PubMed Health⌕ Search

Biomedical subjects

Jan Genzer

Publications and source records attributed to Jan Genzer.

17 recordsLinked to original sources
PubMed2007

Study of the packing density and molecular orientation of bimolecular self-assembled monolayers of aromatic and aliphatic organosilanes on silica.

Bimolecular self-assembled monolayers (SAMs) of aromatic and aliphatic chlorosilanes were self-assembled onto silica, and their characteristics were established by contact angle measurement, near-edge X-ray absorption fine structure spectroscopy, and Fourier transform infrared spectroscopy. Three aromatic constituents (phenyltrichlorosilane, benzyltrichlorosilane, and phenethyltrichlorosilane) were studied in combination with four aliphatic coadsorbates (butyltrichlorosilane, butyldimethylchlorosilane, octadecyltrichlorosilane, and octadecyldimethylchlorosilane). Our results demonstrate that whereas SAMs made of trichlorinated organosilanes are densely packed, SAMs prepared from monochlorinated species are less dense and poorly ordered. In mixed systems, trichlorinated aromatics and trichlorinated aliphatics formed SAMs with highly tunable compositions; their surfaces were compositionally homogeneous with no large-scale domain separation. The homogeneous nature of the resulting SAM was a consequence of the formation of in-plane siloxane linkages among neighboring molecules. In contrast, when mixing monochlorinated aliphatics with trichlorinated aromatics, molecular segregation occurred. Although the two shortest aromatic species did not display significant changes in orientation upon mixing with aliphatics, the aromatic species with the longest polymethylene spacer, phenethyltrichlorosilane, displayed markedly different orientation behavior in mixtures of short- and long-chain aliphatics.

Journal Article↗
PubMed2006

Tunable instability mechanisms of polymer thin films by molecular self-assembly.

Incorporation of a block copolymer into a thin polymer film is observed to alter both the rate and mechanism by which the film dewets from an immiscible polymer substrate. Films with little or no copolymer dewet by classical nucleation and growth of circular holes, and the dewetting rate decreases with increasing copolymer concentration. Increasing the copolymer content at constant film thickness generates copolymer micelles that adsorb/aggregate along the polymer/polymer interface and promote nonclassical dewetting fluctuations similar in appearance to spinodal dewetting. At higher copolymer concentrations, dewetting proceeds after a lengthy induction period by the nucleation and growth of flower-shaped holes suggestive of film pinning or viscous fingering. Atomic force microscopy of the polymer/polymer interface after removal of the top film by selective dissolution reveals substantial structural development due to copolymer self-assembly.

Microscopy, Atomic Force↗
PubMed2006

Formation mechanisms and properties of semifluorinated molecular gradients on silica surfaces.

The goal of this study is to elucidate the formation of molecular gradients made of semifluorinated organosilanes (SFOs) on flat substrates by using a methodology developed by Chaudhury and Whitesides (Science 1992, 256, 1539). We use surface-sensitive combinatorial near-edge X-ray absorption fine structure (combi-NEXAFS) spectroscopy to measure the position-dependent concentration and orientation of SFO molecules in SFO molecular gradients on flat silica surfaces. Using the combi-NEXAFS data, we establish the correlation between the fraction of the F(CF(2))(8)(CH(2))(2)- species on the substrate and the average tilt angle of the -(CF(2))(8)F group in the SFO as a function of the deposition gas medium (air vs nitrogen) and the end group around the silicon atom (monofunctional vs trifunctional). In addition, we utilize the gradient geometry to comprehend the mechanism of formation of SFO self-assembled monolayers (SAMs). Specifically, we provide evidence that depending on the nature of the end group in the SFO and the vapor phase the SFO molecules add themselves into the existing SAMs either as individual molecules or as multimolecular complexes.

Journal Article↗
PubMed2006

Computer simulation study of molecular recognition in model DNA microarrays.

