedings of the Sem Annual Conference and Exposition on Experimental and Applied Mechanics 2007}, Volume = {1}, Pages = {624-625}, Year = {2007}, Month = {November}, Key = {fds263367} } @article{fds319139, Author = {Garcia, A and Hucknall, A and Johannes, M and Clark, R and Chilkoti, A and Zauscher, S}, Title = {POLY 627-Fabrication of bioconjugated and hybrid polymeric nanostructures by field-induced scanning probe lithography}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {234}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2007}, Month = {August}, Key = {fds319139} } @booklet{Valiaev07, Author = {Valiaev, A and Lim, DW and Oas, TG and Chilkoti, A and Zauscher, S}, Title = {Force-induced prolyl cis-trans isomerization in elastin-like polypeptides.}, Journal = {Journal of the American Chemical Society}, Volume = {129}, Number = {20}, Pages = {6491-6497}, Year = {2007}, Month = {May}, ISSN = {0002-7863}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17469821}, Abstract = {Elastin-like polypeptides (ELPs) are stimulus-responsive polymers that contain repeats of five amino acids, Val-Pro-Gly-Xaa-Gly (VPGXG), where Xaa is a guest residue that can be any amino acid with the exception of proline. While studying the conformational mechanics of ELPs over a range of solvent conditions by single-molecule force spectroscopy, we noticed that some force-extension curves showed temperature-independent, extensional transitions that could not be fitted with a freely jointed chain or worm-like chain model. Here we show that the observed molecular elongation results from the force-induced peptidyl-prolyl cis-trans isomerization in prolines, which are repeated every fifth residue in the main chain of ELPs. Control experiments with poly(L-proline) demonstrate the similarity of the conformational transition between poly(L-proline) and ELPs. In contrast, the force-extension behavior of poly(L-lysine) showed no deviation in the relevant force range. Force-extension curves in hysteresis experiments showed an elongational difference between extension and relaxation pathways that suggests that the cis conformational state of the prolines could be exhausted on the time scale of the experiment. We present further computational evidence for this mechanism by Monte Carlo simulation of the force-extension behavior using an elastically coupled, two-state model. We believe ours is the first demonstration of force-induced prolyl cis-trans isomerization in proline-containing polypeptides. Our results suggest that single-molecule force spectroscopy could provide an alternate means to assay this important conformational transition in polypeptides.}, Doi = {10.1021/ja070147r}, Key = {Valiaev07} } @booklet{Darling07, Author = {Darling, EM and Zauscher, S and Block, JA and Guilak, F}, Title = {A thin-layer model for viscoelastic, stress-relaxation testing of cells using atomic force microscopy: do cell properties reflect metastatic potential?}, Journal = {Biophysical Journal}, Volume = {92}, Number = {5}, Pages = {1784-1791}, Year = {2007}, Month = {March}, ISSN = {0006-3495}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17158567}, Abstract = {Atomic force microscopy has rapidly become a valuable tool for quantifying the biophysical properties of single cells. The interpretation of atomic force microscopy-based indentation tests, however, is highly dependent on the use of an appropriate theoretical model of the testing configuration. In this study, a novel, thin-layer viscoelastic model for stress relaxation was developed to quantify the mechanical properties of chondrosarcoma cells in different configurations to examine the hypothesis that viscoelastic properties reflect the metastatic potential and invasiveness of the cell using three well-characterized human chondrosarcoma cell lines (JJ012, FS090, 105KC) that show increasing chondrocytic differentiation and decreasing malignancy, respectively. Single-cell stress relaxation tests were conducted at 2 h and 2 days after plating to determine cell mechanical properties in either spherical or spread morphologies and analyzed using the new theoretical model. At both time points, JJ012 cells had the lowest moduli of the cell lines examined, whereas FS090 typically had the highest. At 2 days, all cells showed an increase in stiffness and a decrease in apparent viscosity compared to the 2-h time point. Fluorescent labeling showed that the F-actin structure in spread cells was significantly different between FS090 cells and JJ012/105KC cells. Taken together with results of previous studies, these findings indicate that cell transformation and tumorigenicity are associated with a decrease in cell modulus and apparent viscosity, suggesting that cell mechanical properties may provide insight into the metastatic potential and invasiveness of a cell.}, Doi = {10.1529/biophysj.106.083097}, Key = {Darling07} } @booklet{Lee07, Author = {W. K. Lee and S. H. Chen and A. Chilkoti and S. Zauscher}, Title = {Fabrication of gold nanowires by electric-field-induced scanning probe lithography and in situ chemical development}, Journal = {Small}, Volume = {3}, Number = {2}, Pages = {249 -- 254}, Year = {2007}, Month = {February}, ISSN = {1613-6810}, Key = {Lee07} } @article{070810435270, Author = {Lee, W-K and Chen, S and Chilkoti, A and Zauscher, S}, Title = {Fabrication of gold nanowires by electric-field-induced scanning probe lithography and in situ chemical development.}, Journal = {Small (Weinheim an Der Bergstrasse, Germany)}, Volume = {3}, Number = {2}, Pages = {249-254}, Year = {2007}, Month = {February}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17199247}, Keywords = {Biosensors;Electric field effects;Gold;Lithography;Surface plasmon resonance;}, Abstract = {A new approach to fabricate surface-confined gold nanostructures by electric-field-induced scanning probe lithography (SPL) for electronic and plasmonic applications, which enables precise control over the feature dimension and position at the nanometer-length scale, is discussed. The approach promises massively parallel implementation through an anodization stamping process and has potential for the fabrication of nanoelectronic devices, biosensors, and surface plasmonic sensors. Clusters of gold atoms are concomitantly deposited during the patterning of SiO<sub>2</sub> nanostructures by the SPL. Other metallic nanowires can be fabricated by using gold seeds and an appropriately matched developing route, which suggests that different functional nanowires can also be fabricated. This approach has potential for the fabrication of nanoelectronic devices, biosensors, and surface plasmonic sensors.}, Doi = {10.1002/smll.200600396}, Key = {070810435270} } @booklet{Chang07, Author = {D. P. Chang and J. E. Dolbow and S. Zauscher}, Title = {Switchable friction of stimulus-responsive hydrogels}, Journal = {Langmuir}, Volume = {23}, Number = {1}, Pages = {250 -- 257}, Year = {2007}, Month = {January}, ISSN = {0743-7463}, Abstract = {Poly(N-isopropylacrylamide) (pNIPAAm) gels are stimulus-responsive hydrogels that exhibit large reversible changes in their volume and surface physicochemical properties near the lower critical solution temperature (LCST) in response to external stimuli, such as a change in temperature or solvent composition. Here we report how different phase states, induced isothermally by changes in the solvent composition, affect the tribological properties of pNIPAAm hydrogels. Our measurements indicate that gels in a collapsed conformation (above the LCST) exhibit significantly more friction than swollen gels (below the LCST) at low shear rates. These differences arise from changes in the surface roughness, adhesive interactions, and chain entanglements of the gel surfaces associated with the phase transition. Importantly, we show that the changes in friction, triggered by an external stimulus, are reversible. These reversible and possibly tunable changes in friction may have a significant impact on the design of coatings for biosensors and for actuation devices based on stimulus-responsive hydrogels.}, Key = {Chang07} } @booklet{Lee07a, Author = {W. K. Lee and M. Patra and P. Linse and S. Zauscher}, Title = {Scaling behavior of nanopatterned polymer brushes}, Journal = {Small}, Volume = {3}, Number = {1}, Pages = {63 -- 66}, Year = {2007}, Month = {January}, ISSN = {1613-6810}, Key = {Lee07a} } @booklet{Valiaev07a, Author = {A. Valiaev and N. I. Abu-lail and D. W. Lim and A. Chilkoti and S. Zauscher}, Title = {Microcantilever sensing and actuation with end-grafted stimulus-responsive elastin-like polypeptides}, Journal = {Langmuir}, Volume = {23}, Number = {1}, Pages = {339 -- 344}, Year = {2007}, Month = {January}, ISSN = {0743-7463}, Abstract = {Stimulus-responsive elastin-like polypeptides (ELPs) grafted onto surfaces are of significant technical interest because they can be exploited for force generation, in sensing applications, or as molecular switches with tunable properties. Changes in the conformational state of grafted ELPs, induced by a phase transition or changes in osmotic pressure, lead to significant changes in the surface stress in the ELP graft layer and translate into detectable changes in microcantilever deflection. In this study, we investigate the conformational mechanics of ELPs in response to changes in solution pH and ionic strength using atomic force microscopy (AFM) microcantilever deflection and quartz crystal microbalance (QCM) measurements. We show that the use of genetically encoded, surface-grafted ELPs is exciting for cantilever actuation and sensing because commonly available microfabricated cantilever springs offer a simple and nonintrusive way to detect changes in solvent type, temperature, and pH, promising great potential for sensing applications in microfluidic devices.}, Key = {Valiaev07a} } @booklet{Lam07, Author = {Lam, Y and Alam, MS and Zauscher, S}, Title = {Molecular-recognition force spectroscopy of induced-fit antibody binding to HIV-1 env gp120 and a nano-mechanical approach to understanding neutralizing antibody unbinding behavior}, Journal = {Biophysical Journal}, Pages = {514A-514A}, Publisher = {BIOPHYSICAL SOCIETY}, Year = {2007}, Month = {January}, ISSN = {0006-3495}, url = {http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000243972403254&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=47d3190e77e5a3a53558812f597b0b92}, Key = {Lam07} } @article{070410390784, Author = {Chang, DP and Dolbow, JE and Zauscher, S}, Title = {Switchable friction of stimulus-responsive hydrogels.}, Journal = {Langmuir : the Acs Journal of Surfaces and Colloids}, Volume = {23}, Number = {1}, Pages = {250-257}, Year = {2007}, Month = {January}, ISSN = {0743-7463}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17190511}, Keywords = {Adhesives;Biosensors;Coatings;Phase transitions;Physical chemistry;Solvents;Surface roughness;}, Abstract = {Poly(N-isopropylacrylamide) (pNIPAAm) gels are stimulus-responsive hydrogels that exhibit large reversible changes in their volume and surface physicochemical properties near the lower critical solution temperature (LCST) in response to external stimuli, such as a change in temperature or solvent composition. Here we report how different phase states, induced isothermally by changes in the solvent composition, affect the tribological properties of pNIPAAm hydrogels. Our measurements indicate that gels in a collapsed conformation (above the LCST) exhibit significantly more friction than swollen gels (below the LCST) at low shear rates. These differences arise from changes in the surface roughness, adhesive interactions, and chain entanglements of the gel surfaces associated with the phase transition. Importantly, we show that the changes in friction, triggered by an external stimulus, are reversible. These reversible and possibly tunable changes in friction may have a significant impact on the design of coatings for biosensors and for actuation devices based on stimulus-responsive hydrogels.