Depth profiling of latex blends of fluorinated and fluorine‐free acrylates with laser‐induced secondary mass spectrometry

We explored phase separation and self‐assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser‐induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film‐forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine‐free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine‐free or low‐fluorine polymers, self‐assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 360–367, 2003     

Template atom transfer radical polymerization of a diaminopyrimidine‐derivatized monomer in the presence of a uracil‐containing polymer

Uracil‐derivatized monomer 6‐undecyl‐1‐(4‐vinylbenzyl)uracil and diaminopyrimidine‐derivatized monomer 2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine (DMP) were synthesized and polymerized by atom transfer radical polymerization (ATRP). A well‐defined, highly soluble, uracil‐containing polymer, poly[6‐undecyl‐1‐(4‐vinylbenzyl)uracil] (PUVU), was prepared in dioxane at 90 °C with CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine as the catalyst and methyl α‐bromophenylacetate as the initiator. PUVU was further used as a template for the ATRP of DMP. The enhanced apparent rate constant of the DMP polymerization in the presence of PUVU indicated that the ATRP of DMP occurred along the PUVU template. The template polymerization produced a stable and insoluble macromolecular complex, PUVU/poly(2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine). An X‐ray diffraction study confirmed that the complex had strandlike domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6607–6615, 2006     

Effect of the environment on the stability of surfactant–polypeptide self‐assembled complexes: Molecular dynamics simulations of stoichiometric complexes formed by N‐dodecyltrimethylammonium and poly(α,L‐glutamate) in chloroform,methanol, and water

A series of molecular dynamics simulations have been performed to study the supramolecular structure of self‐assembled complexes formed by N‐dodecyltrimethylammonium cations and the synthetic polypeptide poly(α,L ‐glutamate). The influence of the type of solvent has been investigated, considering explicit environments of chloroform, water, and methanol on a stoichiometric complex containing 15 residues. In chloroform, the complex stabilizes in a regular structure: the polypeptide adopts an α‐helix conformation that is regularly surrounded by surfactant molecules to form electrostatic interactions through a multiple interaction pattern. However, this structure destabilizes in methanol and water: (a) the α‐helix unfolds in the two solvents and (b) the electrostatic links between the surfactant molecules and the polyanion are disrupted in aqueous solution, although these interactions are still preserved in methanol. The role of the solvent environment in stabilizing or destabilizing the polypeptide secondary structure, the organization of the surfactant molecules, and predominantly the surfactant–polypeptide supramolecular organization is discussed in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1122–1133, 2006     

Reactions of esters of tetracoordinated phosphorus acids with nucleophilic reagents in highly organized media

Characteristic features of reactions involving esters of phosphorus-containing acids in highly organized media (micelles, liquid crystals, vesicles, and emulsions) are surveyed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 298–312, February, 1996.     

Conformational changes of the amyloid beta-peptide (1-40) adsorbed on solid surfaces

The conformational change of the 39-43 residues of the amyloid beta-peptide (Abeta) toward a beta-sheet enriched state promotes self-aggregation of the peptide molecules and constitutes the major peptide component of the amyloid plaques in Alzheimer patients. The crucial question behind the self-aggregation of Abeta is related to the different pathways the peptide may take after cleavage from the amyloid precursor proteins at cellular membranes. This work is aiming at determining the conformation of the Abeta (1-40) adsorbed on hydrophobic Teflon and hydrophilic silica particles, as model sorbent surfaces mimicking the apolar transmembrane environment and the polar, charged membrane surface, respectively. The mechanism by which the Abeta interacts with solid surfaces strongly depends on the hydrophobic/hydrophilic character of the particles. Hydrophobic and electrostatic interactions contribute differently in each case, causing a completely different conformational change of the adsorbed molecules on the two surfaces. When hydrophobic interactions between the peptide and the sorbent prevail, the adsorbed Abeta (1-40) mainly adopts an alpha-helix conformation due to H-bonding in the apolar part of the peptide that is oriented towards the surface. On the other hand, when the peptide adsorbs by electrostatic interactions beta-sheet formation is promoted due to intermolecular association between the apolar parts of the adsorbed peptide. Irrespective of the characteristics of the solid sorbent, crowding the surface results in intermolecular association between adsorbed molecules leading to a strong aggregation tendency of the Abeta (1-40). [Diagram: see text] CD spectra of Abeta (1-40) at pH 7: A) in solution ([Abeta]=0.2 mg.ml(-1)) freshly prepared (line) and after overnight incubation (symbols);B) on Teflon (Gamma=0.5 mg.m(-2)).     

高功率激光驱动器中小尺度自聚焦和噪声模型

 建立了一套线性的近似分析方法，研究高功率激光驱动器中强激光传输的小尺度自聚焦效应和相位噪声对光束传输和光束质量的影响，给出了系统噪声强度、B积分值与光束近场调制对比度之间的定量关系。研究表明,为保证输出光束质量，即近场调制对比度小于给定值，系统内的噪声强度必须符合一定的谱分布。     

Synthesis of well‐defined side chain fullerene polymers and study of their self‐aggregation behaviors

Monoalkynyl‐functionalized fullerene was precisely synthesized starting with pristine fullerene (C₆₀) and characterized by multiple techniques. Methyl methacrylate and 6‐azido hexyl methacrylate were then randomly copolymerized via reversible addition fragmentation chain transfer polymerization to build polymer backbones with well‐controlled molecular weights and copolymer compositions. Finally, these two moieties were covalently assembled into a series of well‐defined side chain fullerene polymers (SFPs) via the copper‐mediated click reaction which was verified by Fourier transform infrared spectroscopy and ¹H NMR. The fullerene loadings of the resultant polymers were estimated by thermogravimetric analysis and UV–vis spectroscopy, demonstrating consistent and high conversions in most of the samples. The morphology studies of the SFPs were performed both in solution and on solid substrates. Very intriguing self‐aggregation behaviors were detected by both gel permeation chromatography and dynamic light scattering analyses. Furthermore, the scanning electron microscopic images of these polymers showed the formation of various supramolecular nanoparticle assemblies and crystalline‐like clusters depending on the fullerene contents and polymer chain lengths. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3572–3582