Protein adsorption and reversible cell attachment are investigated as a function of the grafting density of poly(N‐isopropyl acrylamide) (PNIPAM) brushes. Prior studies demonstrated that the thermally driven collapse of grafted PNIPAM above the lower critical solution temperature of 32 °C is not required for protein adsorption. Here, the dependence of reversible, protein‐mediated cell adhesion on the polymer chain density, above and below the lower critical solution temperature, is reported. Above 32 °C, protein adsorption on PNIPAM brushes grafted from a non‐adsorbing, oligo(ethylene oxide)‐coated surface exhibits a maximum with respect to the grafting density. Few cells attach to either dilute or densely grafted PNIPAM chains, independent of whether the polymer brush collapses above 32 °C. However, both cells and proteins adsorb reversibly at intermediate chain densities. This supports a model in which the proteins, which support reversible cell attachment, adsorb by penetrating the brushes at intermediate grafting densities, under poor solvent conditions. In this scenario, reversible protein adsorption to PNIPAM brushes is determined by the thermal modulation of relative protein‐segment attraction and osmotic repulsion.
Various ladder‐like structured poly(phenyl‐co‐methacryl silsesquioxane)s (LPMSQ)s with high molecular weight (Mw = 10,000 ∼ 40,000) were synthesized by direct hydrolysis and polymerization in the presence of base catalyst at 25 °C. Synthesized LPMSQs mainly showed ladder‐like structure and photo‐cure reaction by 100 mW/cm2 (360 nm) for 10 s without any photo‐cure initiators. Chemical composition and structural analysis of the obtained LPMSQs were characterized using 1H NMR, 29Si NMR, Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and X‐ray diffraction (XRD). Physical properties of LPMSQs before and after photcuring were analyzed by Nanoindentation. Surface modulus increased to 8GPa and hardness of thin films increased from 100 to 400 MPa. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
A label free biosensor based upon a vertically emitting distributed feedback ͑DFB͒ laser has been demonstrated. The DFB laser comprises a replica-molded, one-dimensional dielectric grating coated with laser dye-doped polymer as the gain medium. Adsorption of biomolecules onto the laser surface alters the DFB laser emission wavelength, thereby permitting the kinetic adsorption of a protein polymer monolayer or the specific binding of small molecules to be quantified. A bulk sensitivity of 16.6 nm per refractive index unit and the detection of a monolayer of the protein polymer poly͑Lys, Phe͒ have been observed with this biosensor. The sensor represents a departure from conventional passive resonant optical sensors from the standpoint that the device actively generates its own narrowband high intensity output without stringent requirements on the coupling alignments, resulting in a simple, robust illumination and detection configuration.
Through fine-tuning of the myriad of reaction conditions for an aqueous base-catalyzed hydrolysis−polycondensation reaction, a facile synthesis of structurally controlled polyphenylsilsesquioxanes was developed. Mechanism and kinetic studies indicated that the condensation reaction proceeded through a T 1 structured dimer, which was quantitatively and in situ formed through mild hydrolysis of a phenyltrimethoxysilane (PTMS) monomer, to give either the cage-structured polyhedral oligomeric silsesquioxanes (POSS) or the corresponding ladderlike silsesquioxane (LPSQ) with excellent yields. Ladderlike and POSS materials were selectively achieved at higher and lower initial concentrations of PTMS, respectively, and an in-depth spectroscopic analysis of both compounds clearly revealed their structural differences with different molecular weights.
We report the use of computational chemistry methods to design a chemically responsive liquid crystal (LC). Specifically, we used electronic structure calculations to model the binding of nitrile-containing mesogens (4′-n-pentyl-4biphenylcarbonitrile) to metal perchlorate salts (with explicit description of the perchlorate anion), which we call the coordinately saturated anion model (CSAM). The model results were validated against experimental data. We then used the CSAM to predict that selective fluorination can reduce the strength of binding of nitrile-containing nematic LCs to metalsalt-decorated surfaces and thus generate a faster reordering of the LC in response to competitive binding of dimethylmethylphosphonate (DMMP). We tested this prediction via synthesis of fluorinated compounds 3-fluoro-4′-pentyl[1,1′-biphenyl]-4-carbonitrile and 4-fluoro-4′-pentyl-1,1′-biphenyl, and subsequent experimental measurements of the orientational response of LCs containing these compounds to DMMP. These experimental measurements confirmed the theoretical predictions, thus providing the first demonstration of a chemoresponsive LC system designed from computational chemistry.
A replica-molded plastic-based vertically emitting distributed feedback (DFB) laser has been demonstrated for label-free chemical and biomolecular detection in which the emission wavelength is modulated by changes in bulk and surface-adsorbed material permittivity. A one-dimensional surface grating formed in UV-curable polymer on a flexible plastic substrate is coated with a thin polymer film incorporating organic laser dye. When optically pumped with a ∼10 ns pulse at λ=532 nm, the DFB laser exhibits stimulated emission in the λ=585–620 nm wavelength range with a linewidth as narrow as δλ=0.09 nm. While exposed to chemical solutions with different refractive indices and adsorbed charged polymer monolayers, the laser sensor demonstrates single mode emission over a tuning range of ∼14 nm and the ability to perform kinetic monitoring of surface-adsorbed mass. A protein-protein interaction experiment is used to demonstrate the capability to characterize antibody-antigen affinity binding constants.
This study investigated the impact of the protein adsorption mechanism(s) on the efficiency of thermally controlled cell adhesion and release from poly(N-isopropyl acrylamide) brushes. Large format polymer gradients were used to screen for grafting densities and substrate chemistries that alter both cell adhesion at 37 °C and rapid cell release at 25 °C. In particular, the grafting conditions investigated allowed protein adsorption to the underlying substrate, penetration of the brush only, or adsorption to the outer edge of the film. At an average molecular weight of 30 kDa (degree of polymerization N ∼ 270), the results show that robust protein adsorption to polymer brushes impairs rapid cell release below the lower critical solution temperature. Conversely, grafting conditions that permit protein penetration of the brush but block strong adsorption to the underlying substrate support cell adhesion above the transition temperature and ensure efficient cell recovery at lower temperature. These findings demonstrate the impact of protein adsorption mechanisms, surface chemistry, and polymer properties on thermally controlled cell capture and release.
The topography of poly (N-isopropyl acrylamide) brushes end-grafted from initiator-terminated monolayers was imaged by atomic force microscopy, as a function of the area per chain and of solvent quality. Measurements were done in air and in water, below and above the lower critical solution temperature. At low grafting densities and molecular weights, area-averaged ellipsometry measurements did not detect changes in the volume of water-swollen, end-grafted polymer films above the lower critical solution temperature. However, atomic force microscopy images revealed surface features that suggest the formation of lateral aggregates or "octopus micelles". At high grafting densities and molecular weights, the films collapsed uniformly, as detected by both AFM imaging and ellipsometry. These findings reconcile in part prior results suggesting that some poly(N-isopropyl acrylamide) chains do not collapse in poor solvent, and they also reveal more complex collapse behavior above the lower critical solution temperature than is commonly assumed. This behavior would influence the ability to tune the functional properties of poly(N-isopropyl acrylamide) coatings.
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