Tetraaqua(1,10-phenanthroline-kappa(2) N, N ')copper(II)naphthalene-1,5-disulfonate dihydrate

In the title structure, [Cu(C12H8N2)(H2O)(4)](C10H6S2O6)center dot-2H(2)O, the cation lies on a crystallographic twofold rotation axis and the anion lies on a centre of inversion. The Cu-II atom is coordinated by two N atoms of a 1,10-phenanthroline ligand and four O atoms from four water ligands in a distorted octahedral geometry. The unique Cu-O distances are 2.054 (2) and 2.088 (2) angstrom and the Cu-N distance is 2.073 (2) angstrom. In the crystal structure, a three-dimensional supramolecular framework is constructed by extensive intermolecular O-H center dot center dot center dot O hydrogen bonds.

Synthesis and evaluation of a thiourea-modified chitosan derivative applied for adsorption of Hg(II) from synthetic wastewater

In this work, a thiourea-modified chitosan derivative (TMCD) was synthesized through two steps, O-carboxymethylated first and then modified by a polymeric Schiff's base of thiourea/glutaraldehyde. The adsorption behavior of mercury (II) ions onto TMCD was investigated through batch method. The maximum adsorption capacity for Hg(II) was found to be 6.29 mmol/g at pH 5.0 and both kinetic and thermodynamic parameters of the adsorption process were obtained. The results indicated that adsorption process was spontaneous exothermic reaction and kinetically followed pseudo-second-order model. The adsorption experiments also demonstrated TMCD had high adsorption selectivity towards Hg(II) ions when coexisted with Cu(II), Zn(II), Cd(II) and Ca(II) in solution and it could be easily regenerated and efficiently reused. (C) 2010 Elsevier B.V. All rights reserved.

Ca 2+对叶绿体膜流动性及光系统II叶绿素蛋白质复合物的影响

通过实验我们证明Ca2+对叶绿体膜的流动性，对PS I和PS II叶绿素蛋白质复合物的相对含量，以及PS I和PS II的多肽均有影响。 Ca2+对叶绿体膜表层的流动性影响不大，但降低了叶绿体膜深层脂质分子的流动性。从另一个角度阐明了Ca2+抑制光能从PS II向PS I传递的机制。 Ca2+可使PS I的21，23，110KD的多肽转移至PS II，LHCP1和LHCP2中的CF1的两个亚基（55，60KD）转至CPa和LHCP3，从而增加了PS II的捕光截面，引起激发能在两个系统之间的分配的改变。 用免疫学方法可以证明CPIa2和LHCP2的Ab为复合抗体，CPIa1的Ab为单抗，我们可以推测向日葵的不同叶绿素蛋白质复合物具有同源性。

ApcD is necessary for efficient energy transfer from phycobilisomes to photosystem I and helps to prevent photoinhibition in the cyanobacterium Synechococcus sp PCC 7002

Phyrobilisomes (PBS) are the major light-harvesting, protein-pigment complexes in cyanobacteria and red algae. PBS absorb and transfer light energy to photosystem (PS) II as well as PS I, and the distribution of light energy from PBS to the two photosystems is regulated by light conditions through a mechanism known as state transitions. In this study the quantum efficiency of excitation energy transfer from PBS to PS I in the cyanobacterium Synechococcus sp. PCC 7002 was determined, and the results showed that energy transfer from PBS to PS I is extremely efficient. The results further demonstrated that energy transfer from PBS to PS I occurred directly and that efficient energy transfer was dependent upon the allophycocyanin-B alpha subunit, ApcD. In the absence of ApcD, cells were unable to perform state transitions and were trapped in state 1. Action spectra showed that light energy transfer from PBS to PS I was severely impaired in the absence of ApcD. An apcD mutant grew more slowly than the wild type in light preferentially absorbed by phyrobiliproteins and was more sensitive to high light intensity. On the other hand, a mutant lacking ApcF, which is required for efficient energy transfer from PBS to PS II, showed greater resistance to high light treatment. Therefore, state transitions in cyanobacteria have two roles: (1) they regulate light energy distribution between the two photosystems; and (2) they help to protect cells from the effects of light energy excess at high light intensities. (C) 2009 Elsevier B.V. All rights reserved.