}, Doi = {10.1021/la0617006}, Key = {070410390784} } @article{070410390786, Author = {Valiaev, A and Abu-Lail, NI and Lim, DW and Chilkoti, A and Zauscher, S}, Title = {Microcantilever sensing and actuation with end-grafted stimulus-responsive elastin-like polypeptides.}, Journal = {Langmuir : the Acs Journal of Surfaces and Colloids}, Volume = {23}, Number = {1}, Pages = {339-344}, Year = {2007}, Month = {January}, ISSN = {0743-7463}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17190524}, Keywords = {Atomic force microscopy;Graft copolymers;Phase transitions;Quartz;pH effects;}, Abstract = {Stimulus-responsive elastin-like polypeptides (ELPs) grafted onto surfaces are of significant technical interest because they can be exploited for force generation, in sensing applications, or as molecular switches with tunable properties. Changes in the conformational state of grafted ELPs, induced by a phase transition or changes in osmotic pressure, lead to significant changes in the surface stress in the ELP graft layer and translate into detectable changes in microcantilever deflection. In this study, we investigate the conformational mechanics of ELPs in response to changes in solution pH and ionic strength using atomic force microscopy (AFM) microcantilever deflection and quartz crystal microbalance (QCM) measurements. We show that the use of genetically encoded, surface-grafted ELPs is exciting for cantilever actuation and sensing because commonly available microfabricated cantilever springs offer a simple and nonintrusive way to detect changes in solvent type, temperature, and pH, promising great potential for sensing applications in microfluidic devices.}, Doi = {10.1021/la0616698}, Key = {070410390786} } @article{070410384139, Author = {Lee, W-K and Patra, M and Linse, P and Zauscher, S}, Title = {Scaling behavior of nanopatterned polymer brushes.}, Journal = {Small (Weinheim an Der Bergstrasse, Germany)}, Volume = {3}, Number = {1}, Pages = {63-66}, Year = {2007}, Month = {January}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17294470}, Keywords = {Atomic force microscopy;Computer simulation;Grain boundaries;Molecular dynamics;Molecular weight;Organic polymers;Pattern recognition;}, Abstract = {The scaling behavior of poly(N-isopropyacrylamide) (pNIPAAM) polymer brushes was investigated. The brush height of different footprint sizes, polymer molecular weights and surface-grafting densities was analyzed using scaling relations obtained from coarse grained model. Molecular dynamics simulation method was used for development of scaling relation of brush height in terms of features widths at various chain lengths and grafting densities. The theoretical prediction was validated by comparing the predicted scaling behavior of the brush height with that obtained from height measurements on nano- and micropatterned pNIPAAM polymer brushed. It was observed that polymer heights measured in dry states vary as function of patterned feature width for various reaction time and polymer height increases at small feature width. Result shows that scaling prediction provide a useful tool for the design and fabrication of polymeric and bio-macromolecular nanostructures on surfaces.}, Doi = {10.1002/smll.200600414}, Key = {070410384139} } @article{065010304059, Author = {Lam, Y and Abu-Lail, NI and Alam, MS and Zauscher, S}, Title = {Using microcantilever deflection to detect HIV-1 envelope glycoprotein gp120.}, Journal = {Nanomedicine}, Volume = {2}, Number = {4}, Pages = {222-229}, Year = {2006}, Month = {December}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17292147}, Keywords = {Monoclonal antibodies;Viruses;Glycols;Solutions;Molecular biology;Binding energy;Biosensors;}, Abstract = {Microcantilevers have been used over the last decade to detect biomolecules from solution. Specific binding events on one surface of the microcantilever create a differential stress, resulting in measurable deflection. Here we use this principle to detect human immunodeficiency virus type 1 (HIV-1) envelope glycoprotein (Env) gp120 from solution. We observed deflections approximately twice that of the baseline (in PBS) upon specific binding of gp120 to cantilevers decorated on one side with monoclonal antibodies (mAbs) A32 or T8. Subsequent incubation with mAb 17b (known to bind an A32-induced epitope on gp120) further increased deflection of A32- but not T8-presenting cantilevers. This work shows the capability of microcantilever deflection sensors to detect an induced-fit interaction at test concentrations of 8 microg/mL gp120 and 0.17 mg/mL 17b. Further development of this technique could lead to a portable, low-cost device for the effective detection of HIV-1.}, Doi = {10.1016/j.nano.2006.10.002}, Key = {065010304059} } @article{065010301595, Author = {Loveless, DM and Abu-Lail, NI and Kaholek, M and Zauscher, S and Craig, SL}, Title = {Reversibly cross-linked surface-grafted polymer brushes.}, Journal = {Angewandte Chemie International Edition}, Volume = {45}, Number = {46}, Pages = {7812-7814}, Year = {2006}, Month = {November}, ISSN = {1433-7851}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17066386}, Keywords = {Crosslinking;Thin films;Reaction kinetics;Supramolecular chemistry;Surface chemistry;}, Abstract = {Detailed brush work: Structurally and thermodynamically similar cross-linkers have opposite effects on the lateral resistance of grafted thin films of poly(4-vinylpyridine) brushes. The chemically reversible changes in mechanics are influenced by the dissimilar kinetics of the cross-linking interaction. (Figure Presented). © 2006 Wiley-VCH Verlag GmbH and Co. KGaA.}, Doi = {10.1002/anie.200602508}, Key = {065010301595} } @article{fds319140, Author = {Chang, DP and Dolbow, JE and Zauscher, S}, Title = {POLY 101-Switchable friction of stimulus-responsive hydrogels}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {232}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2006}, Month = {September}, Key = {fds319140} } @article{063610102645, Author = {Kaholek, M and Lee, WK and Feng, J and Lamattina, B and Dyer, DJ and Zauscher, S}, Title = {Weak polyelectrolyte brush arrays fabricated by combining electron-beam lithography with surface-initiated photopolymerization}, Journal = {Chemistry of Materials}, Volume = {18}, Number = {16}, Pages = {3660-3664}, Publisher = {American Chemical Society (ACS)}, Year = {2006}, Month = {August}, ISSN = {0897-4756}, url = {http://dx.doi.org/10.1021/cm060276r}, Keywords = {Polyelectrolytes;Electron beam lithography;Photopolymerization;pH effects;Salts;Ultraviolet radiation;Free radical polymerization;Initiators (chemical);Ionic strength;}, Abstract = {We present a simple "top-down/bottom-up" strategy to fabricate nano- and micropatterned polymer brush arrays composed of pH- and salt-sensitive, weak polyelectrolyte copolymers [poly(N-isopropy-lacrylamide-co- methacrylic acid, 3:1, poly (NIPAAM-co-MAA)]. In our approach, a silicon surface is first patterned with gold, using "lift-off' electron-beam lithography ("top-down"), and the resulting pattern is then amplified by surface-initiated photopolymerization by conventional, UV-light-induced free radical polymerization ("bottom-up") from an immobilized 2,2′-azobisisobutyronitrile (AIBN) type initiator. The use of pH- and ionic-strength-sensitive comonomers in the copolymer brush enables large, externally triggered conformational changes of the micro- and nanopatterned polymer brushes. We observed that the height of nanopatterned ionized polymer brushes increases with increasing feature size of the pattern. The design and fabrication of surfaces with conformationally switchable, patterned polymeric structures is important for sensing and actuation applications on the micro- and nanoscales. © 2006 American Chemical Society.}, Doi = {10.1021/cm060276r}, Key = {063610102645} } @article{fds263359, Author = {Abu-Lail, N and Jay, GD and Coles, J and Guilak, F and Zauscher, S}, Title = {Friction reducing properties of lubricin (PRG4): A nanoscale study of chondroprotection}, Journal = {European Cells and Materials}, Volume = {12}, Number = {SUPPL.1}, Pages = {48}, Year = {2006}, Month = {August}, ISSN = {1473-2262}, Key = {fds263359} } @article{fds263352, Author = {Kenan, DJ and Walsh, EB and Meyers, SR and O'Toole, GA and Carruthers, EG and Lee, WK and Zauscher, S and Prata, CAH and Grinstaff, MW}, Title = {Peptide-PEG amphiphiles as cytophobic coatings for mammalian and bacterial cells.}, Journal = {Chemistry & Biology}, Volume = {13}, Number = {7}, Pages = {695-700}, Year = {2006}, Month = {July}, ISSN = {1074-5521}, url = {http://www.ncbi.nlm.nih.gov/pubmed/16873017}, Abstract = {Amphiphilic macromolecules containing a polystyrene-adherent peptide domain and a cell-repellent poly(ethylene glycol) domain were designed, synthesized, and evaluated as a cytophobic surface coating. Such cytophobic, or cell-repellent, coatings are of interest for varied medical and biotechnological applications. The composition of the polystyrene binding peptide domain was identified using an M13 phage display library. ELISA and atomic force spectroscopy were used to evaluate the binding affinity of the amphiphile peptide domain to polystyrene. When coated onto polystyrene, the amphiphile reduced cell adhesion of two distinct mammalian cell lines and pathogenic Staphylococcus aureus strains.}, Doi = {10.1016/j.chembiol.2006.06.013}, Key = {fds263352} } @article{06259950330, Author = {Lee, W-K and Caster, KC and Kim, J and Zauscher, S}, Title = {Nanopatterned polymer brushes by combining AFM anodization lithography with ring-opening metathesis polymerization in the liquid and vapor phase.}, Journal = {Small (Weinheim an Der Bergstrasse, Germany)}, Volume = {2}, Number = {7}, Pages = {848-853}, Year = {2006}, Month = {July}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17193132}, Keywords = {Nanostructured materials;Polymers;Ring opening polymerization;Atomic force microscopy;Anodic oxidation;Catalysts;}, Abstract = {The fabrication of patterned polymeric nanostructures enables the development of miniaturized sensing and diagnostic applications. The atomic force microscopy (AFM) anodization, a form of field-induces scanning probe lithography (FISPL) offers a powerful means to nanopattern semiconductor surfaces with silicon oxide features that can be used for subsequent modification with Ru-based metathesis catalysts. A prototypical method is developed to fabricate nanopatterned polymers structures by combining AFM anodization lithography on silicon substrates with surface-initiated ROMP. EFM phase imaging was used to characterize the electronic state of the resulting nanopatterned polymer structures. Nanopatterns of two chemically different polymers were fabricated on a single substrate by a step-and-repeat patterning and polymerization approach. This process provides a universal platform for surface-initiated polymerization and means to fabricate complex polymeric structures.}, Doi = {10.1002/smll.200500470}, Key = {06259950330} } @article{fds263358, Author = {Darling, EM and Zauscher, S and Guilak, F}, Title = {Viscoelastic properties of zonal articular chondrocytes measured by atomic force microscopy.