DNA microarrays have been widely adopted by the scientific community for a variety of applications. To improve the performance of microarrays there is a need for a fundamental understanding of the interplay between the various factors that affect microarray sensitivity and specificity. We use lattice Monte Carlo simulations to study the thermodynamics and kinetics of hybridization of single-stranded target genes in solution with complementary probe DNA molecules immobilized on a microarray surface. The target molecules in our system contain 48 segments and the probes tethered on a hard surface contain 8-24 segments. The segments on the probe and target are distinct and each segment represents a sequence of nucleotides ( approximately 11 nucleotides). Each probe segment interacts exclusively with its unique complementary target segment with a single hybridization energy; all other interactions are zero. We examine how the probe length, temperature, or hybridization energy, and the stretch along the target that the probe segments complement, affect the extent of hybridization. For systems containing single probe and single target molecules, we observe that as the probe length increases, the probability of binding all probe segments to the target decreases, implying that the specificity decreases. We observe that probes 12-16 segments ( approximately 132-176 nucleotides) long gave the highest specificity and sensitivity. This agrees with the experimental results obtained by another research group, who found an optimal probe length of 150 nucleotides. As the hybridization energy increases, the longer probes are able to bind all their segments to the target, thus improving their specificity. The hybridization kinetics reveals that the segments at the ends of the probe are most likely to start the hybridization. The segments toward the center of the probe remain bound to the target for a longer time than the segments at the ends of the probe.

Computer Simulation↗
PubMed2006

Design of random copolymers with statistically controlled monomer sequence distributions via Monte Carlo simulations.

We use Monte Carlo simulations to model the formation of random copolymers with tunable monomer sequence distributions. Our scheme is based on the original idea proposed a few years ago by Khokhlov and Khalatur [Physica A 249, 253 (1998); Phys. Rev. Lett. 82, 3456 (1999)], who showed that the distribution of species B in A-B random copolymers can be regulated by (a) adjusting the coil size of a homopolymer A and (b) chemically modifying ("coloring") monomers that reside at (or close to) the periphery of the coil with species B. In contrast to Khokhlov and Khalatur's work, who modeled the polymer modification by performing the coloring instantaneously, we let the chemical coloring reaction progress over time using computer simulations. We show that similar to Khokhlov and Khalatur's work, the blockiness (i.e., number of consecutive monomers) of the B species along the A-B copolymer increases with increasing degree of collapse of the parent homopolymer A. A simple analysis of the A-B monomer sequences in the copolymers reveals that monomer sequence distributions in homopolymers "colored" under collapsed conformations possess certain degrees of self-similarity, while there is no correlation found among the monomer sequence distributions formed by coloring homopolymers with expanded conformations.

Journal Article↗
PubMed2006

Effects of synthetic amphiphilic alpha-helical peptides on the electrochemical and structural properties of supported hybrid bilayers on gold.

Amphiphilic alpha-helices were formed from designed synthetic peptides comprising alanine, phenylalanine, and lysine residues. The insertion of the alpha-helical peptides into hybrid bilayers assembled on gold was studied by a variety of methods to assess the resulting structural characteristics, such as electrical resistance and molecular orientation. Self-assembled monolayers (SAMs) of dodecanethiol (DDT); octadecanethiol (ODT); and 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol (DPPTE) were formed on gold substrates with and without incorporated peptide. Supported hybrid bilayers and multilayers of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) were formed on SAMs by the "paint-freeze" method of bilayer formation. Modeling of electrochemical impedance spectroscopy data using equivalent electrochemical circuits revealed that the addition of peptide decreased dramatically the resistive element of the bilayer films while maintaining the value of the capacitive element, indicating successful incorporation of peptide into a well-formed bilayer. Near-edge X-ray absorption fine structure spectroscopy data provided evidence that the molecules in the SAMs and hybrid multilayers were ordered even in the presence of peptide. The peptide insertion into the SAM was confirmed by observing the pi* resonance peak correlating with phenylalanine and a peak in the nitrogen K-edge regime attributable to the peptide bond.

Electrochemistry↗
PubMed2006

Recent developments in superhydrophobic surfaces and their relevance to marine fouling: a review.

In this review, a brief synopsis of superhydrophobicity (i.e. extreme non-wettability) and its implications on marine fouling are presented. A short overview of wettability and recent experimental developments aimed at fabricating superhydrophobic surfaces by tailoring their chemical nature and physical appearance (i.e. substratum texture) are reviewed. The formation of responsive/"smart" surfaces, which adjust their physico-chemical properties to variations in some outside physical stimulus, including light, temperature, electric field, or solvent, is also described. Finally, implications of tailoring the surface chemistry, texture, and responsiveness of surfaces on the design of effective marine fouling coatings are considered and discussed.