流动注射－分光光度法测定痕量元素

本论文采用不同的流动注射分析流路和技术对流动注射－分光光度法测定痕量元素进行了研究。建立了锌合金中铜、多种合金中稀土总量的快速测定及高灵敏的催化光度分析痕量锰的分析方法。（一）锌合金中铜的流动注射分光光度分析 研究了和种显色条件和仪器参数对灵敏度和分析速度的影响，并进行了选择。建立了以高选择性的BCO（双环已酮草酰二腙）为显色剂的单流路流动注射－分光光度分析方法。方法具有简便、快速（每小时分析90个样、精度高特点，用于锌合金实际样品分析的结果与常规分光光度法一致。测定的线性范围为0～10ppm Cu(II)。（二）合并带法流动注射分析合金中稀土总量 采用高灵敏和高选择性的DBC-偶氮氯膦的显色剂，结合经济的流动注射合并带技术，对多种合金中的稀土总量的快速测定进行了研究，分别提出了合金中轻、重稀土总量的分析方法。实验表明，方法简便、快速（每小时可测120个样以上），节省试剂、灵敏度高，适用性广（目前已用于铝、锌和镁合金中稀土总量的测定）。分析结果的精度和准确度都令人满意。（三）停流法－催化动力学分析痕量锰 采用停流技术，研究了各种条件对锰催化高碘酸钾与孔雀绿反应体系的影响，提出了痕量锰的催化动力学高灵敏分析方法。方法具有操作极为简便、灵敏、快速（5个样次/小时）选择性好等优点。水样中PPb级的Mn(II)可以不经预浓缩直接测定。分析结果的精密度和标准加入回收实验都较满意。测定的线性范围为0-7.2PPb Mn(II)。

流动注射法测定无机成分的研究

本篇做了以下两方面的工作：停流流动注射分光光度法间接测定钴方法的建立及其在草药中钴含量的测定。本方法将Fe（III）－1.10邻菲啰啉－Co（II）的氧化还原体系应用于流动注射分析，首先克服了本体系反应时间长、分析速度慢的缺点，从而使分析频率由4次／小时提高到120次／小时，进一步试验表明，本方法具有很高的选择性，性质类似的Ni（II）、Cu（II）等元素，其干扰允许量也高达钴浓度的102倍以上。这在测钴的其它方法中是少见的。本体系比较稳定，温度高于25℃时，灵敏度几乎不随温度变化。为了使本法在F1A上的灵敏度不受较大的损失，实验中，设计了短反应营络中部停流的方法，一方面，减少了试样在营络中运行所造成的扩散；另一方面，停流使得本方法的灵敏度外高。试验中，还设计了短反应营络套营式的恒温方法，简单而易行。本方法的线性分析范围分别为0～12ppm（19℃），0～10ppm（35℃），0～6ppm（40℃）。测定下限为0.7ppm(10s)，RSD=1.3％。这与方法就体系本身来说，在分析上的应用尚是第一次，而且实验中所设计的F1A停流方法也是文献中不曾报导的。论文的后半部分对草药中钴的含量进行了测定。首先确立了试样的消解方法，对几种常用于治疗肝病的草药（麦皮、川练子、桔叶、元胡、郁金）及维生素B_(12)中钴含量预以测定，结果是，草药中，川练子中钴的含量较高。为了探查钴在草药煎制过程中的转移情况，本文模拟中药煎制过程，制取乙醇及水的川练子浸提液，并对浸提液及残渣中钴的含量邓以测定。结果表明，对于钴的提取，水煎的交果比乙醇浸提的效果好。在浸提液的测试过程中，还建立了吸收基底的数字校正模型（包括恒定及变化基底的校正）由此法得到的浸提液及残渣中钴含量的字值与川练子总体测定值相符。以上的测定结果，对于以钴为纽带，探讨中西医药的联系有一定的参考价值。

