Spectroscopic studies of copper, silver and gold-metallothioneins

Metallothionein is a ubiquitous protein with a wide range of proposed physiological roles, including the transport, storage and detoxification of essential and nonessential trace metals. The amino acid sequence of isoform 2a of rabbit liver metallothionein, the isoform used in our spectroscopic studies, includes 20 cysteinyl groups out of 62 amino acids. Metallothioneins in general represent an impressive chelating agent for a wide range of metals. Structural studies carried out by a number of research groups (using (1)H and (113)Cd NMR, X-ray crystallography, more recently EXAFS, as well as optical spectroscopy) have established that there are three structural motifs for metal binding to mammalian metallothioneins. These three structures are defined by metal to protein stoichiometric ratios, which we believe specifically determine the coordination geometry adopted by the metal in the metal binding site at that metal to protein molar ratio. Tetrahedral geometry is associated with the thiolate coordination of the metals in the M(7)-MT species, for M = Zn(II), Cd(II), and possibly also Hg(II), trigonal coordination is proposed in the M(11-12)-MT species, for M = Ag(I), Cu(I), and possibly also Hg(II), and digonal coordination is proposed for the metal in the M(17-18)-MT species for M = Hg(II), and Ag(I). The M(7)-MT species has been completely characterized for M = Cd(II) and Zn(II). (113)Cd NMR spectroscopic and x-ray crystallographic data show that mammalian Cd(7)-MT and Zn(7)-MT have a two domain structure, with metal-thiolate clusters of the form M(4)(S(cys))(11) (the alpha domain) and M(3)(S(cys))(9) (the beta domain). A similar two domain structure involving Cu(6)(S(cys))(11) (alpha) and Cu(6)(S(cys))(9) (beta) copper-thiolate clusters has been proposed for the Cu(12)-MT species. Copper-, silver- and gold-containing metallothioneins luminesce in the 500-600 nm region from excited triplet, metal-based states that are populated by absorption into the 260-300 nm region of the metal-thiolate charge transfer states. The luminescence spectrum provides a very sensitive probe of the metal-thiolate cluster structures that form when Ag(I), Au(I), and Cu(I) are added to metallothionein. CD spectroscopy has been used in our laboratory to probe the formation of species that exhibit well-defined three-dimensional structures. Saturation of the optical signals during titrations of MT with Cu(I) or Ag(I) clearly show formation of unique metal-thiolate structures at specific metal:protein ratios. However, we have proposed that these M=7, 12 and 18 structures form within a continuum of stoichiometries. Compounds prepared at these specific molar ratios have been examined by X-ray Absorption Spectroscopy (XAS) and bond lengths have been determined for the metal-thiolate clusters through the EXAFS technique. The stoichiometric ratio data from the optical experiments and the bond lengths from the XAS experiments are used to propose structures for the metal-thiolate binding site with reference to known inorganic metal-thiolate compounds.     

混凝浑液面沉速与混凝剂投加量的关系研究

探讨了黄河高浊度水混凝沉淀浑液面沉速与自然沉速之间的相关性,经过对实验数据进行线性回归提出了混凝过程中浑液面沉速与自然沉速、含沙量、PAM投加量之间的经验公式。运用该经验公式得出的浑液面沉速计算值与实测相对误差在0.43%～12.27%之间。     

基于高速局域网的连续搅拌反应釜(CSTR)控制系统

提出基于客户－服务器模式的连续搅拌反应釜（CSTR）控制系统。系统充分利用网络设备和技术，扩大了实时控制设备的应用范围和资源利用率，方便了学生学习和巩固基本的控制理论和技术。本系统可提供的操作（控制策略）有PID控制和鲁棒控制，同时还提供传输可执行文件和反馈执行结果的功能，以便测试实验者自行编写的算法程序。     

Influence of organophilic clay and preparation methods on EVA/montmorillonite nanocomposites