}, Journal = {Osteoarthritis and Cartilage}, Volume = {14}, Number = {6}, Pages = {571-579}, Year = {2006}, Month = {June}, ISSN = {1063-4584}, url = {http://www.ncbi.nlm.nih.gov/pubmed/16478668}, Abstract = {<h4>Objective</h4>Articular chondrocytes respond to chemical and mechanical signals depending on their zone of origin with respect to distance from the tissue surface. However, little is known of the zonal variations in cellular mechanical properties in cartilage. The goal of this study was to determine the zonal variations in the elastic and viscoelastic properties of porcine chondrocytes using atomic force microscopy (AFM), and to validate this method against micropipette aspiration.<h4>Methods</h4>A theoretical solution for stress relaxation of a viscoelastic, incompressible, isotropic surface indented with a hard, spherical indenter (5 microm diameter) was derived and fit to experimental stress-relaxation data for AFM indentation of chondrocytes isolated from the superficial or middle/deep zones of cartilage.<h4>Results</h4>The instantaneous moduli of chondrocytes were 0.55+/-0.23 kPa for superficial cells (S) and 0.29+/-0.14 kPa for middle/deep cells (M/D) (P<0.0001), and the relaxed moduli were 0.31+/-0.15 kPa (S) and 0.17+/-0.09 kPa (M/D) (P<0.0001). The apparent viscosities were 1.15+/-0.66 kPas (S) and 0.61+/-0.69 kPa-s (M/D) (P<0.0001). Results from the micropipette aspiration test showed similar cell moduli but higher apparent viscosities, indicating that mechanical properties measured by these two techniques are similar.<h4>Conclusion</h4>Our findings suggest that chondrocyte biomechanical properties differ significantly with the zone of origin, consistent with previous studies showing zonal differences in chondrocyte biosynthetic activity and gene expression. Given the versatility and dynamic testing capabilities of AFM, the ability to conduct stress-relaxation measurements using this technique may provide further insight into the viscoelastic properties of isolated cells.}, Doi = {10.1016/j.joca.2005.12.003}, Key = {fds263358} } @article{06249932007, Author = {Jung, J and Kim, KW and Na, K and Kuholek, M and Zauscher, S and Hyun, J}, Title = {Fabrication of micropatterned gold nanoparticle arrays as a template for surface-initiated polymerization of stimuli-responsive polymers}, Journal = {Macromolecular Rapid Communications}, Volume = {27}, Number = {10}, Pages = {776-780}, Publisher = {WILEY}, Year = {2006}, Month = {May}, ISSN = {1022-1336}, url = {http://dx.doi.org/10.1002/marc.200600069}, Keywords = {Gold;Polystyrenes;Polymerization;Silicon;Adsorption;}, Abstract = {This paper demonstrates a new, reliable, and simple method for fabricating micropatterned nanoparticle arrays that can serve as templates for the surface-initiated polymerization of polymer brushes. As a proof of concept, we micropatterned gold nanoparticles (Au-NPs, ≈10 nm) onto glass, silicon, polystyrene, and gold surfaces by a simple three-step process: (1) microcontact printing of soluble polymer, (2) incubation with a solution of Au-NPs, and (3) lift-off of the template in a mixture of ethanol and deionized water. 40 μm wide features were successfully fabricated without any significant defects or nonspecific adsorption on the background. To demonstrate the utility of these Au-NP templates, we subsequently polymerized N-isopropylacry-lamide by surface-initiated polymerization, using a surface-bound initiator. © 2006 WILEY-VCH Verlag Gimbh & Co. KGaA.}, Doi = {10.1002/marc.200600069}, Key = {06249932007} } @article{fds263362, Author = {Abu-Lail, NI and Ohashi, T and Clark, RL and Erickson, HP and Zauscher, S}, Title = {Understanding the elasticity of fibronectin fibrils: unfolding strengths of FN-III and GFP domains measured by single molecule force spectroscopy.}, Journal = {Matrix Biology : Journal of the International Society for Matrix Biology}, Volume = {25}, Number = {3}, Pages = {175-184}, Year = {2006}, Month = {April}, ISSN = {0945-053X}, url = {http://www.ncbi.nlm.nih.gov/pubmed/16343877}, Abstract = {While it is well established that fibronectin (FN) matrix fibrils are elastic, the mechanism of fibril elasticity during extension is still debated. To investigate the molecular origin of FN fibril elasticity, we used single molecule force spectroscopy (SMFS) to determine the unfolding behavior of a recombinant FN-III protein construct that contained eight FN-III domains ((1-8)FN-III) and two green fluorescent protein (GFP) domains. FN-III domains were distinguished from GFP domains by their shorter unfolding lengths. The unfolding strengths of both domains were determined for a wide range of pulling rates (50 to 1,745 nm/s). We found that the mechanical stabilities of FN-III and GFP domains were very similar to each other over the entire range of pulling speeds. FN fibrils containing GFP remain brightly fluorescent, even when stretched, meaning that GFP domains remain largely folded. Since GFP and FN-III have equal unfolding strengths, this suggests that FN-III domains are not extensively unraveled in stretched FN fibrils. Our results thus favor an alternative model, which invokes a conformational change from a compact to an extended conformation, as the basis for FN fibril elasticity.}, Doi = {10.1016/j.matbio.2005.10.007}, Key = {fds263362} } @article{06099727804, Author = {Abu-Lail, NI and Kaholek, M and LaMattina, B and Clark, RL and Zauscher, S}, Title = {Micro-cantilevers with end-grafted stimulus-responsive polymer brushes for actuation and sensing}, Journal = {Sensors and Actuators. B, Chemical}, Volume = {114}, Number = {1}, Pages = {371-378}, Publisher = {Elsevier BV}, Year = {2006}, Month = {March}, ISSN = {0925-4005}, url = {http://dx.doi.org/10.1016/j.snb.2005.06.003}, Keywords = {Sensors;Brushes;Copolymers;Macromolecules;Polymerization;Drug products;Atomic force microscopy;Organic solvents;Fluidic devices;Ionic strength;Phase transitions;Osmosis;Conformations;}, Abstract = {Stimulus-responsive macromolecules have attracted significant interest due to their potential applications in molecular motors, drug delivery, sensors, and actuation devices. Poly(N-isopropylacrylamide) (pNIPAAM) alone or as a copolymer is a stimulus-responsive polymer that undergoes an inverse phase transition triggered by changes in the solvent quality, such as temperature, ionic strength, pH, or co-solvent concentration. Associated with this phase transition is a significant conformational change. We show that micro-cantilevers, decorated on one side with a pNIPAAM brush or poly(N-isopropylacrylamide-co-N-vinylimidazole) (pNIPAAM-VI) (7:3) brush, can be used to detect and transduce this phase transition behavior. Changes in the conformational state of the brush, induced by the phase transition or changes in osmotic pressure, cause significant changes in the surface stress in the brush that leads to detectable changes in cantilever deflection. We show that the use of pNIPAAM and its copolymers is exciting for cantilever actuation and sensing because commonly available micro-fabricated cantilever springs offer a simple and non-intrusive way to detect changes in solvent type, temperature, and pH, promising great potential for sensing applications in micro-fluidic devices. © 2005 Elsevier B.V. All rights reserved.}, Doi = {10.1016/j.snb.2005.06.003}, Key = {06099727804} } @article{fds319141, Author = {Lee, W-K and Chen, S and Chilkoti, A and Zauscher, S}, Title = {Fabrication of bioconjugated polymeric nanostructures and metal nanowires by electric field-induced scanning probe lithography}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {231}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2006}, Month = {March}, Key = {fds319141} } @article{fds319142, Author = {Abu-Lail, N and Kaholek, M and Valiaev, A and Lim, D-W and Chilkoti, A and LaMattina, B and Clark, R and Zauscher, S}, Title = {Micro-cantilevers decorated with tethered stimulus-responsive polymer brushes and polypeptides for actuation and sensing}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {231}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2006}, Month = {March}, Key = {fds319142} } @article{06109738972, Author = {Uner, B and Ramasubramanian, MK and Zauscher, S and Kadla, JF}, Title = {Adhesion interactions between poly(vinyl alcohol) and iron-oxide surfaces: The effect of acetylation}, Journal = {Journal of Applied Polymer Science}, Volume = {99}, Number = {6}, Pages = {3528-3534}, Publisher = {WILEY}, Year = {2006}, Month = {February}, ISSN = {0021-8995}, url = {http://dx.doi.org/10.1002/app.22980}, Keywords = {Polyvinyl alcohols;Iron oxides;Hydroxylation;Hydrogen bonds;Fourier transform infrared spectroscopy;Atomic force microscopy;}, Abstract = {Atomic force microscopy with chemically functionalized colloidal probes was used to study "acid-base" interactions between poly(vinyl alcohol) (PVA) and a metal surface. By using well-defined model surfaces, we have studied the adhesion forces between a hydroxylated surface and cantilever tips with varying hydroxyl content. Decreasing the amount of available hydroxyl groups dramatically reduced the observed adhesion force. The calculated bond energy for each cantilever tip was found to be in the range of typical hydrogen bond energies, i.e., 10-40 kJ/mol, suggesting that the acid-base interactions are pre dominately hydrogen bonding. Similarly, the force versus distance curves using PVA functionalized colloidal probes showed a strong dependence on the chemical functionality of the tip and the degree of acetylation of the intervening PVA. It was observed that, with an increase in the acetyl content of the PVA, the adhesion force decreased. © 2006 Wiley Periodicals, Inc.}, Doi = {10.1002/app.22980}, Key = {06109738972} } @booklet{Loveless06, Author = {D. M. Loveless and N. I. Abu-lail and M. Kaholek and S. Zauscher and S. L. Craig}, Title = {Reversibly cross-linked surface-grafted polymer brushes}, Journal = {Angewandte Chemie-international Edition}, Volume = {45}, Number = {46}, Pages = {7812 -- 7814}, Year = {2006}, ISSN = {1433-7851}, Key = {Loveless06} } @article{05509543649, Author = {Bastidas, JC and Venditti, R and Pawlak, J and Gilbert, R and Zauscher, S and Kadla, JF}, Title = {Chemical force microscopy of cellulosic fibers}, Journal = {Carbohydrate Polymers}, Volume = {62}, Number = {4}, Pages = {369-378}, Publisher = {Elsevier BV}, Year = {2005}, Month = {December}, ISSN = {0144-8617}, url = {http://dx.doi.org/10.1016/j.carbpol.2005.08.058}, Keywords = {Cellulose;Bleached pulp;Kraft pulp;pH effects;Surface roughness;X ray photoelectron spectroscopy;Fourier transform infrared spectroscopy;Atomic force microscopy;}, Abstract = {Atomic force microscopy with chemically modified cantilever tips (chemical force microscopy) was used to study the pull-off forces (adhesion forces) on cellulose model surfaces and bleached softwood kraft pulp fibers in aqueous media. It was found that for the -COOH terminated tips, the adhesion forces are dependent on pH, whereas for the -CH3 and -OH terminated tips adhesion is not strongly affected by pH. Comparison between the cellulose model surfaces and cellulosic fibers under our experimental conditions reveal that surface roughness does not affect adhesion strongly. X-ray photoelectron spectroscopy (XPS) and Fourier Transformed Infrared (FTIR) spectroscopy reveal that both substrate surfaces have homogeneous chemical composition. The results show that chemical force microscopy can be used for the chemical characterization of cellulose surfaces at a nano-level. © 2005 Elsevier Ltd. All rights reserved.