Using polymer brushes to tune the structure-plasmonic relationship in polymer nanocomposites containing nanorods

The thermodynamic factors that affect the dispersion of polymer-brush grafted gold nanorods (NRs) added to polymer matrix films have been studied by experiment and theory. When the brush (degree of polymerization N) and matrix (degree of polymerization P) have a favorable interaction (enthalpy driven), NRs uniformly disperse in the matrix, independent of P/N. When the brush and matrix are chemically similar, NRs randomly disperse for P/N \u3c 2 (i.e., wet brush), but align side-by-side for P/N \u3e 2. UV-visible spectroscopy is used to investigate the structure-optical property relationship as function of P/N. For P/N \u3e 2, self-consistent field theory (SCFT) and density functional theory (DFT) indicate that NR aggregation correlates with rod-rod interactions greater than -5kT. As NR aspect ratio (AR) increases, dry and wet brush behavior is observed for ARs from 2.5 to 6.3. For P/N \u3c 2, long NRs exhibit much longer range local order than short NRs and corresponding strong blue shift in the longitudinal surface plasmon resonance (LSPR). Chemically mixed brushes on NR surfaces provide another means to tune NR dispersion. To induce end-to-end linking, Au NRs are selectively functionalized with dithols and peptides to create permanent and revisable linking as well as a red shift in the LSPR

Breakdown of Dynamic Scaling in Thin Film Binary Liquids Undergoing Phase Separation

The kinetics of phase separation in thin polymer blend films displaying discrete and bicontinuous domain morphologies are examined. For discrete domains, the correlation length ξ grows as t1/3, in agreement with a coalescence model. By plotting ξ/d vs t/ti (initiation time), universal growth behavior is obtained for thickness values (d) from 1000 to 190 nm. In contrast, bicontinuous domains grow with a decreasing exponent, 0.62 to 0.28, as d decreases from 900 to 90 nm (i.e., no universal growth). This slowing down with reduced dimensionality suggests suppression of lateral hydrodynamic pumping

Polymer conformations in polymer nanocomposites containing spherical nanoparticles

We investigate the effect of various spherical nanoparticles on chain dimensions in polymer melts for high nanoparticle loading which is larger than the percolation threshold, using molecular dynamics simulations. We show that polymer chains are unperturbed by the presence of repulsive nanoparticles. In contrast polymer chains can be perturbed by the presence of attractive nanoparticles when the polymer radius of gyration is larger than the nanoparticle radius. At high nanoparticle loading, chains can be stretched and flattened by the nanoparticles, even oligomers can expand under the presence of attractive nanoparticles of very small size

Biomimetic dextran coatings on silicon wafers : thin film properties and wetting

There has been much recent interest in polysaccharide coatings for biotechnology applications. We obtained highly wettable dextran coatings applied to flat silicon wafer surfaces through a two-step process: in the first step, the silicon is aminated by the deposition of a selfassembled monolayer of 3-aminopropyltriethoxysilane (APTES); in the second step, polydisperse and low dispersity dextrans with molecular weights ranging from 1 kDa to 100 kDa are covalently grafted along the backbone to the surface amino groups to achieve strong interfacial anchoring. The effect of dextran concentration on film thickness and contact angle is investigated. Atomic force microscopy (AFM) has been employed to characterize surface roughness and coverage of the dextrans as well as the APTES monolayers. The synthetic surfaces were also tested for gas bubble adhesion properties

Entanglements in polymer nanocomposites containing spherical nanoparticles

We investigate the polymer packing around nanoparticles and polymer/nanoparticle topological constraints (entanglements) in nanocomposites containing spherical nanoparticles in comparison to pure polymer melts using molecular dynamics (MD) simulations. The polymer–nanoparticle attraction leads to good dispersion of nanoparticles. We observe an increase in the number of topological constraints (decrease of total entanglement length Ne with nanoparticle loading in the polymer matrix) in nanocomposites due to nanoparticles, as evidenced by larger contour lengths of the primitive paths. An increase of the nanoparticle radius reduces the polymer–particle entanglements. These studies demonstrate that the interaction between polymers and nanoparticles does not affect the total entanglement length because in nanocomposites with small nanoparticles, the polymer–nanoparticles topological constraints dominat

Dextran grafted silicon substrates : preparation, characterization and biomedical applications

Biodevices used in the cardiovascular system suffer from well-known problems associated with surface-induced gas embolism and thrombosis. In order to improve the biocompatibility of these devices, biomimetic coatings show good promise. We recently synthesized a coating layer of dextran, a relatively simple and well characterized neutral polysaccharide, with the purpose of mimicking the cells\u27 glycocalyx layer, that prevents non-specific cells-protein interactions. Systematic physical chemical characterization was performed on coatings obtained both from commonly used polydisperse dextrans and low-dispersity dextrans in the 1-100 kDalton molecular weight range. We have combined standard surface analysis techniques, such as ellipsometry, contact angle measurements and AFM, with less traditional vibrational spectroscopy techniques in the characterization of our biomimetic coatings. FTIR, micro-FTIR and micro-Raman spectroscopies were utilized to correlate the conformational and molecular aspects of the grafted poly- and monodisperse dextran chains to their attractive biological properties

Effect of Nano-to Micro-Scale Surface Topography on the Orientation of Endothelial Cells

The effect of grating textures on the alignment of cell shape and intracellular actin cytoskeleton has been investigated in bovine aortic endothelial cells (BAECs) cultured on a model cross-linked poly(dimethylsiloxane) (PDMS). Grating-textured PDMS substrates, having a variation in channel depths of 200 nm, 500 nm, 1 µm and 5 µm, were coated with fibronectin (Fn) to promote endothelial cell adhesion and cell orientation. As cells adhered to the Fn-coated surface, the underlying grating texture has shown to direct the alignment of cell shape, F-actin and focal contacts parallel to the channels. Cell alignment was observed to increase with increasing channel depths, reaching the maximum orientation where most cells aligned parallel to channels on 1-µm textured surface. Immunofluorescence studies showed that F-actin stress fibers and vinculin at focal contacts also aligned parallel to the channels. Cell proliferation was found to be independent of grating textures and the alignment of cell shape was maintained at confluence