手性氨基酸的毛细管电泳拆分研究

以咔唑-9-乙基氯甲酸酯（CEOC）作柱前荧光衍生试剂，在毛细管区带电泳和胶束电动色谱条件下，以不同配比的β-环糊精（β-CD）和脱氧胆酸钠（SDC）作手性选择剂，在两种不同分离模式下，对氨基酸衍生物进行了手性分离，同时对分离过程中的相关参数进行了优化，分别实现了8种和10种氨基酸的快速手性分离。     

气相色谱－质谱法测定赤鳞鱼肉中的脂肪酸

 利用气相色谱质谱（ＧＣ／ＭＳ）电子轰击方法，对６种不同年龄和不同性别的赤鳞鱼肉中的饱和、不饱和脂肪酸（经甲酯化后）进行了测定，用色谱法作了定量，共鉴定出１８种脂肪酸。     

高效液相色谱-电感耦合等离子体质谱法分析尿中6种砷形态

采用高效液相色谱-电感耦合等离子体质谱法（HPLC-ICP-MS）分析人尿中砷甜菜碱（AsB）、二甲基砷（DMA）、砷胆碱（AsC）、亚砷酸盐（As（Ⅲ））、一甲基砷（MMA）、砷酸盐（As(V)）6种砷形态。样品经水稀释后，采用Dionex IonPac As7阴离子交换色谱柱为分析柱，20 mmol/L碳酸铵（2%甲醇）和100 mmol/L碳酸铵（含2%甲醇）为流动相，梯度洗脱，HPLC-ICP-MS分析砷形态。6种砷形态在0～100μg/L范围内线性关系良好，相关系数（r）均大于0.999，检出限为0.05～0.15μg/L，不同浓度水平砷形态的相对标准偏差（RSD）均小于5.0%。3种不同浓度水平的加标回收率为91.8%～108%，有证标准物质“冷冻人尿中砷形态”（NIST SRM 3669）中5种砷形态的测定结果在标准值范围内。实验结果表明，该方法准确可靠、灵敏度高、分析时间短，适用于人尿中砷形态的分析测定。同时研究了食用不同含砷食物后尿中砷形态的种类，结果显示不同的含砷食品，其砷在人体内的代谢转化不同。     

吸水膨胀弹性体在不同介质中的溶胀行为

研究了由共硫化法制得的三种吸水膨胀弹性体（ＷＳＥ）在不同介质中的溶胀行为，得出了溶胀速率方程和动力学参数，确定了不同介质对平衡溶胀度（Ｑｅ）的影响规律．     

Mo(W)-Co(Ni,Fe)簇合物的加氢脱硫催化活性

对线型、立方烷型和笼状３种不同构型的Ｍｏ（Ｗ）－Ｃｏ（Ｎｉ，Ｆｅ）－Ｓ（Ｏ）簇共１２种化俣物进行了噻吩加氢硫和环己烯加氢的催化活性研究，讨论了簇合物的组成，金属原子的配比、价态与催化活性的关系，探讨了不同构型对活性的影响。     

Mo（W）－Co（Ni，Fe）簇合物的加氢脱硫催化活性

对线型、立方烷型和笼状３种不同构型的Ｍｏ（Ｗ）－Ｃｏ（Ｎｉ，Ｆｅ）－Ｓ（Ｏ）簇共１２种化合物进行了噻吩加氢脱硫和环己烯加氢的催化活性研究．讨论了簇合物的组成，金属原子的配比、价态与催化活性的关系．探讨了不同构型对活性的影响．     

氧化还原体系溶液进样对原子吸收火焰的增温作用

研究了氧化还原体系溶液进样对原子吸收光谱法中空气-乙炔火焰的增温作用。应用双波长吸收法，首先采用镓（Ga）标准溶液进样，在不同乙炔流量、不同观察高度条件下对空气-乙炔火焰的温度进行测量，验证空气-乙炔火焰的温度分布情况，然后选定高氯酸、硝酸、无水乙醇、蔗糖4种试剂，以适当浓度、不同组合配制6种氧化还原体系介质的Ga标准溶液、使用其进样，在不同Ga标准溶液、乙炔流量与观察高度条件下进样，对空气-乙炔火焰温度进行测量，验证利用氧化还原体系介质溶液进样提高空气-乙炔火焰温度的可行性。结果表明，所选定试剂作为溶液介质进样增温空气-乙炔火焰是可行的，不同介质溶液进样对空气-乙炔火焰的增温效果有差异。根据实验数据确定了6种介质溶液进样、空气-乙炔火焰温度达到最高时的乙炔气流量和火焰观察高度，为使用空气-乙炔火焰原子吸收光谱法测定某些难熔元素如（Mo）、（Ba）、（Al）、（Sn）、（W）、（V）奠定了基础。     