}, Doi = {10.1016/j.carbpol.2005.08.058}, Key = {05509543649} } @article{05439431733, Author = {Chow, DC and Lee, W-K and Zauscher, S and Chilkoti, A}, Title = {Enzymatic fabrication of DNA nanostructures: extension of a self-assembled oligonucleotide monolayer on gold arrays.}, Journal = {Journal of the American Chemical Society}, Volume = {127}, Number = {41}, Pages = {14122-14123}, Year = {2005}, Month = {October}, ISSN = {0002-7863}, url = {http://www.ncbi.nlm.nih.gov/pubmed/16218572}, Abstract = {Nucleic acid nanostructures are useful as templates for bionanofabrication of composite molecular nanostructures in materials science, molecular electronics, and biosensing. Here, we demonstrate that terminal deoxynucleotidyl transferase, which repetitively adds mononucleotides to the 3' end of a short DNA initiator, can be used to rapidly fabricate DNA nanostructures up to 121 nm high with lateral dimensions from 0.1 to 4 mum in 2 h. These programmable scaffolds can potentially be employed to build more complex nanostructures consisting of natural or unnatural nucleotides with selective docking sites along the single-stranded DNA.}, Doi = {10.1021/ja052491z}, Key = {05439431733} } @article{fds319144, Author = {Valiaev, A and Abu-Lail, NI and Lim, DW and Chilkoti, A and Zauscher, S}, Title = {Stimulus-responsive elastin-like polypetides as coatings for microcantilevers: Applications for sensing and actuation}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {230}, Pages = {U4317-U4318}, Publisher = {AMER CHEMICAL SOC}, Year = {2005}, Month = {August}, Key = {fds319144} } @article{fds319145, Author = {Chow, DC and Chilkoti, A and Lee, WK and Zauscher, S}, Title = {Rapid fabrication of DNA nanostructures by enzymatic reactions}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {230}, Pages = {U1069-U1069}, Publisher = {AMER CHEMICAL SOC}, Year = {2005}, Month = {August}, Key = {fds319145} } @article{fds263364, Author = {Valiaev, A and Dong, WL and Chilkoti, A and Schmidler, S and Zauscher, S}, Title = {Polypeptide-solvent interactions measured by single molecule force spectroscopy}, Journal = {Materials Research Society Symposium Proceedings}, Volume = {898}, Pages = {92-97}, Year = {2005}, Month = {January}, ISSN = {0272-9172}, url = {http://dx.doi.org/10.1557/proc-0898-l06-06-nn04-06}, Abstract = {Stimulus-responsive biomolecules have attracted a large research interest because of their potential application in various areas such as drug delivery, actuators and sensing devices at the nanoscale. Using single-molecule force spectroscopy (SMFS) we studied elastin-like polypeptides (ELPs). These stimulus-responsive polypeptides undergo an inverse temperature transition, accompanied by a large conformational change, when the solvent quality is changed by increasing the temperature or by addition of salt. Understanding the relationship between peptide sequence and mechanisms of force generation can provide a route to engineer ELPs with desirable mechano-chemical properties. Here we studied the effect of solvent quality and type of guest residue on the mechanical properties of ELPs on the single-molecule level. We used a novel statistical approach to estimate polymer elasticity parameters from model fits to the data. With this approach we were able to resolve small changes in the Kuhn segment length distributions associated with different molecular architectures. We then show that these mechanical differences likely arise from differences in the hydrophobic hydration of sidegoups, in line with recent predictions from molecular dynamics simulations. © 2006 Materials Research Society.}, Doi = {10.1557/proc-0898-l06-06-nn04-06}, Key = {fds263364} } @article{05519594637, Author = {Chow, DC and Johannes, MS and Lee, WK and Clark, RL and Zauscher, S and Chilkoti, A}, Title = {Nanofabrication with biomolecules}, Journal = {Materials Today}, Volume = {8}, Number = {12 SUPPL. 1}, Pages = {30-39}, Publisher = {Elsevier BV}, Year = {2005}, Month = {January}, ISSN = {1369-7021}, url = {http://dx.doi.org/10.1016/S1369-7021(05)71287-6}, Keywords = {Proteins;Problem solving;}, Abstract = {The advances made in biotechnology and nanotechnology for building complex bionanostructures on surfaces with nanometer precision are discussed. The use of biomolecules for nanoscale has become an effective solution for difficult positioning problems in the fabrication of nanostructures. To fabricate efficiently with biomolecules and make use of their unique properties, a radical shift away from the high energy, high vacuum processing paradigm of conventional micro and nanofabrication is needed. An exciting opportunities for bionanofabrication have also emerged in the field of synthetic biology and recombinant protein engineering.}, Doi = {10.1016/S1369-7021(05)71287-6}, Key = {05519594637} } @article{fds319149, Author = {Valiaev, A and Lim, DW and Oas, T and Clark, RL and Chilkoti, A and Zauscher, S}, Title = {Force-induced proline cis-trans isomerization in elastin-like polypeptides}, Journal = {Biophysical Journal}, Volume = {88}, Number = {1}, Pages = {168A-168A}, Publisher = {BIOPHYSICAL SOCIETY}, Year = {2005}, Month = {January}, Key = {fds319149} } @article{05329283237, Author = {Kim, J and Liu, Y and Ahn, SJ and Zauscher, S and Karty, JM and Yamanaka, Y and Craig, SL}, Title = {Self-assembly and properties of main-chain reversible polymer brushes}, Journal = {Advanced Materials}, Volume = {17}, Number = {14}, Pages = {1749-1753}, Publisher = {WILEY}, Year = {2005}, url = {http://dx.doi.org/10.1002/adma.200401355}, Keywords = {DNA;Self assembly;Monomers;Synthesis (chemical);Electrostatics;Free energy;Thermodynamics;Polymerization;Atomic force microscopy;Scanning electron microscopy;Adhesives;}, Abstract = {The compressive and adhesive mechanical properties of self-assembled polymer brushes were investigated using DNA-based modules. The effects of surface anchor density, association strength, and monomer flexibility on the properties were also investigated. Reversible polymer brush properties were examined using atomic force microscopy. It was observed that the effective polymer brush height and resulting adhesive interactions were strongly dependent on surface anchor density and the thermodynamics, concentration, and conformational flexibility of the monomer.}, Doi = {10.1002/adma.200401355}, Key = {05329283237} } @article{04268228648, Author = {Hyun, J and Lee, W-K and Nath, N and Chilkoti, A and Zauscher, S}, Title = {Capture and release of proteins on the nanoscale by stimuli-responsive elastin-like polypeptide "switches".}, Journal = {Journal of the American Chemical Society}, Volume = {126}, Number = {23}, Pages = {7330-7335}, Year = {2004}, Month = {June}, ISSN = {0002-7863}, url = {http://www.ncbi.nlm.nih.gov/pubmed/15186170}, Keywords = {Polypeptides;Nanostructured materials;Nanotechnology;Lithography;Ionic strength;Hydrophobicity;Hydrophilicity;Atomic force microscopy;}, Abstract = {This article describes the fabrication and characterization of stimulus-responsive elastin-like polypeptide (ELP) nanostructures grafted onto omega-substituted thiolates that were patterned onto gold surfaces by dip-pen nanolithography (DPN). In response to external stimuli such as changes in temperature or ionic strength, ELPs undergo a switchable and reversible, hydrophilic-hydrophobic phase transition at a lower critical solution temperature (LCST). We exploited this phase transition behavior to reversibly immobilize a thioredoxin-ELP (Trx-ELP) fusion protein onto the ELP nanopattern above the LCST. Subsequent binding of an anti-thioredoxin monoclonal antibody (anti-Trx) to the surface-captured thioredoxin showed the presentation of the immobilized protein in a sterically accessible orientation in the nanoarray. We also showed that the resulting Trx-ELP/anti-Trx complex formed above the LCST could be reversibly dissociated below the LCST. These results demonstrate the intriguing potential of ELP nanostructures as generic, reversible, biomolecular switches for on-chip capture and release of a small number (order 100-200) of protein molecules in integrated, nanoscale bioanalytical devices. We also investigated the molecular mechanism underlying this switch by measuring the height changes that accompany the binding and desorption steps and by adhesion force spectroscopy using atomic force microscopy.}, Doi = {10.1021/ja049721e}, Key = {04268228648} } @article{8515974, Author = {Kaholek, M and Lee, WK and LaMattina, B and Caster, KC and Zauscher, S}, Title = {Fabrication of Stimulus-Responsive Nanopatterned Polymer Brushes by Scanning-Probe Lithography}, Journal = {Nano Letters}, Volume = {4}, Number = {2}, Pages = {373-376}, Publisher = {American Chemical Society (ACS)}, Year = {2004}, Month = {February}, url = {http://dx.doi.org/10.1021/nl035054w}, Keywords = {nanolithography;nanopatterning;nanostructured materials;polymerisation;polymers;}, Abstract = {Stimulus-responsive, surface confined poly(N-isopropylacrylamide) (pNIPAAM) brush nanopatterns were prepared on gold-coated silicon substrates in a "grafting-from" approach that combines "nanoshaving", a scanning probe lithography method, with surface-initiated polymerization using atom transfer radical polymerization (ATRP). The reversible, stimulus-responsive conformational height change of these nanopatterned polymer brushes was demonstrated by inverse transition cycling in water, and water-methanol mixtures (1:1, v:v). Our findings are consistent with the behavior of laterally confined and covalently attached polymer chains, where chain mobility is restricted largely to the out-of-plane direction. Our nanofabrication approach is generic and can likely be extended to a wide range of vinyl monomers.}, Doi = {10.1021/nl035054w}, Key = {8515974} } @article{04408386601, Author = {Kaholek, M and Lee, W-K and Ahn, S-J and Ma, H and Caster, KC and LaMattina, B and Zauscher, S}, Title = {Stimulus-responsive poly(N-isopropylacrylamide) brushes and nanopatterns prepared by surface-initiated polymerization}, Journal = {Chemistry of Materials}, Volume = {16}, Number = {19}, Pages = {3688-3696}, Publisher = {American Chemical Society (ACS)}, Year = {2004}, url = {http://dx.doi.org/10.1021/cm049562y}, Keywords = {Monolayers;Lithography;Water;Nanotechnology;Actuators;}, Abstract = {In this paper we report the surface-initiated polymerization of poly(N-isopropylacrylamide) (pNIPAAM), a stimulus-responsive polymer, from monolayers of ω-mercaptoundecyl bromoisobutyrate on gold-coated surfaces. pNIPAAM was polymerized in aqueous solution at a low methanol concentration at room temperature to maintain the growing pNIPAAM chains in a hydrophilic and an extended conformational state. Under these conditions thick polymer brush layers (up to 500 nm in the swollen state) are produced after 1 h of polymerization. We present a new and simple strategy to fabricate stimulus-responsive, surface-confined pNIPAAM brush nanopatterns prepared in a "grafting- from" approach that combines "nanoshaving", a scanning probe lithography method, with surface-initiated polymerization. The reversible, stimulus-responsive conformational height change of bulk and nanopatterned polymer brushes was demonstrated by repeated cycling in water and water/methanol mixtures (1:1, v/v). Our findings are consistent with the behavior of laterally confined and covalently attached polymer chains, where chain mobility is restricted largely to the out-of-plane direction. The present work is significant because the triggered control of interfacial properties on the nanometer scale holds significant promise for actuation in bio-nanotechnology applications where polymeric actuators may manipulate the transport, separation, and detection of biomolecules.