Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

Magnetic poly(N‐isopropylacrylamide) microspheres by dispersion and inverse emulsion polymerization

The aim of this study was to develop novel thermally responsive polymer microspheres with magnetic properties. Dispersion and inverse emulsion copolymerization of N‐isopropylacrylamide (NIPAAm) and N,N′‐methylenebisacrylamide (MBAAm) was investigated in the presence of γ‐Fe₂O₃ nanoparticles. The resulting microspheres were characterized in terms of morphology, size, polydispersity, iron content, and temperature‐dependent swelling using optical microscopy, transmission electron microscopy, scanning electron microscopy, QELS, and AAS. The effects of several variables, such as the concentration of γ‐Fe₂O₃, MBAAm crosslinking agent, Span 80 surfactant, 2,2′‐azobis(2‐methyloctanenitrile) (AMON) initiator, and polymerization temperature on the properties of the microspheres were studied. Swelling and thermoresponsive behavior of the microspheres containing γ‐Fe₂O₃ nanoparticles were also investigated. The microspheres contained about 8 wt % of iron. The presence of magnetic nanoparticles and their concentration changes did not have any significant effect on the temperature sensitivity of the composites. The particles gradually shrink into an increasingly collapsed state when the temperature is raised to 40 °C since the increase in temperature weakens the hydration and PNIPAAm chains gradually become more hydrophobic, which leads to the collapse of the particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5884–5898, 2007     

Multiphysical modeling and meshless simulation of electric‐sensitive hydrogels

According to a multiphase mixture theory, we have mathematically developed a multiphysical model with chemoelectromechanical coupling considerations, termed the multieffect‐coupling electric‐stimulus (MECe) model, to simulate the responsive behavior of electric‐sensitive hydrogels immersed in a bath solution under an externally applied electric field. For solutions of the MECe model consisting of coupled nonlinear partial differential governing equations, a meshless Hermite–Cloud method with a hierarchical iteration technique has been used for a one‐dimensional steady‐state analysis of a hydrogel strip. The computed results are compared with the experimental data, and there is very good agreement. Simulations within the domains of both hydrogels and surrounding solutions also present distributions of the ionic concentrations and electric potential as well as the hydrogel displacement. The effects of various physical parameters on the response behavior of electric‐stimulus responsive hydrogels are discussed in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1514–1531, 2004     

多壁碳纳米管膜湿敏特性的研究

研究了多壁碳纳米管(MWNTs)薄膜的湿敏特性，实验所用的多壁碳纳米管是用热灯丝化学气相沉积法(CVD)合成的.分别对未修饰和修饰的多壁碳纳米管膜温度和湿度特性进行研究后发现，修饰的多壁碳纳米管对温度和湿度非常敏感，且对湿度的响应时间和恢复时间短，重复性好.而未修饰的多壁碳纳米管对温度和湿度不太敏感.对修饰多壁碳纳米管的湿敏特性进行了理论分析，给出了其理论表示式. 关键词： 多壁碳纳米管 化学修饰 湿敏特性 物理吸附     

Probability relations involving several subsystems

We consider the question of factorizability in tensor product spaces, and argue that the correlations associated with entangled states are even more problematic in the general case involving any tensor product of Hilbert spaces, than in the Einstein, Podolsky, and Rosen case with only two [1].     

二维光电位置敏感器件的非线性修正

根据二维光电位置敏感器件 (PSD)的工作原理 ,分析了影响PSD线性度的主要因素 ,提出了一种用神经网络对PSD进行非线性修正的方法。以PSD的输入输出数据对作为样本训练的神经网络 ,利用神经网络所具有地能够以任意精度逼近非线性函数的能力 ,实现PSD的输出与实际光点位置之间的映射 ,在神经网络的输出端得到线性响应。该方法的优点是不需要很大的数据存储量即可得到很好的修正效果。结果表明 ,修正后的PSD能在较宽的位置范围内输出高线性度的信号     

利用计算机辅助装调检测矩形大口径离轴非球面的方法研究

通过非球面的零位补偿法,完成了对矩形大口径离轴非球面镜的检测。先用光学设计软件Zemax从理论上分析了在检测中会出现的现象,并结合计算机辅助装调技术,确定在检测过程中相对敏感的自由度,然后控制这些量,使补偿器和非球面的相对关系与理论设计相吻合,在Zygo相位干涉仪上测得最终结果。在λ=632.8nm时,中心圆口径与两个边缘圆口径面形误差RMS分别为0.022λ,0.037λ,0.032λ。检测结果,达到预期目的。     

Stimuli‐responsive polymers. VIII. Polyesters and poly(ester amides) containing azobenzene and chiral binaphthylene segments: Highly adaptive materials endowed with light‐, heat‐, and solvent‐regulated optical rotatory power

Azobenzene‐modified polyesters and poly(ester amide)s fitted with chiral, atropisomeric binaphthylene segments were prepared by a series of low‐temperature polycondensation reactions carried out in polar solvent media. When compared with their polyaramide counterparts studied earlier, these materials had significantly improved solubility behaviors and were readily dissolved by a wide range of organic solvents. In solution, each of these constructs underwent photoinduced oscillations in optical rotatory power when subjected to multiple UV‐light/visible‐light illumination cycles that drove trans?cis isomerization reactions along their polymer chains. Light‐regulated chiroptical perturbations were dependent on polymer backbone structures and were further modulated by well‐coordinated temperature fluctuations and by the nature of the solvent medium employed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 207–218, 2006     

Copolymerization of N‐vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control

Free‐radical copolymerizations of N‐vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) were investigated to synthesize temperature‐responsive reactive copolymers with minimized compositional heterogeneity. The average copolymer composition was determined by Fourier transform infrared and nuclear magnetic resonance techniques. The reactivity ratios for VCL and GMA were found to be 0.0365 ± 0.0009 and 6.44 ± 0.36 by the Fineman–Ross method and 0.039 ± 0.006 and 6.75 ± 0.29 by the Kelen–Tudos method, respectively. When prepared by batch polymerization, VCL–GMA copolymers had a highly heterogeneous composition and fractions of different solubilities in water. The use of a gradual feeding technique, which included the sequential addition of more reactive GMA monomer into the reaction, yielded copolymers with much more homogeneous composition. The produced copolymers with 0.9 and 0.11 fractional GMA contents preserved their temperature‐responsive properties and precipitated from aqueous solutions when the temperature exceeded 31 °C. The GMA units in the VCL–GMA copolymers were capable of reacting with amino end‐functionalized poly(ethylene oxide) at room temperature to produce poly(N‐vinylcaprolactam)–poly(ethylene oxide) graft copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 183–191, 2006