Synthesis of A2B star block copolymers from a heterotrifunctional initiator

We described the obtention of A₂B star block copolymers through the use of a new heterotrifunctional initiator. That way, well‐defined (PCL)₂‐arm‐PtBuMA and (PCL)₂‐arm‐PS star block copolymers have been synthesized from a heterotrifunctional initiator bearing two hydroxyl groups able to initiate ROP of CL (with AlEt₃ or Sn(Oct)₂ as coinitiator) and a bromide function able to initiate ATRP of tBuMA or styrene. Firstly, we have proceeded using a sequential process (two‐steps), leading to an intermediate macroinitiator. Secondly, attempt to polymerize these two monomers in a simultaneous process (one‐step), that is directly from the mixture of monomers, initiator, coinitiators, and solvent, has been realized and has shown that some interferences between the two polymerizations occurred, leading to an inhibition of ATRP when Sn(Oct)₂ was used and an unexpected increase in control when AlEt₃ was used as catalyst for the ROP (obtention of well‐defined (PCL)₂‐arm‐PtBuMA with pdi of 1.18). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1796–1806, 2006     

Block copolymer mediated synthesis of amphiphilic gold nanoparticles in water and an aqueous tetrahydrofuran medium: An approach for the preparation of polymer–gold nanocomposites

The synthesis of polymer‐matrix‐compatible amphiphilic gold (Au) nanoparticles with well‐defined triblock polymer poly[2‐(N,N‐dimethylamino)ethyl methacrylate]‐b‐poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate] and diblock polymers poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate], polystyrene‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate], and poly(t‐butyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate] in water and in aqueous tetrahydrofuran (tetrahydrofuran/H₂O = 20:1 v/v) at room temperature is reported. All these amphiphilic block copolymers were synthesized with atom transfer radical polymerization. The variations of the position of the plasmon resonance band and the core diameter of such block copolymer functionalized Au particles with the variation of the surface functionality, solvent, and molecular weight of the hydrophobic and hydrophilic parts of the block copolymers were systematically studied. Different types of polymer–Au nanocomposite films [poly(methyl methacrylate)–Au, poly(t‐butyl methacrylate)–Au, polystyrene–Au, poly(vinyl alcohol)–Au, and poly(vinyl pyrrolidone)–Au] were prepared through the blending of appropriate functionalized Au nanoparticles with the respective polymer matrices {e.g., blending poly[2‐(N,N‐dimethylamino)ethyl methacrylate]‐b‐poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate‐stabilized Au with the poly(methyl methacrylate)matrix only}. The compatibility of specific block copolymer modified Au nanoparticles with a specific homopolymer matrix was determined by a combination of ultraviolet–visible spectroscopy, transmission electron microscopy, and differential scanning calorimetry analyses. The facile formation of polymer–Au nanocomposites with a specific block copolymer stabilized Au particle was attributed to the good compatibility of block copolymer coated Au particles with a specific polymer matrix. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1841–1854, 2006     

Comprehensive study on the formation of polyelectrolyte complexes from (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] and poly(2‐acrylamido‐2‐methylpropane sodium sulfonate)

Polyelectrolyte complexes (PECs) have been prepared from well‐defined (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) and high molecular weight poly(2‐acrylamido‐2‐methylpropane sodium sulfonate) (PAMPSNa) after a thorough study of their viscometric properties. The effect of pH and quaternization degree of PDMAEMA on PECs stoichiometry has been examined. PEC‐based materials have been characterized in terms of thermal stability, equilibrium swelling degree, and free/bound water composition. The stoichiometry and swellability of the physically crosslinked hydrogels obtained from fully quaternized PDMAEMA/PAMPSNa complexes do not depend on pH. In contrast, PECs made of non quaternized PDMAEMA and PAMPSNa are highly affected by pH, and could reversibly disintegrate at pH ≥ 9. Partially quaternized PDMAEMA/PAMPSNa PECs exhibit intermediate properties and form stable loose structures in the whole investigated pH range. Finally, stable dispersions of PECs nanoparticles have been successfully produced from dilute solutions of the complementary polyelectrolytes. The nanoparticle average diameter as determined by dynamic light scattering proved to depend on the molar fraction of DMAEMA‐based subunits and on the initial polyelectrolyte concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5468–5479, 2006     

Kerr介质中级联三能级原子与压缩相干态相互作用的光子统计演化

本文研究了存在Kerr介质的高Q腔中压缩相干态与级联三能级原子相互作用的光子统计演化规律,讨论了光场参数、Kerr介质及相干振幅对平均光子数的影响.     