}, Doi = {10.1021/cm049562y}, Key = {04408386601} } @article{05038794680, Author = {Ahn, SJ and Kaholek, M and Lee, W-K and LaMattina, B and LaBean, TH and Zauscher, S}, Title = {Surface-initiated polymerization on nanopatterns fabricated by electron-beam lithography}, Journal = {Advanced Materials}, Volume = {16}, Number = {23-24}, Pages = {2141-2145}, Publisher = {WILEY}, Year = {2004}, ISSN = {0935-9648}, url = {http://dx.doi.org/10.1002/adma.200401055}, Keywords = {Nanostructured materials;Gold;Methanol;Monomers;Self assembly;Ellipsometry;Fourier transform infrared spectroscopy;Photolithography;Electron beam lithography;Scanning electron microscopy;}, Abstract = {A new 'top-down/bottom-up' approach for fabricating patterned polymer-brush arrays on the micrometer and nanometer length scales was reported. It was suggested that patterns with well-defined feature dimensions, shapes, and inter-feature spacings can be easily created over large areas by lift-off electron beam lithography (EBL). The utility of combining lift-off EBL for fabrication of Au patterns and surface-initiated polymerization to form micro- and nanostructures of stimulus-responsive polymer brushes on silicon surfaces was demonstrated. The fabrication approach was found to allow a high level of lateral control in patterning surfaces with complex polymer-brush structures over large surface area.}, Doi = {10.1002/adma.200401055}, Key = {05038794680} } @article{03487761138, Author = {Valiaev, A and Clark, RL and Chilkoti, A and Zauscher, S}, Title = {Conformational Mechanics of Stimulus-Responsive Polypeptides}, Journal = {Smart Structures and Materials 2005: Active Materials: Behavior and Mechanics}, Volume = {5053}, Pages = {31-40}, Publisher = {SPIE}, Address = {San Diego, CA, United States}, Year = {2003}, Month = {November}, url = {http://dx.doi.org/10.1117/12.484700}, Keywords = {Phase transitions;Conformations;Interfaces (materials);Elasticity;Hydrophobicity;Molecular structure;Molecular dynamics;Nuclear magnetic resonance spectroscopy;Computer simulation;}, Abstract = {Stimulus-responsive polymers and polypeptides (SRPs) experience a significant entropic response when exposed to an environmental stimulus, such as a change in temperature. This phase transition directly affects polymer conformation and can potentially be harnessed for force generation in actuation devices on nano- and micro-scales. While interfacial applications of SRPs have been prototypically demonstrated, a systematic investigation of the phase transition behavior at the solid-liquid interface and on the single-molecule level is lacking. In this paper we present results from force-spectroscopy measurements probing the force-extension and conformational behavior of one SRP, elastin-like polypeptides (ELF), below and above their transition temperature. The results indicate that there is no significant difference in the force extension behavior at intermediate and large extensions, but the behavior is dramatically different at small extensions. Results also demonstrated that above the phase transition temperature large, unspecific adhesion forces often gave way to constant force steps upon extension, indicating a collapsed, potentially entangled, hydrophobic state of the ELP. The extension behavior below the phase transition temperature, however, closely followed that of a random polymer coil, without any significant unspecific adhesion forces. The excellent fit of a simple extended freely jointed chain model to the data at intermediate and large extensions suggests that the ELP is in a random conformational state without significant secondary structure. Forces associated with a phase transition therefore arise likely from entropic conformational changes associated with a hydrophobic collapse.}, Doi = {10.1117/12.484700}, Key = {03487761138} } @article{7840110, Author = {Powers, JD and Sanders, N and Zauscher, S}, Title = {Force interactions between calcium carbonate and chemically functionalized colloidal probes: The effect of calcium ion and polyelectrolyte addition}, Journal = {International Paper and Coating Chemistry Symposium, Proceedings}, Pages = {23-29}, Address = {Montreal, Que., Canada}, Year = {2003}, Month = {November}, Keywords = {adhesion;adsorption;calcium compounds;coating techniques;fibres;monolayers;paper making;polymer electrolytes;}, Abstract = {An understanding of fundamental interactions of micron-sized pigments in papermaking and paper coating processes is important in controlling the interactions between the pigment and cellulose fibers, flocculants and binder. This research established, for the first time, the effects of calcium ion concentration and anionic polyelectrolyte (sodium salt of polyacrylic acid) on interactions between a freshly-cleaved calcite (CaCO3) surface and a chemically-functionalized colloidal probe by direct force measurements using an atomic force microscope. In the absence of polyelectrolyte, adhesive interactions increased with increasing polarity of the probe. The adhesive interaction between calcite and a carboxylate-terminated probe increased strongly with increasing Ca2+ ion concentration and leveled off at about 0.1 M after most available Ca2+ adsorption sites had been occupied. The extent of steric interactions in the presence of polyacrylate depended on polymer concentration and suggested a flat polymer conformation up to monolayer coverage, and an extended polymer conformation above full coverage. Increasing the Ca2+ ion concentration caused a significant compression of the polyacrylate layer, Adhesion between CaCO3 and carboxylate-terminated probes increased with increasing polyelectrolyte concentration. In addition, for any given polymer concentration, adhesion increased also with increasing Ca2+ ion concentration, suggesting a Ca2+ ion mediated polymer bridging mechanism. For a given ion concentration, adhesion force leveled off or peaked at approximately monolayer surface coverage of polymer. These results will be critically discussed in context of published data on retention of dispersed and undispersed calcium carbonate pigments and in context of published data on the dispersion of calcium carbonate with adsorbed polyacrylates.}, Key = {7840110} } @article{03317571981, Author = {Ahn, SJ and Lee, WK and Zauscher, S}, Title = {Fabrication of stimulus-responsive polymeric nanostructures by proximal probes}, Journal = {Materials Research Society Symposium Proceedings}, Volume = {735}, Pages = {111-116}, Address = {Boston, MA, United States}, Year = {2003}, Month = {July}, Keywords = {Polymers;Free radical polymerization;Nanotechnology;Surfaces;Self assembly;Gold;}, Abstract = {The triggered control of interfacial properties on the nanometer scale holds significant promise for actuation in bio-nanotechnology applications where polymeric actuators may manipulate the transport, separation, and detection of biomolecules. To fabricate patterned, stimulus-responsive polymer brushes we have developed several methods that combine surface initiated polymerization (SIP) with dip-pen nanolithography (DPN). Surface-confined, stimulus-responsive polymer brush nanopatterns were fabricated by amplification of DPN patterned, self-assembled monolayers of 16-mercaptohexadecanoic acid on gold surfaces by SIP of N-isopropylacrylamide (NIPAAm). While free radical polymerization yielded only short polymer brushes (DP<50), atom transfer free radical polymerization (ATRP) produced thick, uniform polymer brushes. For free radical polymerization the thickness of the polymer brush layer is a function of the lateral feature size and the initiator density and is maximal at pattern boundaries.}, Key = {03317571981} } @article{02507262693, Author = {Garoff, N and Zauscher, S}, Title = {The influence of fatty acids and humidity on friction and adhesion of hydrophilic polymer surfaces}, Journal = {Langmuir : the Acs Journal of Surfaces and Colloids}, Volume = {18}, Number = {18}, Pages = {6921-6927}, Publisher = {American Chemical Society (ACS)}, Year = {2002}, Month = {September}, url = {http://dx.doi.org/10.1021/la025787g}, Keywords = {Cellulose;Friction;Adhesion;Fatty acids;Atmospheric humidity;Hydrophilicity;Monolayers;Sorption;}, Abstract = {Monolayers of saturated fatty acids of different chain lengths and of 9-cis-octadecenoic acid were physisorbed onto regenerated cellulose surfaces to study their effect on friction and adhesion. Lateral and normal force measurements on these surfaces were carried out at different humidities using an atomic force microscope with chemically functionalized silicon nitride cantilevers. Friction and adhesion of clean cellulose increased significantly with humidity. Adhesion forces at high humidity were predicted well by theory that accounted for the effect of the Laplace pressure due to capillary condensation. The magnitude of friction and adhesion and their dependence on humidity decreased with increasing hydrophobicity of the contacting surfaces. Friction of cellulose surfaces impregnated with different saturated fatty acids decreased sharply from a high level to a low level at a carbon chain length above 14 carbon atoms. Contact angle data indicated that only saturated fatty acids with 16 carbon atoms or more in the carbon chain formed vertically oriented monolayers on cellulose. Our results suggest that friction of hydrophitic polymer surfaces under ambient conditions is greatly influenced by capillary condensation. Furthermore, lubrication by fatty acids is achieved through the formation of vertically oriented, hydrophobic monolayers that can withstand the normal and shear stresses during sliding and increase the hydrophobicity of the polymer surface, thereby decreasing the degree of capillary condensation.}, Doi = {10.1021/la025787g}, Key = {02507262693} } @article{fds319161, Author = {Zauscher, S and Garoff, N}, Title = {The influence of fatty acids and humidity on the friction of hydrophilic polymer surfaces.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {223}, Pages = {U454-U455}, Publisher = {AMER CHEMICAL SOC}, Year = {2002}, Month = {April}, Key = {fds319161} } @article{7655306, Author = {Hyun, J and Ahn, SJ and Lee, WK and Chilkoti, A and Zauscher, S}, Title = {Molecular recognition-mediated fabrication of protein nanostructures by dip-pen lithography}, Journal = {Nano Lett. (Usa)}, Volume = {2}, Number = {11}, Pages = {1203-1207}, Publisher = {American Chemical Society (ACS)}, Year = {2002}, url = {http://dx.doi.org/10.1021/n10257364}, Keywords = {biological techniques;monolayers;nanolithography;nanotechnology;proteins;}, Abstract = {We describe the molecular recognition-mediated, stepwise fabrication of patterned protein nanostructures with feature sizes on the order of 200 nm. First, a self-assembled monolayer (SAM) of 16-mercaplohexadecanoic acid (MHA) is patterned onto gold by dip-pen nanolithography (DPN), and the unpatterned regions are passivated with a protein-resistant oligoethylene glycol-terminated alkanethiol SAM. Next, an amine-terminated biotin derivative is covalently conjugated with the chemically activated MHA SAM nanopattern. The surface is then incubated with streptavidin to form streptavidin nanostructures, mediated by molecular recognition between biotin and streptavidin. Finally, protein nanopatterns are fabricated by molecular recognition-mediated immobilization of biotinylated protein from solution. Our fabrication methodology is generically applicable because of the ubiquity of biotin-tagged molecules}, Doi = {10.1021/n10257364}, Key = {7655306} } @article{fds319160, Author = {Uner, B and Kadla, JF and Ramasubramanian, MK and Zauscher, S and Hubbe, M and van Zanten, JH}, Title = {Determination of adhesion forces between adhesives and metal/paper surfaces using atomic force microscopy.