具有生物兴趣的金属络合物的制备与结构研究

维生素B_1(V_(B_1))是一种动物体内不可缺少的生物催化剂，它的生物功能只有在某些二价金属离子存在时才能得以发挥。本工作制备了维生素B_1与Mn(II)，Co(II)，Cu(II)，Zn(II)，Cd(II)，Hg(II)等六种过渡金属的络合物，对其进行了元素分析及红外光谱，核磁共振增，紫外一可见光谱，萤光光谱，X-射线晶体结构，热重等性质的测定。研究了上述络合物的结构特性及生成机理。结果表明。V_(B_1)与上述金属离子可以生成三种类型的络合物—离子型、M-N 配位型号以及M-O配位与离子键共存型。其中最后一种类型的V_(B_1)—金属络合物是本工作中新的发现。我们首次制得了属于M-O配位与离子键共存类型的V_(B_1)-Hg络全物并测定了它的晶体结构，首次测定了Zn-V_(B_1)络合物的晶体结构。根据光谱学，波谱学性质推测了其他络合物的化学结构。本工作还制备了维生素P的主要组分芦丁和四氯四碘萤光素二个系列各十三种稀土元素 络合物并对其进行了元素分析及热重，电导，红外光谱、紫外—可见光谱等性质的测定，研究了这些络合物的化学结构及生成机理。

铜（III）及相关化合物的合成和性质的研究，稀土复合氟化物电性、氧敏和氢敏性质

本论文包括两部分内容。第一部分为“Cu(III)及相关化合物的合成和性质的研究”；第二部分为“稀土复合氟化物的电性、氧敏和氢敏性质”。第一部分的主要内容有：1.制备了Na_4H[Cu(H_2TeO_6)_2]·17H_2O和Na_4K[Cu(HIO_6)_2]·12H_2O的Cu(III)单晶配合物。2.在比较相应的Cu(II)化合物的条件下，详细地研究了这二个Cu(III)配合物的电子光谱和Cu2p光电子能谱，由于价态升高，场强参数增大，Cu(III)化合物的d-d跃迁相对于Cu(II)化合物d-d跃迁，发生“蓝移”。3.成功地实现了用O_3和电化学方法对强碱溶液中Cu(II)配合物的氧化，获得了二个新的Cu(III)固态配合物Ba_4K[Cu(H_2TeO_6)_2] (OH)_4·6H_2O和Ba_3K[Cu(HIO_6)_2] (KOH)_(0.5)(OH)_2·8H_2O利用化学分析、磁学性质、电子光谱和Cu2p XPS，对这二个化合物进行了表征。4.对BaCuO_(2.5)的合成、电学性质、磁学性质、Cu(III) ESR和Cu2p XPS进行了研究。5.以Na_4K[Cu(HIO_6)_2]·12H_2O和BaCuO_(2.5)为参照物，用电子光谱和Cu2p XPS，确认了YBa_2Cu_3O_(7-5)中的高价态的铜。6.考察了以Cu（III）化合物作为Cu部分原料所合成的YBCO系超导材料的电学性质。第二部分的主要内容有：1.测试了元件“BiF_3(Bi)/Ce_(0.95)Ca_(0.05)F_(2.95)/Pt”的氧敏、氢敏等性能。从室温到130 ℃，元件的氧敏机理为“双电子反应”，电动势（EMF）与氧分压遵循Nernst关系式。室温时，元件对空气中100Pa或1000Pa氢气的响应时间仅为15秒或短于5秒；氢分压在16Pa～1000Pa范围内，EMF与氢分压的对数呈线性关系，斜率为-116mV/decade, 敏感机理表现为“混合电极电势”。元件具有良好的氢敏性能，并有一定的选择性。2.合成并测试了La_(1-x)Pb_xF_(3-x)(X = 0.00 ～ 0.15)的电导率，La_(0.95)Pb_(0.05)F_(2.95)的电导率最高，比LaF_3高约一个数量级。以La_(0.95)Pb_(0.05)F_(2.95)为固体电解质材料，Pd或Pt为敏感电极，BiF_3(Bi)或PbF_2(Pb)为参比电极，制成了四个元件。其中，“BiF_3(Bi)/La_(0.95)Pb_(0.05)F_(2.95)/Pt”具有最好的氧敏、氢敏性能。从室温到150 ℃，元件的EMF与1gPo_2附合Nernst关系式。150 ℃时，元件对氧气的响应时间仅为80秒。室温下，元件对空气中100Pa或1000Pa氢气的响应时间仅为75秒或15秒，元件的电动势EMF与氢分压的关系可表示为“E=E_o-96lgP_(H2)(mV)”。元件对CO有较差的敏感性能，而对空气中甲烷、乙烷或乙炔（≤1000Pa）不具敏感性能。3.合成并测试了Ln_(1-x)Pb_xF_(3-x)(Ln=Ce、Pr、Nd和Gd、Dy、Ho、Yb)的电性。前四个系列为离子导体材料，后三个系列可能为P型半导体。随着Ln原子序数增大，LnF_3导电性能变差；La~(3+)、Ce~(3+)、Pr~(3+)、Nd~(3+)与Pb~(2+)离子半径差异较小，LnF_3和PbF_2可以形成固溶体；而Gd~(3+)、Dy~(3+)、Ho~(3+)、Yb~(3+)与Pb~(2+)离子半径差异较大，LnF_3和PbF_2难以形成固溶体。

