Hierarchical structuring of materials offers exciting opportunities to construct functional devices that exploit the ordering at different length scales to impart key functional properties. Herein, multiple processes are combined to create complex materials organized at the molecular, nano, and microscales for selective detection of testosterone by label-free opto-chemical sensing. Molecular imprinting is used to construct molecular scale analyte-selective cavities. Microphase separation produces a porous polymer film within which sensitized silver halide nanocolloids are dispersed by a process of infusion and controled precipitation, then converted to periodic layers of silver nanoparticles by holographic patterning followed by chemical development. Testosterone binding is followed via wavelength changes of the holographic reflection peak as a function of testosterone concentration and incubation time. Polymer cross-linking and film porosity are optimized with respect to the needs of both molecular recognition and hologram quality. The silver halide infusion step does not destroy the molecular selectivity of the molecularly imprinted polymers (MIP). Selective, label-free sensing of testosterone is possible at concentrations down to 1 μm. The approach is generic and should be applicable to many types of molecules and conventional MIP formulations, individually or in multiplexed arrays.

Uniformly sized porous polymer particles with different polarity namely poly(divinylbenzene), poly(vinyl acetate-co-divinylbenzene), poly(ethylene dimethacrylate), and poly (glycidyl methacrylate-co-ethylene dimethacrylate) were prepared in the micron-size range by a seeded polymerization method. Parameters affecting the particle morphologies including monomer mixture content, porogen content, and polystyrene (PS) seed latexes were varied, and the morphologies of the resulting particles were investigated by scanning electron and confocal microscopy. The results obtained indicated that the particle shape depended dominantly on the molecular weight of the PS seed template. Deformed particles, including collapsed spheres and spheres with holes were obtained when high molecular weight PS seeds were used, whereas well-defined polymer particles were produced easily by using low molecular weight seeds. The use of 1,1-diphenylethylene as a chain terminator during seed polymerization is proposed in this work as an efficient method to lower molecular weight of PS in seed particles while keeping seed size small. This low molecular weight seed template retained its spherical geometry after swelling and polymerization with different second stage monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

There is widespread interest in responsive polymers that show cloud point behavior, but little attention is paid to their solid state thermal properties. To manufacture products based on such polymers, it may be necessary to subject them to high temperatures; hence, it is important to investigate their thermal behavior. In this study, we characterized a family of poly(N-isopropylacrylamide-co-hydroxymethylacrylamide) copolymers. Although poly(N-isopropylacrylamide) shows very high thermal stability (up to 360 °C), introduction of hydroxy side chains leads to a significant reduction in stability and new degradation processes become apparent. Thermogravimetric analysis and fourier transform infrared spectroscopy (FT-IR) indicate that the first degradation process involves a chemical dehydration step (110–240 °C), supported by the nonreversing heat flow response in modulated temperature differential scanning calorimetry. Water loss scales with the fraction of hydroxy monomer in the copolymer. Glass transition temperatures (T_g) are higher than the temperatures causing dehydration; hence, these values relate to newly-formed copolymer structures produced by controlled heating under nitrogen. Fourier transform-Raman (FT-Raman) spectra suggest that this transition involves imine formation. The T_g increases as the fraction of hydroxy groups in the original copolymer increases. Further heating leads to degradation and mass loss, and more complex changes in the FT-IR spectra, consistent with formation of unsaturated species. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010