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {223}, Pages = {U130-U130}, Year = {2002}, Key = {fds319160} } @article{fds319162, Author = {Zauscher, S}, Title = {Friction of hydrogel surfaces.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {221}, Pages = {U346-U346}, Publisher = {AMER CHEMICAL SOC}, Year = {2001}, Month = {April}, Key = {fds319162} } @article{01015463804, Author = {Zauscher, S and Klingenberg, DJ}, Title = {Friction between cellulose surfaces measured with colloidal probe microscopy}, Journal = {Colloids and Surfaces A: Physicochemical and Engineering Aspects}, Volume = {178}, Number = {1-3}, Pages = {213-229}, Publisher = {Elsevier BV}, Year = {2001}, Month = {March}, ISSN = {0927-7757}, url = {http://dx.doi.org/10.1016/S0927-7757(00)00704-4}, Keywords = {Cellulose;Colloids;Microscopic examination;Friction;Particle size analysis;}, Abstract = {Colloidal probe microscopy was employed to study sliding friction between model cellulose surfaces in aqueous solutions. Regardless of scan size, friction exhibits irregular stick-slip behavior related to surface roughness. At small scan sizes (∼10 nm), the coefficient of friction decreases with increasing load. Above a critical scan size of about 100 nm - corresponding to the average size of asperities on one of the model surfaces - friction forces are independent of scan size, but depend on the load. Hydrodynamic forces contribute little to friction. Small amounts of high molecular weight, polyelectrolytes decrease significantly sliding friction between cellulose surfaces. © 2001 Elsevier Science B.V.}, Doi = {10.1016/S0927-7757(00)00704-4}, Key = {01015463804} } @article{03457709386, Author = {Scott, CT and Simonsen, J and Klingenberg, D and Zauscher, S}, Title = {Pulp extrusions incorporating sludge from the pulp and paper industry}, Journal = {Tappi Proceedings Environmental Conference and Exhibit}, Volume = {1}, Pages = {203-211}, Address = {Denver, CO, United States}, Year = {2000}, Month = {December}, Keywords = {Pulp;Extrusion;Rheology;Drying;}, Abstract = {Pulp extrusion at ultra-high consistency (≅30% solids) has been shown to be a viable process for converting recovered paper, wastepaper, and papermill residues into solid sheets and profiles. We have previously shown that extrusion of ultra-high consistency pulps and "model" sludges requires the addition of a water-soluble polymer (WSP) to alter the rheological properties of the pulp such that an homogenous "pulp paste" can be formed and extruded. This paper discusses our attempts to evaluate the viability of extruding a variety of papermill sludges. Several sludges were acquired from various mills and classified by ash content, contaminant level, and biological activity. Various blends of sludge, newsprint (ONP), and WSP were prepared and extruded into continuous sheets. The sheets were then cut into strips for consolidation by press drying. These strips were further cut into coupons for tensile testing. The results showed that a variety of sludges could be successfully extruded with adequate tensile strength. However, the presence of contaminants (e.g., chips, staples, plastics, silica) and interfering chemistries posed some difficulties in processing these residues.}, Key = {03457709386} } @article{fds263349, Author = {Zauscher, S and Klingenberg, DJ}, Title = {Normal Forces between Cellulose Surfaces Measured with Colloidal Probe Microscopy.}, Journal = {Journal of Colloid and Interface Science}, Volume = {229}, Number = {2}, Pages = {497-510}, Year = {2000}, Month = {September}, url = {http://www.ncbi.nlm.nih.gov/pubmed/10985829}, Abstract = {Colloidal probe microscopy was employed to study interactions between cellulose surfaces in aqueous solutions. Hydrodynamic forces must be accounted for in data analysis. Long-range interactions betweeen cellulose surfaces are governed by double-layer forces and, once surfaces contact, by osmotic repulsive forces and viscoelasticity. Increasing the ionic strength decreases surface potentials and increases adhesive forces. Polyelectrolytes cause strong steric repulsion at high surface coverage, where interactions are sensitive to probe velocity. Polymer bridging occurs at low coverage. The conformation of adsorbed polyelectrolytes depends on the polymer concentration. Copyright 2000 Academic Press.}, Doi = {10.1006/jcis.2000.7008}, Key = {fds263349} } @article{00075245068, Author = {Zauscher, S and Scott, CT and Willett, JL and Klingenberg, DJ}, Title = {Pulp extrusion for recycling wastepapers and paper mill sludges}, Journal = {Tappi Journal}, Volume = {83}, Number = {6}, Pages = {62}, Year = {2000}, Month = {January}, Keywords = {Extrusion;Recycling;Waste paper;Sewage sludge;Paper and pulp mills;Suspensions (fluids);Stiffness;Moisture;Composition effects;Resins;Crosslinking;}, Abstract = {Extrusion processing offers a new method by which pulps from recycled papers and sludges can be processed at ultra-high consistencies to form useful products. However, the method must surmount two problems. First, the fiber suspension must be made to flow homogeneously to achieve good formation. Second, processing equipment must disperse fiber flocs and transport the highly concentrated suspension. Through the extrusion method, mills can manufacture structural fiber composite materials with consistent, predictable properties. Stiffness losses caused by moisture can be controlled by the addition of crosslinkable resins.}, Key = {00075245068} } @article{01226518874, Author = {Zauscher, S and Klingenberg, DJ}, Title = {Surface and friction forces between cellulose surfaces measured with colloidal probe microscopy}, Journal = {Nordic Pulp and Paper Research Journal}, Volume = {15}, Number = {5}, Pages = {459-468}, Publisher = {WALTER DE GRUYTER GMBH}, Address = {Stockholm}, Year = {2000}, Month = {January}, url = {http://dx.doi.org/10.3183/npprj-2000-15-05-p459-468}, Keywords = {Friction;Surfaces;Atomic force microscopy;Polyelectrolytes;Rheology;Viscoelasticity;Ionic strength;Velocity;Surface roughness;Hydrodynamics;}, Abstract = {To better understand interactions that govern the micro-rheological behavior of pulp fiber suspensions, we used colloidal probe microscopy to study normal forces and sliding friction between model cellulose surfaces in polyelectrolyte solutions. Hydrodynamic interactions must be accounted for in data analysis. Long-range interactions are governed by double layer forces, and once surfaces contact, by osmotic repulsive forces and viscoelasticity. Increasing the ionic strength decreases surface potentials and increases adhesive forces. Polyelectrolytes cause strong steric repulsion at high surface coverage, where interactions are sensitive to probe velocity. Polymer bridging occurs at low coverage. Regardless of scan size, friction exhibits irregular stick-slip behavior related to surface roughness. Above a critical scan size of about 100 nm - corresponding to the average size of asperities on one of the model surfaces - lateral forces are independent of scan size but depend on the load. Hydrodynamic forces contribute little to friction. Even small amounts of high molecular weight polyelectrolytes decrease sliding friction between cellulose surfaces significantly.}, Doi = {10.3183/npprj-2000-15-05-p459-468}, Key = {01226518874} } @article{fds319165, Author = {Zauscher, S and Klingenberg, DJ}, Title = {Force imaging cellulose with colloidal probe microscopy.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {216}, Pages = {U347-U347}, Year = {1998}, Key = {fds319165} } @article{98054211822, Author = {Scott, CT and Zauscher, S}, Title = {Pulp extrusion at ultra-high consistencies}, Journal = {Tappi Proceedings Environmental Conference &Amp; Exhibition}, Volume = {2}, Pages = {739-743}, Address = {Minneapolis, MN, USA}, Year = {1997}, Month = {December}, Keywords = {Paper and pulp mills;Natural fibers;Cellulose;Polymers;Rheometers;Waste utilization;Viscosity of liquids;Composition effects;Tensile strength;Elasticity;}, Abstract = {A new process for producing continuous lignocellulosic fiber products is currently under development at the USDA Forest Service, Forest Products Laboratory. The goal of this exploratory research is to utilize conventional pulping techniques to process recovered papers with high filler contents, retain fiber integrity, and produce an engineered extruded product. This process involves the extrusion of wet crumb pulp (primarily derived from recovered paper) at consistencies of 20% to 40% with small amounts of water-soluble polymers added as hydromodifiers. The water-soluble polymers appear to have two important rheological functions in the extrusion process: (a) they bind water to the fiber and (b) they add lubricity to the pulp. A torque rheometer was used to measure the apparent viscosity of various pulp suspensions with water-soluble polymers. The added polymers reduce viscosity dramatically and enhance fiber dispersion. Polymer addition levels ranging from 1% to 3% by weight dry fiber were evaluated. Selected pulp/polymer compositions were then processed by a twin screw extruder. A slit die was designed to produce a thin sheet that could be press-dried and cut into coupons for measurement of tensile properties. Fiber orientation appeared to be random, and tensile properties were nearly equivalent in the flow and cross-flow directions. For most extruded compositions, fail stress and modulus of elasticity ranged from 10 to 20 MPa and 3 to 5 GPa, respectively. These results indicate that pulp extrusion at ultra-high consistencies is possible and poses a viable alternative to the disposal of highly filled recovered papers and papermill sludges.}, Key = {98054211822} } @article{fds263347, Author = {Zauscher, S and Humphrey, PE}, Title = {Orienting lignocellulosic fibers and particles by means of a magnetic field}, Journal = {Wood and Fiber Science}, Volume = {29}, Number = {1}, Pages = {35-46}, Year = {1997}, Month = {December}, Abstract = {Fiber and particle alignment in composite materials may be used to tailor material and object properties to specific performance requirements. The present research demonstrates that alignment of ferromagnetically modified slender wood particles in magnetic fields is feasible. Magnetic torque, which causes rotation, increases linearly with the amount of magnetic material on particle surfaces. Below magnetic saturation, magnetic torque increases with increasing strength of the applied field; closer to magnetic saturation, torque becomes less dependent on the applied field strength. Magnetic torque maxima occur at field-to-particle axis angles above 45°. Polarity switches of the applied magnetic field increase particle rotation rates and may counter permanent magnetization, which otherwise tends to impede full particle alignment.