Optically active core/shell nanoparticles prepared using self‐assembled polymer micelle as reactive nanoreactor

This article reports on optically active core/shell nanoparticles constituted by chiral helical polymers and prepared by a novel approach: using self‐assembled polymer micelles as reactive nanoreactors. Such core/shell nanoparticles were composed of optically active helical‐substituted polyacetylene as the core and thermosensitive poly(N‐isopropylacrylamide) as the shell. The synthetic procedure is divided into three major steps: (1) synthesis of amphiphilic diblock copolymer bearing polymerizable C[tbond]C bonds via atom transfer radical polymerization, followed by (2) self‐assembly of the diblock copolymer to form polymer micelles; and (3) catalytic emulsion polymerization of substituted acetylene monomer conducted using the polymer micelles as reactive nanoreactors leading to the core/shell nanoparticles. The core/shell nanoparticles simultaneously exhibited remarkable optical activity and thermosensitivity. The facile, versatile synthesis methodology opens new approach toward preparing novel multifunctional core/shell nanoparticles.© 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The preparation of amphiphilic core‐shell nanospheres by using water‐soluble macrophotoinitiator

The amphiphilic poly(AM‐co‐SA)‐ITXH macrophotoinitiator was synthesized by precipitation photopolymerization under UV irradiation with isopropylthioxanthone (ITX) as free radical photoinitiator. A novel method has been developed to prepare amphiphilic core‐shell polymer nanospheres via photopolymerization of methyl methacrylate (MMA) in aqueous media, with amphiphilic copolymer macrophotoinitiator poly(AM‐co‐SA)‐ITXH. During polymerization, the amphiphilic macroradicals underwent in situ self‐assembly to form polymeric micelles, which promoted the emulsion polymerization of the monomer. Thus, amphiphilic core‐shell nanospheres ranging from 70 to 140 nm in diameter were produced in the absence of surfactant. The conversion of the monomer, number average molecular weights (M_n), and particle size were found to be highly dependent on the macrophotoinitiator and monomer concentration. The macrophotoinitiator and amphiphilic particles were characterized by FTIR, UV‐vis, ¹H NMR, TEM, DSC, and contact angle measurements. The results showed the particles had well‐defined amphiphilic core‐shell structure. This new method is scientifically and technologically significant because it provides a commercially viable route to a wide variety of novel amphiphilic core‐shell nanospheres. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 936–942, 2010     

Nonisothermal crystallization kinetics of poly(ε‐caprolactone) blocks in double crystalline triblock copolymers containing poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) and poly(ε‐caprolactone) units

The poly(3‐hydroxbutyrate‐co‐3‐hydroxyvalerate)/poly(ε‐caprolactone) block copolymers (PHCLs) with three different weight ratios of PCL blocks (38%, named PHCL‐38; 53%, named PHCL‐53; and 60%, named PHCL‐60) were synthesized by using PHBV with two hydroxyl end groups to initiate ring‐opening polymerization of ε‐caprolactone. During DSC cooling process, melt crystallization of PHCL‐53 at relatively high cooling rates (9, 12, and 15 °C min^?1) and PHCL‐60 at all the selected cooling rates corresponded to PCL blocks so that PHCL‐53 and PHCL‐60 were used to study the nonisothermal crystallization behaviors of PCL blocks. The kinetics of PCL blocks in PHCL‐53 and PHCL‐60 under nonisothermal crystallization conditions were analyzed by Mo equation. Mo equation was successful in describing the nonisothermal crystallization kinetics of PCL blocks in PHCLs. Crystallization activation energy were estimated using Kissinger's method. The results of kinetic parameters showed that both blocks crystallized more difficultly than corresponding homopolymers. With the increase of PCL content, the crystallization rate of PCL block increased gradually. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

同步辐射时间分辨荧光光谱技术

时间分辨光谱技术是研究原子、分子和凝聚态物质的激发动力学，特别是研究发光动力学的有力工具，文章主要介绍以同步辐射为激发光源研究时间分辨光谱的两种方法－时间相关单光子计数法和相移调制法，并比较了两者的优缺点。还讨论了同步辐射光源与其他激发光源相比的特点。     

Semi-classical quantum theory for cyclotron radiation

A semi-classical quantum theory of the cyclotron radiation of the nonrelativistic thermal electrons in a very strong magnetic field is presented. The basic formulae of the absorption coefficient of cyclotron resonancek _vand the absorption (scattering) cross-section of cyclotron resonance σ _v have been derived under the quadrupole approximation. σ _v is an important quantity in the study of the “magnetic inverse-Compton scattering”. It is shown that σ _v is greatly larger than the Thomson cross-sectron σ_T, which is important in discussing the magnetic inverse-Compton scattering of the relativistic electrons in a very strong magnetic field. Project supported by the National Natural Science Foundation of China and the Climbing Plan.     

两点齐性的 Finsler 流形

该文证明任何一个两点齐性的 Finsler 流形一定是黎曼流形. 证明过程中作者将泛函分析中经典的Mazur 定理推广到不一定是绝对齐次的 Minkowski 空间上.     

Thermodynamics of wurtzite GaN from first-principle calculation

The density function perturbation theory (DFPT) is employed to study the linear thermal expansion and heat capacity at constant pressure (with the quasiharmonic approximation) for wurtzite GaN. The calculated results of linear thermal expansion coefficient and heat capacity at constant pressure are compared with the available experimental data in a wide temperature range. Generally these properties calculated agree well with experimental data except at high temperature, thus it suggests the thermal expansion and heat capacity can be well calculated from this first-principle approach.     

Cylindrical molecular brushes with a loose grafting density

A cylindrical molecular brush with a low graft density was synthesized by two steps. Firstly, free radical alternating copolymerization of styrene (St) and N‐[2‐(2‐bromoisobutyryloxy)ethyl] maleimide (BiBEMI) gave a macroinitiator where pendant initiating sites for atom transfer radical polymerization (ATRP) being positioned along the backbone with an interval of four C? C bonds. The backbone‐to‐be with an alternating sequence was verified by elemental analysis (EA). Secondly, grafting poly(tert‐butyl acrylate) chains from the macroinitiator by ATRP produced the novel molecular brush. Size exclusion chromatography, static light scattering (SLS), and ¹H NMR and atomic force microscopy (AFM) were used to characterize the macroinitiator and the molecular brush. The results show that the backbone contains an average 730 repeat units (1 repeat unit = a pair of St and BiBEMI) and the absolute molecular weight of the brush, M_w,SLS, was 4.88 × 10⁶ Da. The brush reveals a number average length L_n to be 96 nm under AFM observation on carbon coated mica, corresponding to the length per main chain monomer unit (L_unit) of 0.066 nm, indicating a less extended conformation due to the low grafting density. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5527–5533, 2009     

大平面二极管虚阴极振荡器的宽脉冲微波辐射

给出了产生宽脉冲微波辐射的大平面天鹅绒二极管虚阴极振荡器的结构和测试装置，测得了二极管中阴－阳极等离子体的闭合速率为３０～４３ｋｍ／ｓ，获得了微波辐射的最大脉宽为１．５μｓ，产生的微波峰值功率约为１５ＭＷ，频率为０．５ＧＨＺ，指出这种平面二极管型虚阴极振荡器在辐射脉宽，辐射频率和辐射功率三者之间存在着物理上的制约关系，认为同轴型虚阴极振荡器是突破这种制约关系的一个新途径．