激光感生碰撞能量转移的四能级理论模型

首次考虑了两个中间态对激光感生碰撞能量转移的影响，发展了激光感生碰撞能量转移的四能级理论模型，推导出态振幅的运动方程，并给出碰撞截面的近似表达式，通过对Ｅｕ－Ｓｒ和Ｃｓ－Ｓｒ系统的数值计算表明，当频率差│ω２１│大小和│ω４３│可以相比时，利用三能级近似理论就难以获得令人满意的计算结果，而四能级理论模型则适合于任何情况下的激光感生碰能量转移。     

Markovian network processes: Congestion-dependent routing and processing

A Markovian network process describes the movement of discrete units among a set of nodes that process the units. There is considerable knowledge of such networks, often called queueing networks, in which the nodes operate independently and the routes of the units are independent. The focus of this study, in contrast, is on networks with dependent nodes and routings. Examples of dependencies are parallel processing across several nodes, blocking of transitions because of capacity constraints on nodes, alternate routing of units to avoid congestion, and accelerating or decelerating the processing rate at a node depending on downstream congestion. We introduce a general network process representing the numbers of units at the nodes and derive its equilibrium distribution. This distribution takes the form of a product of functions of vectors in which the arguments of the functions satisfy an interchangeability property. This new type of distribution may apply to other multi-variate processes as well. A basic idea in our approach is a linking of certain micro-level balance properties of the network routing to the processing rates at the nodes. The link is via routing-balance partitions of nodes that are inherent in any network. A byproduct of this approach is a general characterization of blocking of transitions without the restriction that the process is reversible, which had been a standard assumption. We also give necessary and sufficient conditions under which a unit moving in the network sees a time average for the unmoved units (called the MUSTA property). Finally, we discuss when certain flows between nodes in an open network are Poisson processes.This research was sponsored in part by Air Force Office of Scientific Research contract 84-0367.     

α—氨基酸的快原子轰击质谱

本文研究了１８种α－氨基酸的快原子轰击质谱，发现添加三氟乙酸溶液能显著提高灵敏度，改善谱图。特征碎片主要有中性丢失ＣＯ２Ｈ２，Ｈ２Ｏ，ＮＨ３的离子以及Ｒ＾＋离子。侧链的性质决定了碎片的产生和离子的强弱。     

苯基重氮盐-冠醚分子嵌合物的FAB-MS及其准分子离子生成机理的研究

Fast atom bombardment mass spectra of a series of arenediazonium salts with various substituents complexed with 18-crown-6 and dibenzo-24-crown-8 ethers were examined. The correlation between quasi-molecular ion abundance of various complexes and the properties, coordination ability of donor-acceptor linkages in the complexes were studied. By using molecular orbital calculation we have successfully demonstrated that the correlation cited is related to the electron cloud densities on the heteroatoms α-N and β-N of arenediazonium salts.     

Polychronous kinetics with nonstationary rate constants. Effect of a medium

Characteristic features of the kinetics of solid-state cage reactions with distributed parameters of the relaxing matrix were considered. Depending on the ratio of the constants of the reaction rate and relaxation of environment, the kinetics of chemical conversions can be either exponential or nonexponential. Plausible reasons for the unsteady-state character of the kinetics of the processes of two types,viz., the reactions of alkyl radicals in amorphous alcohol matrices and conversions in biological systems, were discussed. The main reason for the unsteady-state character of the reactions of the first type is a dispersion of the equilibrium distances between the reagents. Kinetics of the reactions of the second type, such as rebinding of the ligands in the heme-containing proteins (e.g., in myoglobin), is determined by the distances in the pairs of reagents and the relaxation transitions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 469–476, March, 1997.