}, Key = {fds263347} } @article{fds304877, Author = {Zauscher, S and Caulfield, DF and Nissan, AH}, Title = {Influence of water on the elastic modulus of paper part 2:Verification of predictions of the H-bond theory}, Journal = {Tappi Journal}, Volume = {80}, Number = {1}, Pages = {214-223}, Year = {1997}, Month = {January}, Abstract = {In Part I, an extension of the theory of hydrogen-bond-dominated solids was proposed. In Part 2, the predictions of the extended theory are tested statistically using recently reported measurements of elastic moduli for 24 papers over a wide range of moisture contents. Moduli were reported both quasi-statically and ultrasonically. Statistial analysis shows that the effect of moisture in lowering the elastic modulus of paper is greater when the modulus is measured quasi-statically. The rate of decrease in the logarithm of modulus with moisture content when measured sonically is about 75% of the rate of decrease measured quasi-statically. The ratio of the two measured moduli for an isotropically equivalent paper is statistically indistinguishable from a ratio obtained from measurements of the effectiveness of water in reducing these elastic modull.This supports one of the new predictions of the extended H-bond theory proposed in Part 1.}, Key = {fds304877} } @article{97023517057, Author = {Zauscher, S and Caulfield, DF and Nissan, AH}, Title = {Influence of water on the elastic modulus of paper}, Journal = {Tappi Journal}, Volume = {80}, Number = {1}, Pages = {214-223}, Year = {1997}, Keywords = {Elastic moduli;Water;Statistical methods;Moisture;Mechanical variables measurement;Hydrogen bonds;}, Abstract = {In Part I, an extension of the theory of hydrogen-bond-dominated solids was proposed. In Part 2, the predictions of the extended theory are tested statistically using recently reported measurements of elastic moduli for 24 papers over a wide range of moisture contents. Moduli were reported both quasi-statically and ultrasonically. Statistical analysis shows that the effect of moisture in lowering the elastic modulus of paper is greater when the modulus is measured quasi-statically. The rate of decrease in the logarithm of modulus with moisture content when measured sonically is about 75% of the rate of decrease measured quasi-statically. The ratio of the two measured moduli for an isotropically equivalent paper is statistically indistinguishable from a ratio obtained from measurements of the effectiveness of water in reducing these elastic moduli. This supports one of the new predictions of the extended H-bond theory proposed in Part I.}, Key = {97023517057} } @article{fds304876, Author = {Zauscher, S and Caulfield, DF and Nissan, AH}, Title = {The influence of water on the elastic modulus of paper. Part I: Extension of the H-bond theory}, Journal = {Tappi Journal}, Volume = {79}, Number = {12}, Pages = {178-182}, Year = {1996}, Month = {December}, Abstract = {In Part I, the theory of hydrogen-bond-dominated solids is extended to explain phenomena concerning the elastic behavior of paper, based on the postulate that the number dencity of effective hydrogen bonds, normalized to on average bond stiffness, is higher for ultrasonic modulus measurements than for quasi-static measurements. This leads to the predictions: (I) The measured elastic modulus of a sheet of paper will depend upon whether the modulus is measured quasi-statically using load-elongation methods of ultrasonically using the time of flight method, and that the ultrasonic modulus, Es, will exceed the quasi-static modulus, Er, (Es > Er). (2) The rate of change of modulus with increasing moisture content, w, follows the rule: In[E] = A - (C.I.) w, where the negative slope of the curve In[E] vs. w is constant over a wide this of moisture contents. But again this slope will also differ whether measured quasi-statically or ultrasonically, with (C.I.)s > (C.I.)r. (3) Moreover, the extended theory predicts that the ratio of moduli at zero moisture content is related to the ratio of slopes by the expression: {[Es]r} / [Es]}3 =[(C.I.) + I] / [(C.I.) + I].}, Key = {fds304876} } @article{98124512315, Author = {Zauscher, S and Klingenber, DJ}, Title = {Rheology and extrusion processability of pulp suspensions}, Journal = {Proceedings of the Conference on the Use of Recycled Wood and Paper in Building Applications}, Pages = {189}, Address = {Madison, WI, USA}, Year = {1996}, Month = {December}, Keywords = {Fibers;Rheology;Polymers;Suspensions (fluids);Strength of materials;Composition effects;Microstructure;Flocculation;Shear stress;}, Abstract = {The mechanism by which water-soluble polymers change suspension rheology is examined. The effect of polymer addition on rheology was evaluated using a torque rheometer where large shear rates and strains prevail. The polymer addition level for sufficient formation was found to be higher than the equilibrium adsorption level. Linear, high molecular-weight polymers were found to yield the largest torque drops. Suspensions of flexible fibers were also observed to behave as elastic solids at low shear rates. Polymer addition has very minimal effect on network strength at practical consistencies.}, Key = {98124512315} } @article{98124512289, Author = {Zauscher, S and Scott, CT}, Title = {Pulp extrusion: A new processing method for recycling recovered wastepaper and papermill sludge and its application for building materials}, Journal = {Proceedings of the Conference on the Use of Recycled Wood and Paper in Building Applications}, Pages = {68-78}, Address = {Madison, WI, USA}, Year = {1996}, Month = {December}, Keywords = {Waste utilization;Sewage sludge;Extrusion;Recycling;Building materials;Composite materials;Strength of materials;Stiffness;Paper and pulp mills;}, Abstract = {Fibers recovered from recycled paper products have desirable mechanical properties and can be used for the manufacture of composite materials. Contrary to their use in papermaking, recycled wood pulp fibers used for composites may require only minimal cleaning and de-inking, thus greatly reducing manufacturing costs. In addition, waste fiber sources which are not used presently could be exploited. In the research presented it is shown that extrusion processing of highly concentrated, aqueous pulp fiber suspensions offers a way to manufacture composite materials which make use of the inherent strength and bonding potential of wood fibers. With this process, fiber composites with mechanical properties comparable to those found in medium density fiberboard and hardboard can be produced continuously. Stiffness loss due to moisture can be controlled by addition of crosslinkable resins, thus offering the possibility to manufacture structural materials with consistent and predictable properties. Tolerance of the extrusion process toward the addition of inorganic materials make it a suitable process for recycling contaminated fibers and papermill sludges.}, Key = {98124512289} } @article{97013501034, Author = {Zauscher, S and Caulfield, DF and Nissan, AH}, Title = {Influence of water on the elastic modulus of paper, Part I}, Journal = {Tappi Journal}, Volume = {79}, Number = {12}, Pages = {178}, Year = {1996}, Abstract = {In Part I, the theory of hydrogen-bond-dominated solids is extended to explain phenomena concerning the elastic behavior of paper, based on the postulate that the number dencity of effective hydrogen bonds, normalized to on average bond stiffness, is higher for ultrasonic modulus measurements than for quasi-static measurements. This leads to the predictions: (I) The measured elastic modulus of a sheet of paper will depend upon whether the modulus is measured quasi-statically using load-elongation methods of ultrasonically using the time of flight method, and that the ultrasonic modulus, Es, will exceed the quasi-static modulus, Er, (Es > Er). (2) The rate of change of modulus with increasing moisture content, w, follows the rule: In[E] = A - (C.I.) w, where the negative slope of the curve In[E] vs. w is constant over a wide this of moisture contents. But again this slope will also differ whether measured quasi-statically or ultrasonically, with (C.I.)s > (C.I.)r. (3) Moreover, the extended theory predicts that the ratio of moduli at zero moisture content is related to the ratio of slopes by the expression: {[Es]r} / [Es]}3 =[(C.I.) + I] / [(C.I.) + I].}, Key = {97013501034} } %% Preprints @article{fds358988, Author = {French, D and Navarro, L and Zauscher, S}, Title = {Bio-inspired peptide-polymer hybrid mucin analogues: Applications in osteoarthritis and kidney stone disease}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {257}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2019}, Month = {March}, Key = {fds358988} } @article{fds358989, Author = {Navarro, L and French, D and Zauscher, S}, Title = {Synthesis of modular brush polymer-protein hybrids using diazotransfer and copper click chemistry}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {257}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2019}, Month = {March}, Key = {fds358989} } @article{fds358987, Author = {Tang, L and Deshpande, S and Yang, Y and Gu, R and Chilkoti, A and Zauscher, S}, Title = {Enzymatic synthesis of aptamer-targeted polynucleotide drugs for cancer therapy}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {257}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2019}, Month = {March}, Key = {fds358987} } @article{fds358990, Author = {Feng, Y and Huang, J and Ngaboyamahina, E and Marusak, K and Glass, J and Mikkelsen, M and Zauscher, S}, Title = {Organic ligands enhance the recombination lifetime and photoelectrochemical performance of biosynthesized CdS nanoparticle thin films}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {256}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2018}, Month = {August}, Key = {fds358990} } @article{fds358991, Author = {Shields, W and White, J and Osta, E and Patel, J and Rajkumar, S and Zauscher, S}, Title = {Encapsulation, protection and programmed release of retinol from silicone particles for topical applications}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {256}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2018}, Month = {August}, Key = {fds358991} } @article{fds358992, Author = {Brittain, W and Rastogi, S and Zauscher, S}, Title = {The enduring utility of azobenzene as a photocontrol unit in hybrid macromolecular systems}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {256}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2018}, Month = {August}, Key = {fds358992} } @article{fds358993, Author = {Tu, Q and Lange, B and Kim, H and Yingling, Y and Blum, V and Zauscher, S}, Title = {Subsurface structure fingerprint of 2D materials and heterostructures by their nanomechanical response}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {253}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2017}, Month = {April}, Key = {fds358993} } @article{fds358995, Author = {Hardy, G and Shapter, J and Alam, M and Zauscher, S}, Title = {Synthesis and characterization of supported lipid bilayer membranes from complex lipid mixtures}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {253}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2017}, Month = {April}, Key = {fds358995} } @article{fds358994, Author = {Feng, Y and Ngaboyamahina, E and Marusak, K and Glass, J and Zauscher, S}, Title = {Hybrid (organic/inorganic) electrode design from bacterially precipitated CdS for PEC/storage applications}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {253}, Year = {2017}, Key = {fds358994} } @article{fds327224, Author = {Tkatchenko, TV and Luo, X and Tkatchenko, AV and Vaz, C and Tanavde, VM and Maurer-Stroh, S and Zauscher, S and Gonzalez, P and Young, TL}, Title = {Large-scale microRNA expression profiling identifies retinal miRNA-mRNA signaling pathways underlying form-deprivation myopia in mice}, Journal = {Investigative Ophthalmology & Visual Science}, Volume = {57}, Number = {12}, Pages = {3 pages}, Publisher = {ASSOC RESEARCH VISION OPHTHALMOLOGY INC}, Year = {2016}, Month = {September}, Key = {fds327224} } @article{fds358996, Author = {Rastogi, S and Gu, R and