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.     

一种用于洗气塔的新型塔顿——淋降式穿流角钢塔板

淋降式穿流角钢塔板由于结构简单、防堵效果好、压降低，已在国内40余座塔中得到成功应用。本文主要介绍了该塔板的基本结构、压降估算、塔内排列新方案以及应用实例。     

新型无卤阻燃剂六苯胺基环三磷腈的合成

由五氯化磷和氯化铵合成了六氯环三磷腈（Ⅰ），通过亲和取代反应由苯胺和Ⅰ合成了六（苯胺基）环三磷腈（Ⅱ），对反应条件进行了优化，并对化合物Ⅰ、Ⅱ进行了元素分析、IR谱和质谱表征。用化合物Ⅱ与ABS树脂共混制备了阻燃ABS树脂，测试了其氧指数和力学性能等指标。     

环糊精和表面活性剂在室温磷光中的应用

介绍了环糊精和表面活性剂作为有序介质在室温磷光中的研究进展．并对各种方法的特点和应用情况作了简要概括。认为环糊精和表面活性剂混合介质能大大提高发光物质的室温磷光．而且操作简便．应用前景广阔。     

窑尾电除尘器燃爆的防范措施

我公司在2004年将700t/d预分解窑生产线改造为1000t／d。改造后，在窑尾75m^2板极式电除尘器前增加了一个电场（原三个电场增至四个）。然而，改造后电除尘器发生了燃爆。本文对该电除尘器燃爆原因进行分析、并提出防范措施。     

结晶紫-硼酸体系的热变色性能研究

选用羧酸类溶剂,采用固相法合成了结晶紫-硼酸系列可逆热致变色材料。考察了结晶紫和硼酸的配比、羧酸类溶剂的种类与用量以及环境温度对其热变色性能的影响。结果表明:以草酸为溶剂时,m(结晶紫)∶m(硼酸)∶m(草酸)=1∶350∶100时,颜料变色敏锐,变色温度降低到58℃,复色时间为16s,可逆性好;以丙二酸为溶剂时,m(结晶紫)∶m(硼酸)∶m(丙二酸)=1∶350∶1000时,颜料加热到68℃时,开始由浅绿色逐渐变为浅黄色,颜料色彩鲜艳,变色敏锐,复色时间仅为8s,可逆性好。DSC检测颜料的热变色过程发现2个样品在55～75℃之间都有很大的吸热峰。     

KHSO_4催化合成甘油类缩醛(酮)的研究

研究了在KHSO4催化下,丙三醇与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正辛醛、二苯甲酮、苯甲醛等十余种醛(酮)的缩合反应。系统考察了反应时间、醛(酮)与醇的配比、KHSO4的用量及催化剂重复使用等因素对反应的影响,优化了反应条件。结果表明,当醛(酮)与丙三醇摩尔比为1∶1.2,催化剂用量为2 g/1mol醛(酮),反应2 h,转化率可达90%以上,选择性可达95%以上。证明KHSO4对该缩合反应有较好的催化活性和选择性。     

超声振动对聚合物结构性能的影响

介绍了聚合物挤出成型过程中的超声振动技术，并对挤出模头引入超声振动后对聚合物物理机械性能、相容性、结晶性能的影响进行了评述。     

半刚性钢-混凝土组合节点受弯承载力的计算

在半刚性钢 -混凝土组合框架中 ,混凝土板中的纵向钢筋增加了节点的强度和刚度 ,但是 ,传统的设计方法往往忽略纵向钢筋的作用而采用简化的计算模型。因此 ,出于经济效益考虑 ,应该根据半刚性组合节点的实际受力性能建立更加准确的计算方法。这里详细介绍了考虑混凝土板纵向钢筋作用的半刚性组合节点受弯承载力的计算方法 ,计算结果表明 ,建议的公式与试验结果吻合良好 ,可供规范制定和工程应用参考。     

遥感器像移与图像参数的分析建模研究

卫星平台运动会产生恶化像质的像移,像移是影响遥感图像质量的重要因素.针对这种情况,建立了像移和图像参数的关系模型,可通过卫星生成图像的内在特征定量研究卫星成像过程中产生的像移,而不必通过产生像移的卫星平台等因素建立物理模型来研究像移.首先模拟了遥感器在轨成像过程,通过人工制造出影响因素的干扰获得了仿真图像数据,然后定量分析了像移与图像参数之间的相关性,选出了相关性较强且适合建模的图像参数,最后通过对这些图像参数构成的向量的降维得到了反映图像质量的综合参数,并建立了综合参数与像移的关系模型,以通过图像综合参数来计算像移.实验结果表明,这种模型能够很好地反映图像综合指标与像移之间的关系.该研究通过图像参数定量研究像移,为在轨运行卫星的遥感器像移与外景条件下的遥感图像要素的相关建模研究提供了部分技术支持.