Multicolor quantum dot-encoded microspheres for the detection of biomolecules

The biocompatible semiconductor quantum dots (QDs) have unique photophysical properties, which provide important advantages over organic dyes and lanthanide probes in fluorescence labeling applications. In this work, multicolor quantum QD-encoded microspheres have been prepared via the layer-by-layer (LbL) assembly approach. Polystyrene microspheres of 3 μm diameter were used as templates for the deposition of different sized CdTe QDs/polyelectrolyte multilayers via electrostatic interactions. Two kinds of biofuntional multicolor microspheres with two different antibodies, anti-human IgG and anti-rabbit IgG were prepared. Human IgG and rabbit IgG can be detected as target antigens in the multiplexed fluoroimmunoassays. Furthermore, a novel microfluidic on-chip device was developed to detect two kinds of antigen-conjugated multicolor QD-encoded microspheres; the microspheres can be distinguished from each other based on their fluorescence signals.     

Description of the Structure and Properties of Atactic Polystyrene Melt Using Integral Equation Theory

The polymer reference interaction site model （PRISM） integral equation theory was used to describe the structure and thermodynamic properties of atactic polystyrene （aPS） melt, in which the monomer of aPS is represented with an eight-site model to characterize its microstructure. The intramolecular structure factors needed in the PRISM calculations were obtained from single chain MD simulations. The calculated results indicate that the results by the integral equation method agrees well with experiments, and can reflect the fine microscopic structure of real aPS melt. This work shows that the PRISM theory is a powerful tool for investigating the structure and properties of complex polymers.     

Sterically hindered aliphatic amines in the controlled synthesis of polystyrene

The kinetic features of radical polymerization of styrene in the presence of primary and secondary aliphatic amines combined with benzoyl peroxide and the molecular-mass characteristics of the resulting polymers were studied. In the presence of peroxide initiators, aliphatic amines, as potential sources of stable aminoxyl radicals, provide the synthesis of polystyrene with a controlled molecular mass without gel effect at a relatively high rate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 159–164, January, 2007.     

Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

Nitroxide mediated living radical polymerization of styrene onto poly (vinyl chloride)

Nitroxide‐mediated ‘living’ free radical polymerisation (LREP) was employed for the first time to prepare graft copolymer by having arylated poly (vinyl chloride) (PVC‐Ph) as a backbone and polystyrene (PS) as branches. The graft copolymerization of styrene was initiated by arylated PVC carrying 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) groups as a macroinitiator. Thus, the arylated PVC was prepared in the mild conditions and these reaction conditions could overcome the problem of gelation and crosslinking in polymers. Then, 1‐hydroxy TEMPO was synthesized by the reduction of TEMPO with sodium ascorbate. This functional nitroxyl compound was coupled with brominated arylated PVC (PVC‐Ph‐Br). The resulting macro‐initiator (PVC‐Ph‐TEMPO) for ‘living’ free radical polymerization was then heated in the presence of styrene to form graft copolymer. DSC, GPC, ¹HNMR, and FT‐IR spectroscopy were employed to investigate the structure of the polymers. Copyright © 2007 John Wiley & Sons, Ltd.     

Continuous Bulk Process for the Production of High‐Impact Polystyrene: Recent Developments in Modeling and Control

This work presents (in a wider perspective), some of our recent developments in the mathematical modeling and control of bulk polymerization for the production of HIPS. The recent model by Casís assumes the polymerization to be heterogeneous, and it calculates (in two phases) the global molecular structure of the three polymeric components of HIPS (free polystyrene, unreacted polybutadiene, and graft copolymer). At present, a model is being developed capable of estimating the average particle morphology (salami or core‐shell). Assuming a continuous bulk HIPS process as homogeneous, Luciani estimated the evolution of the MFI of the final product during changes of grade, with the aim of minimizing the intermediate off‐spec product. Finally, an unpublished simulation is presented that describes the transitions between the steady state of a HIPS‐grade and that of a general‐purpose polystyrene.