Lamas, J and Li, X and Zauscher, S and Brittain, W}, Title = {Synthesis of photoresponsive single stranded DNA aggregates via click chemistry}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {249}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2015}, Month = {March}, Key = {fds358996} } @article{fds319127, Author = {Gu, R and Zauscher, S and Lamas, J and Brittain, W}, Title = {Synthesis of photo-responsive single-stranded DNA micelles via copper-free click chemistry}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {248}, Pages = {2 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2014}, Month = {August}, Key = {fds319127} } @article{fds319128, Author = {Hardy, G and Zauscher, S}, Title = {Hiv-1 Neutralizing Antibodies and Vaccine Antigen Selectively Interact with Phase-Separated Model Membranes}, Journal = {Biophysical Journal}, Volume = {106}, Number = {2}, Pages = {300a-300a}, Publisher = {Elsevier BV}, Year = {2014}, Month = {January}, url = {http://dx.doi.org/10.1016/j.bpj.2013.11.1746}, Doi = {10.1016/j.bpj.2013.11.1746}, Key = {fds319128} } @article{fds319129, Author = {Tang, L and Tjong, V and Gu, R and Chilkoti, A and Zauscher, S}, Title = {Enzyme catalyzed polymerization of DNA amphiphiles that self-assemble into star-like micelles}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {246}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2013}, Month = {September}, Key = {fds319129} } @article{fds319130, Author = {Ferris, R and Yellen, B and Zauscher, S}, Title = {Electric double layer formed by polarized ferroelectric thin films: Implications for sensing and colloidal manipulation in aqueous media}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {246}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2013}, Month = {September}, Key = {fds319130} } @article{fds319131, Author = {Zauscher, S and Yellen, B and Ferris, R}, Title = {Programming smart macromolecular and ferroelectric surfaces for (bio)sensing applications}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {245}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2013}, Month = {April}, Key = {fds319131} } @article{fds319135, Author = {Ferris, R and Zauscher, S}, Title = {Electric field-induced nanolithography to manipulate soft matter on surfaces}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {243}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2012}, Month = {March}, Key = {fds319135} } @article{fds319133, Author = {Zauscher, S}, Title = {Molecular mechanisms of aqueous boundary lubrication by mucinous glycoproteins}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {244}, Year = {2012}, Key = {fds319133} } @article{fds319134, Author = {Ferris, R and Hucknall, A and Kwon, BS and Chilkoti, A and Zauscher, S}, Title = {Field-induced nanolithography for the patterning of non-fouling polymer brushes}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {243}, Year = {2012}, Key = {fds319134} } @article{fds319138, Author = {Chen, T and Zhang, J and Chang, DP and Garcia, A and Zauscher, S}, Title = {PMSE 99-Fabrication of patterned polymer brushes by in situ crosslinking of an initiator precursor by microcontact printing}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {236}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2008}, Month = {August}, Key = {fds319138} } @article{fds319143, Author = {Abu-Lail, NI and Jay, G and Guilak, F and Zauscher, S}, Title = {Effect of glycoproteins on friction in diarthroidal joints and between model surfaces measured with lateral force microscopy}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {231}, Pages = {1 pages}, Publisher = {AMER CHEMICAL SOC}, Year = {2006}, Month = {March}, Key = {fds319143} } @article{fds319146, Author = {Abu-Lail, NI and Kaholek, M and Loveless, DM and Craig, SL and Zauscher, S}, Title = {Atomic force microscopy study of reversibly crosslinked polymer brushes}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {230}, Pages = {U4180-U4180}, Publisher = {AMER CHEMICAL SOC}, Year = {2005}, Month = {August}, Key = {fds319146} } @article{fds319147, Author = {Lee, WK and Kaholek, M and Ahn, SJ and Patra, M and Linse, P and Zauscher, S}, Title = {Progress in fabrication and characterization of nanopatterned polymer brushes}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {230}, Pages = {U4005-U4006}, Publisher = {AMER CHEMICAL SOC}, Year = {2005}, Month = {August}, Key = {fds319147} } @article{fds319148, Author = {Kaholek, M and Lee, W-K and Feng, L and LaMattina, B and Dyer, DJ and Zauscher, S}, Title = {pH, salt, and solvent sensitive polymer brush micro- and nanopatterns fabricated by electron-beam lithography}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {230}, Pages = {U4186-U4186}, Publisher = {AMER CHEMICAL SOC}, Year = {2005}, Month = {August}, Key = {fds319148} } @article{fds319150, Author = {Abulail, NI and Ohashi, T and Clark, R and Erickson, H and Zauscher, S}, Title = {Elasticity of fibronectin fibrils - Insights from the relative unfolding strengths of FN-III domains and GFP}, Journal = {Biophysical Journal}, Volume = {88}, Number = {1}, Pages = {168A-168A}, Publisher = {BIOPHYSICAL SOCIETY}, Year = {2005}, Month = {January}, Key = {fds319150} } @article{fds319151, Author = {Valiaev, A and Lim, DW and Clark, R and Chilkoti, A and Zauscher, S}, Title = {Mechanics of stimulus-responsive elastin-like polypeptides studied by force spectroscopy.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {228}, Pages = {U485-U485}, Publisher = {AMER CHEMICAL SOC}, Year = {2004}, Month = {August}, Key = {fds319151} } @article{fds319152, Author = {Abu-Lail, NI and Kaholek, M and Lam, Y and LaMattina, B and Zauscher, S}, Title = {Micro-cantilever deflection: A tool for characterizing polymer brush properties and biomolecular recognition events.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {228}, Pages = {U487-U487}, Publisher = {AMER CHEMICAL SOC}, Year = {2004}, Month = {August}, Key = {fds319152} } @article{fds319153, Author = {Kaholek, M and Hyun, J and Lee, WK and Chilkoti, A and Zauscher, S}, Title = {Fabrication of "smart" biomolecular and polymeric nanostructures using molecular recognition, surface-initiated nanopolymerization and scanning probe lithography.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {227}, Pages = {U861-U861}, Publisher = {AMER CHEMICAL SOC}, Year = {2004}, Month = {March}, Key = {fds319153} } @article{fds319154, Author = {De Bellis and AC and Zauscher, S}, Title = {Investigation of nanoscale friction in poly(N-isopropylacrylamide) brushes by atomic force microscopy.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {227}, Pages = {U820-U820}, Publisher = {AMER CHEMICAL SOC}, Year = {2004}, Month = {March}, Key = {fds319154} } @article{fds319155, Author = {Kaholek, M and Lee, WK and LaMattina, B and Caster, K and Zauscher, S}, Title = {Preparation and characterization of stimulus-responsive poly(N-isopropyl-acrylamide) brushes and nanopatterns.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {227}, Pages = {U509-U509}, Publisher = {AMER CHEMICAL SOC}, Year = {2004}, Month = {March}, Key = {fds319155} } @article{fds319156, Author = {Zauscher, S and Chilkoti, A and Hyun, J and Lee, WK}, Title = {Fabrication of "smart" protein nanostructures using molecular recognition and dip-pen nano-lithography.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {226}, Pages = {U485-U485}, Publisher = {AMER CHEMICAL SOC}, Year = {2003}, Month = {September}, Key = {fds319156} } @article{fds319157, Author = {Nath, N and Chilkoti, A and Zauscher, S and Hyun, JH and Lee, WK}, Title = {Non-covalent, environmentally modulated molecular recognition between ELP biopolymers: A convenient route to reversible protein arrays.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {226}, Pages = {U410-U410}, Publisher = {AMER CHEMICAL SOC}, Year = {2003}, Month = {September}, Key = {fds319157} } @article{fds319158, Author = {Zauscher, S and Chilkoti, A and Ahn, SJ and Hyun, J and Lee, WK}, Title = {Fabrication of surface confined, stimulus-responsive polymer nanostructures using dip-pen nanolithography.}, Journal = {Abstracts of Papers of the American Chemical Society}, Volume = {225}, Pages = {U655-U655}, Publisher = {AMER CHEMICAL SOC}, Year = {2003}, Month = {March}, Key = {fds319158} } @article{fds319159, Author = {Zauscher, S and Klingenberg, DJ}, Title = {Surface forces and friction between cellulose surfaces in aqueous media}, Journal = {Nanotribology: Critical Assessment and Research Needs}, Pages = {411-440}, Year = {2003}, ISBN = {1-4020-7298-8}, Key = {fds319159} } @article{fds319163, Author = {Zauscher, S and Scott, T and Willett, JL and Klingenberg, DJ}, Title = {Pulp extrusion at ultra-high consistencies: a new processing method for recycling waste papers and papermill sludges}, Journal = {Fifth International Conference on Woodfiber Plastic Composites}, Pages = {307-307}, Year = {1999}, Key = {fds319163} } @article{fds319164, Author = {Scott, CT and Zauscher, S and Klingenberg, DJ}, Title = {Rheology and extrusion of low-grade paper and sludge}, Journal = {Tappi International Environmental Conference, Vols 1 3}, Pages = {685-690}, Year = {1999}, ISBN = {0-89852-736-8}, Key = {fds319164} } %% Journal Articles @article{fds337169, Author = {Tang, L and Gu, R and Aritome, I}, Title = {DNA Brushes: Advances in Synthesis and Applications}, Pages = {627-654}, Publisher = {JOHN WILEY & SONS LTD}, Editor = {Azzaroni, O and Szleifer, I}, Year = {2017}, Month = {December}, ISBN = {9781119455011}, url = {http://dx.doi.org/10.1002/9781119455042.ch22}, Doi = {10.1002/9781119455042.ch22}, Key = {fds337169} } @article{fds327225, Author = {Bhushan, B and Luo, D and Schricker, SR and Sigmund, W and Zauscher, S}, Title = {Handbook of Nanomaterials Properties}, Pages = {1463 pages}, Publisher = {Springer Science & Business Media}, Year = {2014}, Month = {March}, ISBN = {3642311075}, Abstract = {This Handbook of Nanomaterials Properties will be the first single reference work that brings together the various properties with wide breadth and scope.}, Key = {fds327225} } %% Chapter in Book @misc{fds346422, Author = {Deshpande, S and Yang, Y and Chilkoti, A and Zauscher, S}, Title = {Enzymatic synthesis and modification of high molecular weight DNA using terminal deoxynucleotidyl transferase.}, Volume = {627}, Pages = {163-188}, Booktitle = {Methods in Enzymology}, Year = {2019}, Month = {January}, url = {http://dx.doi.org/10.1016/bs.mie.2019.07.044}, Abstract = {The recognition that nucleic acids can be used as polymeric materials led to the blossoming of the field of DNA nanotechnology, with a broad range of applications in biotechnology, biosensors, diagnostics, and drug delivery. These applications require efficient methods to synthesize and chemically modify high molecular weight DNA. Here, we discuss terminal deoxynucleotidyl transferase (TdT)-catalyzed enzymatic polymerization (TcEP) as an alternative to conventional enzymatic and solid-phase DNA synthesis. We describe biochemical requirements for TcEP and provide step-by-step protocols to carry out TcEP in solution and from surfaces.}, Doi = {10.1016/bs.mie.2019.07.044}, Key = {fds346422} } @misc{fds327151, Author = {Zauscher, S and Parlak, Z and Tu, Q}, Title = {Polymeric and Biomolecular Nanostructures: Fabrication by Scanning Probe Lithography}, Volume = {2}, Booktitle = {Handbook of Nanomaterials Properties}, Publisher = {Springer-Verlag, Berlin-Heidelberg}, Editor = {Bhushan, B and Luo, D and Schricker, SR and Sigmund, W and Zauscher, S}, Year = {2014}, Key = {fds327151} } | |
Duke University * Pratt * Reload * Login |