RE(C7H5O3)2(C9H6NO)配合物抗真菌作用的热动力学研究

应用微量热法研究了配合物RE（CTH5O3）2（C9H6NO）（RE代表La，Sm和Nd）对真菌的抗菌作用。在TAM Air热导式等温微量量热仪上，分别测定了桔青霉菌和黑曲霉菌在不同浓度不同稀土配合物及空白条件下生长代谢热谱曲线，并计算得到了真菌在不同条件下的生长代谢速率常数k和传代时间G等热动力学参数。实验表明：3种稀土水杨酸8-羟基喹啉三元配合物对桔青霉菌和黑曲霉菌均有抑制作用，其抑制效果依次为：Sm（Hsal）2（hq）〉La（Hsal）2（hq）〉Nd（Hsal）2（hq）。     

用两种相似多糖类手性固定相拆分阿托品外消旋对映体的比较

分别涂敷纤维素-三（3，5-二甲基苯基氨基甲酸酯）（CDMPC）与直链淀粉-三（3，5-二甲基苯基氰基甲酸酯）（ADMPC）于自制的球形氨丙基硅胶上，制备了两种多糖类手性崮定相。用高效液相色谱法（HPLC）在正相条件下，用两种固定相直接拆分了阿托品（atmpine）外消旋体、在正己烷中加入了不同的醇类改性剂对阿托品进行拆分，并优化了流动相中醇类改性剂的比例：结果发现，阿托品在CDMPC固定相上可以得到基线拆分，而在ADMPC固定相上只能得到部分拆分。     

两种CO(Ⅱ)希夫碱配合物的合成、表征和氧合反应热力学

本文合成了两种新的Ｃｏ（Ⅱ）希夫碱配合物，双（２，４－二羟基苯乙酮）乙二胺合钴（Ⅱ）（Ｃｏ（ＣＯＥＮ）和双（对香兰素）乙二胺－乙氧基－醋酸钴（Ⅱ）（Ｃｏ（ＶＡＥＮ））。通过元素分析、红外光谱、摩尔电导、热分析等测试手段研究了配合的性质，并确定了配合物的组成。用气体吸收测量装置配合物分别在ＤＭＦ、ｐｙ等不同溶剂中于不同温度下的饱和吸氧量，求得氧合反应的平衡常数及热学参数。同时讨论了溶剂和配体结构对配     

Unique {H(SiR(3))(2)}, (H(2)SiR(3)), H(HSiR(3)), and (H(2))SiR(3) ligand sets supported by the {Fe(Cp)(L)} platform (L=CO, PR(3))

This work deals with the type and incidence of nonclassical Si--H and H--H interactions in a family of silylhydride complexes [Fe(Cp)(OC)(SiMe(n)Cl(3-n))H(X)] (X=SiMe(n)Cl(3-n), H, Me, n=0-3) and [Fe(Cp)(Me(3)P)(SiMe(n)Cl(3-n))(2)H] (n=0-3). DFT calculations complemented by atom-in-molecule analysis and calculations of NMR hydrogen-silicon coupling constants revealed a surprising diversity of nonclassical Si--H and H--H interligand interactions. The compounds [Fe(Cp)(L)(SiMe(n)Cl(3-n))(2)H] (L=CO, PMe(3); n=0-3) exhibit an unusual distortion from the ideal piano-stool geometry in that the silyl ligands are strongly shifted toward the hydride and there is a strong trend towards flattening of the {FeSi(2)H} fragment. Such a distortion leads to short Si--H contacts (range 2.030-2.075 A) and large Mayer bond orders. A novel feature of these extended Si--H interactions is that they are rather insensitive towards the substitution at the silicon atom and the orientation of the silyl ligand relatively the Fe--H bond. NMR spectroscopy and bonding features of the related complexes [Fe(Cp)(OC)(SiMe(n)Cl(3-n))H(Me)] (n=0-3) allow for their rationalization as usual eta(2)-Si--H silane sigma-complexes. The series of "dihydride" complexes [Fe(Cp)(OC)(SiMe(n)Cl(3-n))H(2)] (n=0-3) is different from the previous two families in that the type of interligand interactions strongly depends on the substitution on silicon. They can be classified either as usual dihydrogen complexes, for example, [Fe(Cp)(OC)(SiMe(2)Cl)(eta(2)-H(2))], or as compounds with nonclassical H--Si interactions, for example, [Fe(Cp)(OC)(H)(2)(SiMe(3))] (16). These nonclassical interligand interactions are characterized by increased negative J(H,Si) (e.g. -27.5 Hz) and increased J(H,H) (e.g. 67.7 Hz).     