Binding of metal ions with protein studied by a combined technique of microdialysis with liquid chromatography

A method has been developed for the determination of interactions of metal ions and protein by using microdialysis sampling technique combined with pre-column derivation and reversed-phase ion-pair liquid chromatographic (HPLC analysis. Cu(II), Zn(II) and human serum albumin (HSA) were chosen as model metal ions and protein, respectively. The mixed solutions of metal ions and HSA with different molar ratios buffered with 0.1 M Tris-HCl containing 0.1 M NaCl at pH 7.43 were sampled with a mirodialysis probe by keeping perfusion rate at 1 mul/min and the temperature at 37 degreesC. The free concentrations of metal ions in microdialysates were assayed by precolumn derivatization with meso-tetra(4-sulfophenyl)-porphyrin (TPPS4) followed ion-pair HPLC analysis. The recovery (R) of microdialysis sampling was measured in vitro under similar conditions as 65.74% for Cu(II), 70.45% for Zn(II) with R.S.D. below 3.2%. The primary binding constants and number of binding site estimated by the Scatchard plot analysis are 5.04 x 10(6) M-1 and 0.85 for Cu(II), and 9.87 x 10(6) M-1 and 1.10 for Zn(II), respectively. The competition of Cu(II) and Zn(II) at the second binding site on HSA was investigated, and it was observed that there is a second site on HSA to bind Cu(II) and Zn(II), the affinity of Cu(II) is stronger than that of Zn(II) to this second site of HSA. (C) 2001 Elsevier Science B.V. All rights reserved.

The Synthesis and Characterization of a Novel (E,E)-Dioxime and its Mono- and Heterotrinuclear Complexes Containing an 18-Membered Dioxadithiadiazamacrocycle