Ethylene‐vinyl acetate copolymer (EVA)/montmorillonite MMT nanocomposites have been prepared by using different methods: one is from the organophilic montmorillonite (OMT) and the other is from the pristine MMT and reactive compatibilizer hexadecyl trimethyl ammonium bromide (C16). In this study, different kneaders were used (twin‐screw extruder and twin‐roll mill) to prepare nanocomposites. The nanocomposite structures are evidenced by the X‐ray diffraction (XRD) and high‐resolution electronic microscope (HREM). The thermal properties of the nanocomposites were investigated by thermogravimetric analysis (TGA). Moreover, the tensile tests were carried out with a Universal testing machine DCS‐5000. It is shown that different methods and organophilic montmorillonite have influence on EVA/MMT nanocomposites.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2416–2421, 2004     

Effects of an organic phosphorus nucleating agent on crystallization behaviors and mechanical properties of poly(propylene)

The effects of an organic phosphorus nucleating agent on the crystallization behavior and mechanical properties of poly(propylene) were investigated. As the concentration of nucleating agent increased from 0 to 0.8%, the tensile and flexural strengths of the nucleated poly(propylene) resin increased by 15%, the flexural modulus increased by 35%, the crystallization peak temperature increased by 10°C, and the nucleation density (calculated with the nonlinear Voltrra integral equation) increased by 10⁶ times. Mechanical properties increased with nucleation density. Linear equations between the mechanical properties and the logarithmic nucleation density were revealed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 297–301, 2003     

改进的GrabCut方法在舌诊系统中的应用

数字舌象图片的正确分割是实现计算机中医舌诊自动化系统的重要前提,为了高效而准确地分割出舌象,提出了一种基于四叉树与GrabCut的舌象分割方法.该方法首先利用四叉树分解对采集的舌象初分割,然后用相似区域的颜色均值优化GrabCut算法中高斯混合模型参数,最终完成舌象分割.实验结果表明：该算法使得舌象分割效率大大提高,具有很好的实用性.     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.     

喷射电沉积块体纳米晶Co-Ni合金工艺的研究

利用扫描电子显微镜（SEM），能谱仪（EDS）及X射线衍射（XRD）等分析方法研究了工艺参数对电解液喷射电沉积法制备块体纳米晶Co-Ni合金沉积层成分及结构的影响。结果表明；在本实验条件下，随电解液喷射速度的增加，沉积层中钴含量增加，而晶粒尺寸减小；随电解液温度的升高，沉积层中钴含量减小到一定值后增大，晶粒尺寸呈相反的趋势。沉积层的表面形貌为胞状结构。     

Electrochemical behaviour of copper/LDPE composites in the simulated uterine solution

Two metal/insulator composites, copper/low-density polyethylene (LDPE) microcomposites and copper/LDPE nanocomposites, were prepared in a uniform metal mass fraction. The corrosion characteristics of the two composites in the simulated uterine solution have been studied by cyclic voltammetry, potentiodynamic polarization measurement and electrochemical impedance spectroscopy. Results obtained during this study show that there are obvious differences on the corrosive rates and mechanisms between the two materials. The nanocomposites have stable corrosive reaction, hardly passivation, low corrosion rate and high transformation ratio of copper to soluble cupric ions compared with microcomposites, which indicate that the nanocomposites are perfect to be the novel material for intrauterine device. The corrosion behaviour of the microcomposites was controlled by both the processes of the pervasion of Cu²⁺ and the transfer of the charge, while that of the nanocomposites was only controlled by the transfer of the charge. This paper also compared the corrosion behaviours of the composites and bulk copper in the simulated uterine solution, there were more insoluble subproducts in the corrosion process of bulk copper than the composites. Further, the electrochemical method in this study is proved to be useful to characterize the corrosion behaviour of high electrical resistivity materials.     

短纤维/橡胶发泡复合材料的微观结构及拉伸破坏机理

对锦纶短纤维增强的NR发泡材料的微观结构及拉伸破坏行为进行了研究，并分析了其破坏机理。采用未处理短纤维增强的NR发泡材料中短纤维成为泡孔的成核点，并大部分悬空在泡孔中，拉伸破坏时泡壁与短纤维结合处容易出现应力集中，成为裂纹的起始点，失效时短纤维大部分被抽出；预处理短纤维能与橡胶基体之间产生良好的粘合，从而处于橡胶基体中。其短纤维增强的NR发泡体拉伸产生的裂纹扩展时遇到纤维，纤维能起到承载应力、使应力转向、阻止裂纹扩展的作用，一定程度上改善了复合材料的拉伸强度等物理性。