Animals↗
PubMed2005

Creating responsive surfaces with tailored wettability switching kinetics and reconstruction reversibility.

We report on the formation of responsive surfaces with tailorable surface reconstruction kinetics and switching hysteresis by thiolene radical addition of mercaptoalkanols with variable lengths to poly(vinylmethylsiloxane) networks. Exposing these elastomer surfaces to water results in rearrangement of the hydrophilic alkanes at the surface. The rearrangement kinetics decreases with increasing number of the methylene spacers (n) in the mercaptoalkanol. The response kinetics is found to be very fast for n = 2 and 6. For instance, upon exposing to water, the water contact angle on 3-mercaptopropanol-based surfaces decreases by approximately 35 degrees at the rate of 2 degrees /s. The high flexibility of the siloxane backbone endows these materials with switching longevity; the materials were able to switch their wettability over 10 cycles with minimum hysteresis. Increasing the number of methylene spacers to n = 11 decreases the surface reorganization dramatically. Formation of semicrystalline regions in such materials (detected via IR) is responsible for initial "sluggish" kinetics and eventual surface "freezing".

Journal Article↗
PubMed2005

Evolution of surface morphologies in multivariant assemblies of surface-tethered diblock copolymers after selective solvent treatment.

We study systematically the topography behavior of PHEMA-b-PMMA block as a function of the PHEMA and PMMA block lengths after selectively collapsing the top (PMMA) block by using surface-anchored assemblies of poly(2-hydroxyethyl methacrylate-b-methyl methacrylate), PHEMA-b-PMMA, block copolymer with orthogonally varying lengths of each block. Our experimental results are in excellent qualitative agreement with topology diagrams predicted by self-consistent field calculations of Zhulina and co-workers.

Polyhydroxyethyl Methacrylate↗
PubMed2005

Designing pattern-recognition surfaces for selective adsorption of copolymer sequences using lattice monte carlo simulation.

We describe a simulation method to design surfaces for recognizing specific monomer sequences in copolymers. We fix the monomer sequence statistics of the AB copolymers on a surface containing two types of sites and allow the simulation to iterate towards an optimal surface pattern that can recognize and selectively adsorb the sequence in the copolymer. During the simulation the surface pattern is designed by switching identities of two randomly picked sites. For copolymers with less blocky sequences the designed surfaces recognize the correct sequence well when the segment-surface interactions dominate over the intersegment interactions. For copolymers with more blocky sequences recognition is good when the segment-surface interactions are only slightly stronger than the intersegment interactions.

Adsorption↗
PubMed2005

Nanomechanics of opposing glycosaminoglycan macromolecules.

In this study, the net intermolecular interaction force between a chondroitin sulfate glycosaminoglycan (GAG)-functionalized probe tip and an opposing GAG-functionalized planar substrate was measured as a function of probe tip-substrate separation distance in aqueous electrolyte solutions using the technique of high resolution force spectroscopy. A range of GAG grafting densities as near as possible to native cartilage was used. A long-range repulsive force between GAGs on the probe tip and substrate was observed, which increased nonlinearly with decreasing separation distance between probe tip and substrate. Data obtained in 0.1 M NaCl was well predicted by a recently developed Poisson-Boltzmann-based theoretical model that describes normal electrostatic double layer interaction forces between two opposing surfaces of end-grafted, cylindrical rods of constant volume charge density and finite length, which interdigitate upon compression. Based on these results, the nanomechanical data and interdigitated rod model were used together to estimate the electrostatic component of the equilibrium modulus of cartilage tissue, which was then compared to that of normal adult human ankle cartilage measured in uniaxial confined compression.

Biomechanical Phenomena↗
PubMed2005

Nested self-similar wrinkling patterns in skins.