     

在CPS微球表面固载氨基酚型双齿席夫碱氧钒(Ⅳ)配合物及其催化氧化性能

使乙醛酸(GA)与氯甲基化交联聚苯乙烯(CMCPS)微球发生酯化反应,将醛基(AG)引入交联聚苯乙烯(CPS)微球表面,得到改性微球CPS-AG;再以间氨基苯酚(MAP)为试剂,使微球CPS-AG表面的AG发生席夫碱反应,制得了表面键合有氨基酚型双齿席夫碱配基的功能微球CPS-AGAP;最后,使微球CPS-AGAP与硫酸氧钒发生配位螯合反应,获得了表面固载有氨基酚型双齿席夫碱氧钒(Ⅳ)配合物的固体催化剂微球CPS-[VO(AGAP)2]。重点考察了主要因素对GA与CMCPS微球的酯化反应的影响。采用红外光谱(FT-IR)、固体紫外(UV)及扫描电子显微镜(SEM)对催化剂微球进行了充分表征。分别将微球CPS-[VO(AGAP)2]用于环己醇和乙苯的分子氧氧化过程,考察其催化活性。实验结果表明,溶剂的极性有利于GA与CMCPS微球之间的酯化反应,极性较强的N,N-二甲基乙酰胺为适宜的反应溶剂,90℃为适宜的反应温度。在适宜的反应条件下,CMCPS微球的氯甲基转化率可以达到82%。在分子氧氧化环己醇和乙苯的过程中,非均相催化剂CPS-[VO(AGAP)2]微球均表现出良好的催化活性。     

Polymer swelling. XXV. Structure‐affinity correlation studies that involve poly(styrene‐co‐divinylbenzene) exposed to acetylenic liquids

The adsorption parameters (α) established for the monosubstituted acetylenic liquids in this investigation are consistent with expectation based on analogies with the log α_f = log α_i ‐ D_s(N_f − N_i) relationships reported earlier for the many homologous series of liquids ZR, in which Z is a functional group having strong affinity for the pendent phenyl group of polystyrene and R is an alkyl substituent that is varied systematically. The order of relative Z‐affinities, based on α for the respective ZCH₂CH₃ molecules, confirm that the nature of Z is the major factor that affects α and that electronic and steric contributions from R are modifying effects, which are reflected in D_s. Comparisons of the results observed for HCC(CH₂)_nZ′ liquids with those for HCC(CH₂)_nH and with analogous pairs of Z(CH₂)_nZ′ series confirm that Z′ at the other end of the polymethylene chain can have a moderate positive effect or a marked negative effect on α, depending on whether the mode of adsorption to pendent phenyl groups is mono‐ or bidentate. This study also confirms that a sharp reversal in the roles played by the molecules participating in the adsorption process occurs when all of the hydrogen atoms covalently bonded to the center of unsaturation are replaced by alkyl substituents. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2611–2633, 1999     

Rheology of molten polystyrene with dissolved supercritical and near-critical gases

The viscosities of polystyrene melts containing three different dissolved gases, carbon dioxide, and the refrigerants R134a (1,1,1,2-tetrafluoroethane) and R152a (1,1-difluoroethane) are investigated at pressures up to 20 MPa. These pressures reach near-critical and supercritical conditions for the three gas components, and produce polymer–gas solutions containing up to 10 wt % gas. The measurements are performed in a sealed high-pressure capillary rheometer at 150 and 175°C, and at shear rates ranging from 1–2,000 s⁻¹. Very large reductions in melt viscosity are observed at high gas loading; at 150°C, 10 wt % R152a reduces the Newtonian viscosity by nearly three orders of magnitude relative to pure polystyrene. The viscosity data for all three polystyrene–gas systems follows ideal viscoelastic scaling, whereby the set of viscosity curves for a polymer-gas system can be scaled to a master curve of reduced viscosity vs. reduced shear rate identical to the viscosity curve for the pure polymer. The viscoelastic scaling factors representing the effect of dissolved gas content on rheological behavior are found to follow roughly the same variation with composition for all three polystyrene gas systems. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2771–2781, 1999