KineticsandMechanismStudiesontheInteractionofTetramethoxylbenzoquinonewithPiperidines

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七种卤乙酸在紫外辐照下的光降解行为(英文)

针对典型的氯消毒副产物卤乙酸,研究选取了7种卤乙酸,包括3种氯乙酸,3种溴乙酸和1种碘乙酸,研究其在紫外辐照下的光降解行为;并针对卤乙酸的类型和卤化程度,对比和分析了不同卤乙酸的光降解规律。结果表明:7种卤乙酸都能够被紫外降解,动力学研究结果显示,氯乙酸,溴乙酸和碘乙酸的光降解行为有很大不同,其中溴乙酸满足一级动力学模型。离子色谱检测分析了7种卤乙酸光降解过程中卤素离子的释放结果发现,碳卤键在紫外照射下发生了断裂,实现了脱卤和脱毒。为水中卤乙酸的高效去除提供了一定的技术参考和理论支撑。     

Al_(88)Co_4Y_6Er_2非晶合金的晶化动力学行为

采用单辊旋淬法制备了Al88Co4Y6Er2非晶合金,差热分析手段研究了该非晶合金晶化动力学性能.根据约化玻璃转变温度Trg,发现Er(2at%)元素部分取代Al88Co4Y8非晶合金中的Y元素后,得到的Al88Co4Y6Er2非晶合金具有更强的玻璃形成能力.计算得到Al88Co4Y6Er2非晶合金的晶化激活能,初始晶化激活能为381 kJ·mol-1,发现Al88Co4Y6Er2非晶合金具有很好的热稳定性.     

镁基储氢材料的热力学和动力学*

金属和合金的吸放氢反应是储氢材料进行的基本物理化学反应。它应服从基本的热力学和动力学规律。为此,想要改善储氢材料的性能,研发新型的储氢材料就需要对此过程的理论和实验两方面作深入的研究。通过热力学和相图能估算储氢的能力,预估吸放氢的可能温度,但要使储氢材料变得切实可行,还需要靠动力学方面的工作。笔者从热力学和相图入手,研究了储氢材料的特征,分析了传统的动力学处理方法的缺陷,提出了新的动力学模型,从而将为寻求新型的储氢材料提供有效的工具。笔者还总结了从实验上探索的一些新型储氢体系。     

无机功能晶体材料的结晶过程研究

功能晶体材料作为光、声、电等转换的重要介质,已经被广泛应用于能源、信息、航空航天等高新技术领域,是目前国际材料科学与工程学科发展的热点和前沿课题.结晶过程是制备功能材料的核心环节,结晶习性直接影响材料的光、电、磁、催化等功能特性.在无机材料的结晶过程中,晶体组成在微观上经历了从自由态离子到结晶态固体的相变过程.可以借助晶体组成离子的电负性及基团微观对称性的变化,研究结晶过程中聚集体的形成和结构演变规律.利用分子振动光谱能够从分子尺度上揭示非线性光学晶体材料在水溶液结晶过程中结晶学结构的形成过程,克服了传统原位观测手段中缺乏对非长程有序结构的确定.利用结晶生长的化学键合理论从热力学和动力学两个方面指导大块晶体的生长实践,合理调控晶体的生长表/界面热力学和动力学.将结晶生长的化学键合理论应用到大尺寸晶体提拉生长参数的设计和优化,成功搭建了大尺寸晶体智能生长系统,并成功生长了φ2″蓝宝石晶体、φ3″YAG晶体和φ4″铌酸锂晶体.     

Identifying the conformational state of bi-liganded haemoglobin

While most researchers agree on the global features of cooperative ligand binding to haemoglobin (Hb), the internal mechanisms remain open to debate. This is not due to inaccurate measurements, but is rather a consequence of the cooperative ligand binding that decreases the equilibrium populations of the partially liganded states and makes observation of the transitions between these substates more difficult. For example, the equilibrium population of the doubly liganded tetramers is typically less than 5% of the total Hb. As a result many models with widely varying mechanisms may fit the oxygen equilibrium curve, but may not be consistent with observations of other parameters, such as ligand-binding kinetics or subunit association equilibria. The wide range of methods and models has led to divergent conclusions about the properties of specific substates. One notable debate concerns the properties of the doubly liganded forms. The simple two-state model predicts a shift in the allosteric equilibrium based on the number of ligands bound, but not on their distribution within the tetramer. From studies of dimer-tetramer equilibria of various pure and hybrid forms, it was concluded that a tetramer with two ligands bound on the same α β dimer (species 21, an asymmetric hybrid) shows an enhanced tetramer stability, similar to singly liganded Hb, relative to the other three types of doubly liganded tetramers which resemble the triply liganded forms [Ackers et al. (1992), Science 255: 54–63]. The implications of this model and the relevant experiments will be reviewed here. Received 27 April 1998; received after revision 17 July 1998; accepted 10 August 1998     

Recent results on hydrogen and hydration in biology studied by neutron macromolecular crystallography

Neutron diffraction provides an experimental method of directly locating hydrogen atoms in proteins, a technique complimentary to ultra-high-resolution [1, 2] X-ray diffraction. Three different types of neutron diffractometers for biological macromolecules have been constructed in Japan, France and the United States, and they have been used to determine the crystal structures of proteins up to resolution limits of 1.5-2.5 A. Results relating to hydrogen positions and hydration patterns in proteins have been obtained from these studies. Examples include the geometrical details of hydrogen bonds, H/D exchange in proteins and oligonucleotides, the role of hydrogen atoms in enzymatic activity and thermostability, and the dynamical behavior of hydration structures, all of which have been extracted from these structural results and reviewed. Other techniques, such as the growth of large single crystals, the preparation of fully deuterated proteins, the use of cryogenic techniques, and a data base of hydrogen and hydration in proteins, will be described.     

Role of Cys221 and Asn116 in the zinc-binding sites of the Aeromonas hydrophila metallo-β-lactamase

The CphA metallo--lactamase produced by Aeromonas hydrophila exhibits two zinc-binding sites. Maximum activity is obtained upon binding of one zinc ion, whereas binding of the second zinc ion results in a drastic decrease in the hydrolytic activity. In this study, we analyzed the role of Asn116 and Cys221, two residues of the active site. These residues were replaced by site-directed mutagenesis and the different mutants were characterized. The C221S and C221A mutants were seriously impaired in their ability to bind the first, catalytic zinc ion and were nearly completely inactive, indicating a major role for Cys221 in the binding of the catalytic metal ion. By contrast, the binding of the second zinc ion was only slightly affected, at least for the C221S mutant. Mutation of Asn116 did not lead to a drastic decrease in the hydrolytic activity, indicating that this residue does not play a key role in the catalytic mechanism. However, the substitution of Asn116 by a Cys or His residue resulted in an approximately fivefold increase in the affinity for the second, inhibitory zinc ion. Together, these data suggested that the first zinc ion is located in the binding site involving the Cys221 and that the second zinc ion binds in the binding site involving Asn116 and, presumably, His118 and His196.Received 3 March 2003; received after revision 4 August 2003; accepted 25 August 2003     

探索多组分体系高分子相变复杂性的真谛

笔者首先介绍了单组分物质在气液固三态之间的转变,然后介绍了在二元溶液体系中如何采用类比移植的方法进行科学研究,接着介绍基于这一方法对多组分体系高分子的相分离和结晶所展开的研究,两种相变的相互作用揭示了高分子相变复杂性的真谛。