Stiff thin films on soft substrates are both ancient and commonplace in nature; for instance, animal skin comprises a stiff epidermis attached to a soft dermis. Although more recent and rare, artificial skins are increasingly used in a broad range of applications, including flexible electronics, tunable diffraction gratings, force spectroscopy in cells, modern metrology methods, and other devices. Here we show that model elastomeric artificial skins wrinkle in a hierarchical pattern consisting of self-similar buckles extending over five orders of magnitude in length scale, ranging from a few nanometres to a few millimetres. We provide a mechanism for the formation of this hierarchical wrinkling pattern, and quantify our experimental findings with both computations and a simple scaling theory. This allows us to harness the substrates for applications. In particular, we show how to use the multigeneration-wrinkled substrate for separating particles based on their size, while simultaneously forming linear chains of monodisperse particles.

Cross-Linking Reagents↗
PubMed2004

Fast directed motion of "fakir" droplets.

In this Letter, we report on the motion of water droplets on surfaces decorated with molecular gradients comprising semifluorinated (SF) organosilanes. SF molecular gradients deposited on flat silica substrates facilitate faster motion of water droplets relative to the specimens covered with an analogous hydrocarbon gradient. Further increase in the drop speed is achieved by advancing it along porous substrates coated with the SF wettability gradients. The results of our experiments are in quantitative agreement with a simple scaling theory that describes the faster liquid motion in terms of reduced friction at the liquid/substrate interface.

Journal Article↗
PubMed2004

Dewetting behavior of a block copolymer/homopolymer thin film on an immiscible homopolymer substrate.

Numerous previous studies have established that the addition of a microphase-ordered AB diblock copolymer to a thin homopolymer A (hA) film can slow, if not altogether prevent, film rupture and subsequent film dewetting on a hard substrate such as silica. However, only a few reports have examined comparable phenomena when the hA/AB blend resides on a soft B-selective surface, such as homopolymer B (hB). In this work, the dewetting kinetics of thin films composed of polystyrene (PS) and a symmetric poly(styrene-b-methyl methacrylate) (SM) diblock copolymer on a poly(methyl methacrylate) substrate is investigated by hot-stage light microscopy. Without the SM copolymer, the dewetting rate of the PS layer is constant under isothermal conditions and exhibits Arrhenius behavior with an apparent activation energy of approximately 180 kJ/mol. Addition of the copolymer promotes a crossover from early- to late-stage dewetting kinetics, as evidenced by measurably different dewetting rates. Transmission electron microscopy reveals the morphological characteristics of dewetted PS/SM films as functions of film thickness and SM concentration.

Journal Article↗
PubMed2002

Surface modification of Sylgard-184 poly(dimethyl siloxane) networks by ultraviolet and ultraviolet/ozone treatment.

We report on the surface modification of Sylgard-184 poly(dimethyl siloxane) (PDMS) networks by ultraviolet (UV) radiation and ultraviolet/ozone (UVO) treatment. The effects of the UV light wavelength and ambient conditions on the surface properties of Sylgard-184 are probed using a battery of experimental probes, including static contact angle measurements, Fourier transform infrared spectroscopy, near-edge X-ray absorption fine structure, and X-ray reflectivity. Our results reveal that when exposed to UV, the PDMS macromolecules in the surface region of Sylgard-184 undergo chain scission, involving both the main chain backbone and the side groups. The radicals formed during this process recombine and form a network whose wetting properties are similar to those of a UV-modified model PDMS. In contrast to the UV radiation, the UVO treatment causes very significant changes in the surface and near-surface structure of Sylgard-184. Specifically, the molecular oxygen and ozone created during the UVO process interact with the UV-modified specimen. As a result of these interactions, the surface of the sample contains a large number of hydrophilic (mainly -OH) groups. In addition, the material density within the first approximately 5 nm reaches about 50% of that of pure silica. A major conclusion that can be drawn from the results and analysis described in this work is that the presence of the silica fillers in Sylgard-184 does not alter the surface properties of the UVO- and UV-modified Sylgard-184.

Journal Article↗
PubMed2002

Combinatorial study of the mushroom-to-brush crossover in surface anchored polyacrylamide.

We present a method for fabricating anchored polymers with a gradual variation of grafting densities on solid substrates. The technique for generating such structures comprises (i) formation of a molecular gradient of polymerization initiator on the solid substrate and (ii) polymerization from the substrate-bound initiator centers ("grafting from"). We measure the mushroom-to-brush transition in grafted polyacrylamides and show that the mushroom and brush behavior can be described using existing scaling theories.

Journal Article↗