The novel (E,E)-dioxime, 5,6:17,18-dibenzo-11,12-(4-nitrobenzo)-2,3-bis(hydroxyimino)-7,16-dithia-10,13-dioxa-1,4-diazacyclooctadecane) (H2L), has been synthesized from reaction of (E,E)-dichloroglyoxime (1) with 2,3:14,15-dibenzo 8,9-(4-nitrobenzo)-4,13-dithia-7,10-dioxa-1,16-diazahegzadecane (2). The mononuclear Co(III) complex (4) of this dioxime was prepared by oxidation of the cobalt (II) complex. The -capped Co(III) complex (5) was synthesized by using a precursor Co(III) complex and boron trifluoride dietherate. The heterotrinuclear complexes (6) and (7) were prepared by reaction of (5) with NiCl2·6H2O and CdCl2·H2O, respectively. In addition, the homotrinuclear Cu(II) complex (8), has also been prepared by the reaction of this dioxime with CuCl2·H2O. The structures of the dioxime and its complexes were identified by using elemental analysis, 1H- and 13C-NMR, IR, and mass spectral data.

Rapid label-free detection of metal-induced Alzheimer's amyloid beta peptide aggregation by electrochemical method

Amyloid beta peptide plays a critical role in the pathogenesis of Alzheimer's disease (AD). Metal ions are highly enriched in cerebral amyloid deposits in AD and are proposed to be able to mediate A beta conformation. Therefore, a rapid, low-cost, and sensitive detection of metal-induced A beta aggregation and their relation to AD is clearly needed for the clinical diagnosis and treatment. In this report, we study metal-induced A beta aggregation by a rapid, label-free electrochemical method and monitor both the aggregation kinetics and the morphology in the absence or presence of Zn (II) and Cu (II).

Selective oxidation of cyclohexane with hydrogen peroxide in the presence of copper pyrophosphate

Liquid phase oxidation of cyclohexane was carried out under mild reaction condition over copper pyrophosphate catalyst in CH3CN using hydrogen peroxide as an oxidant at the temperature between 25 and 80 degrees C. The copper pyrophosphate catalyst was characterized by means of XRD, FT-IR and water contact angle measurement. It was found that appropriate surface hydrophobicity is the key factor for the excellent performance of the catalyst. In addition, a significant improvement for the cyclohexane conversion in the presence of organic acid was observed.

Chitosan(Chitin)/Cellulose Composite Biosorbents Prepared Using Ionic Liquid for Heavy Metal Ions Adsorption

Chitosan(chitin)/cellulose composites as biodegradable biosorbents were prepared under an environment-friendly preparation processes using ionic liquids. Infrared and X-ray photoelectron spectra indicated the stronger intermolecular hydrogen bond between chitosan and cellulose, and the hydroxyl and amine groups were believed to be the metal ion binding sites. Among the prepared biosorbents, freeze-dried composite had higher adsorption capacity and better stability. The capacity of adsorption was found to be Cu(II) (0.417 mmol/g) > Zn(II) (0.303 mmol/g) > Cr(VI) (0.251 mmol/g) > Ni(II) (0.225 mmol/g) > Ph(II) (0.127 mmol/g) at the same initial concentration 5 mmol L-1. In contrast to some other chitosan-type biosorbents, preparation and component of the biosorbent were obviously more environment friendly. Moreover, adsorption capacity of chitosan in the blending biosorbent could be fully shown.

Structural analysis of PEKEKK(T/I) using WAXD, imaging plates and SAXS

Structures and crystal form transition of the novel aryl ether ketone polymer containing meta-phenylene linkage: PEKEKK(T/I) were investigated by wide angle X-ray diffraction (WAXD), imaging plates (IPs) and small angle X-ray scattering (SAXS). The energy of activation of the decomposition reaction and degree of crystallinity of PEKEKK(T/I) were determined by WAXD and thermo-gravimetric analysis (TGA), respectively. Results obtained from WAXD and IPs show that crystal forms I and II coexist in the PEKEKK(T/I) samples isothermally cold crystallized in the temperature range from 180degreesC to 240degreesC and only form I occurs in PEKEKK(T/I) samples isothermally cold crystallized at 270degreesC. The radius of gyration (Rg), thickness of microregions with electron-density fluctuations (E) and distribution of particle sizes were investigated by SAXS.