基于XPS对硫铁矿去除SeO2-3的机理研究

硒是动植物及人体生长必需的十五种微量元素之一，具有清除体内自由基、抗氧化、增强免疫力等功能，但其安全剂量的范围却很窄。利用扫描电子显微镜（SEM）和X射线衍射仪（XRD）对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体，粒径范围在17～200 nm之间，平均粒径138 nm。XRD衍射图谱中的特征峰与FeS₂衍射图谱中各峰位置基本一致，因此判定硫铁矿中主要化学组分为FeS₂，且图谱中基本没有杂峰，表明制备过程中并未混入杂质，样品纯度较高。实验结果表明，该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪（XPS）对硫铁矿去除水体中SeO2-₃的机理进行了研究。研究结果表明, （1）在较为广泛的实验pH范围（pH 2.2～11.5），硫铁矿均能有效去除水体中SeO2-₃，去除效率（除pH值7.8以外）均达到90%以上；（2）硫铁矿与SeO2-₃发生反应后，其主要组成元素的XPS特征峰结合能有所减小，表明硫铁矿表面发生了一定化学变化；（3）酸碱环境下硫铁矿去除SeO2-₃的机理不完全相同，酸性环境下，硫铁矿对SeO2-₃的去除是单纯的氧化还原过程，即硫铁矿中被酸活化的S2-₂将SeO2-₃还原为单质Se(0)，并且酸性越强，SeO2-₃去除效果越好；碱性环境下，SeO2-₃的去除过程中氧化还原与络合反应并存，硫铁矿表面有络合态Fe(OH)SeO₃和单质Se(0)两种存在形态，且碱性越强，络合态Fe(OH)SeO₃含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-₃为代表的可变价金属阴离子提供重要理论依据和应用基础。     

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     

Electrochemical Detection of As(III) via Iodine Electrogenerated at Platinum,Gold, Diamond or Carbon‐Based Electrodes

The reaction of iodine, electrogenerated from iodide, is used for the detection of As(III) via electrocatalytic reaction in the diffusion layer of a boron‐doped diamond electrode. The merits of this electrode material for this purpose (over platinum, gold or glassy carbon) are demonstrated and the kinetics of the reaction between I₂ and As(III) in acid reported.     

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     

An optical fibre pH sensor based on dye doped mesostructured silica

This paper describes the synthesis and optical pH sensing properties of a pH indicator dye activated mesostructured silica coated optical fibre. The pH-sensitive dye bromothymol blue was incorporated into the mesostructure sol precursor and thin films/coatings were used for pH-sensing applications without prior removal of the surfactant. The pH sensitivity range and operating wavelength were analysed by absorption measurements on layer dip-coated on glass slides. The pH sensing properties of coated optical fibre were tested by evanescent wave method. Experiments were carried out by using a series of solutions of known pH. No leaching was observed (except at very high pH) and an excellent reversibility was obtained between pH=2 and 5.     

Urea method for the synthesis of hydrotalcites

Mg-Al, Zn-Al and Ni-Al hydrotalcite-like compounds with high crystallinity were synthesized by using the decomposing property of urea at high temperature. The crystallinity and the regularly of the samples were much preferable to those synthesized by other methods. This revised version was published online in June 2006 with corrections to the Cover Date.