Syntheses and structures of the infinite chain compounds Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14)

The alkali metal/group 4 metal/polychalcogenides Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) have been synthesized by means of the reactive flux method at 823 or 873 K. Cs(4)Ti(3)Se(13) crystallizes in a new structure type in space group C(2)(2)-P2(1) with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) A, b = 32.468(2) A, c = 14.6747(8) A, beta = 100.008(1) degrees. Cs(4)Ti(3)Se(13) is composed of four independent one-dimensional [Ti(3)Se(13)(4-)] chains separated by Cs(+) cations. These chains adopt hexagonal closest packing along the [100] direction. The [Ti(3)Se(13)(4-)] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs(4)Ti(3)Se(13). The compounds Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) crystallize in the K(4)Ti(3)S(14) structure type with four formula units in space group C(2)(h)()(6)-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) A, b = 8.1169(5) A, c = 13.1992(8) A, beta = 112.835(1) degrees for Rb(4)Ti(3)S(14);a = 21.329(3) A, b = 8.415(1) A, c = 13.678(2) A, beta = 113.801(2) degrees for Cs(4)Ti(3)S(14); a = 21.643(2) A, b = 8.1848(8) A, c = 13.331(1) A, beta = 111.762(2) degrees for Rb(4)Hf(3)S(14); a = 22.605(7) A, b = 8.552(3) A, c = 13.880(4) A, beta = 110.919(9) degrees for Rb(4)Zr(3)Se(14); a = 22.826(5) A, b = 8.841(2) A, c = 14.278(3) A, beta = 111.456(4) degrees for Cs(4)Zr(3)Se(14); and a = 22.758(5) A, b = 8.844(2) A, c = 14.276(3) A, beta = 111.88(3) degrees for Cs(4)Hf(3)Se(14). These A(4)M(3)Q(14) compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed [M(3)Q(14)(4-)] chains that run in the [101] direction and are separated by A(+) cations. Each [M(3)Q(14)(4-)] chain is built from a [M(3)Q(14)] unit that consists of two MQ(7) pentagonal bipyramids or one distorted MQ(8) bicapped octahedron bonded together by edge- or face-sharing. Each [M(3)Q(14)] unit contains six Q(2)(2-) dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) A for S-S and 2.367(1)-2.391(2) A for Se-Se. The A(4)M(3)Q(14) compounds can be formulated as (A(+))(4)(M(4+))(3)(Q(2)(2-))(6)(Q(2-))(2).     

Organic acid solutions in the chromatography of inorganic ions VIII. Cation-exchange of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media

Summary The cation-exchange behaviour of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the ammonium form. Separation of Fe(III)/Cu(II), Fe(III)/Cu(II)/Zn(II), Fe(III)/Co(II)/Mn(II), Cu(II)/Ni(II)/Mn(II), Fe(III)/Cu(II)/Co(II)/Mn(II), Fe(III)/Cu(II)/Ni(II)/Cd(II), Yb(III)/Eu(III), Sc(III)/Y(III),Sc(III)/Yb(III)/Dy(III) and Nb(V)/Yb(III)/Ho(III) has been achieved, among others.This work was supported by C.N.R. of Italy.     

Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)

The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H₂O)₆](H₂­PO₂)₂, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF₂. The Co^II(Ni^II) atoms have a pseudo‐face‐centred cubic cell, with a = b～ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.     

(K_(0.485)Na_(0.485)Li_(0.03))NbO_3-Pb(Zr_(0.53)Ti_(0.47))O_3陶瓷的介电铁电性能

采用传统电子陶瓷工艺制备新型钙钛矿体系(1-x)(K_(0.485)Na_(0.485)Li_(0.03))NbO_3-Pb(Zr_(0.53)Ti_(0.47))O_3陶瓷,研究了该体系陶瓷的介电铁电性能.X射线衍射分析表明:所有陶瓷样品都具有单一的钙钛矿结构,在0.65≤x≤0.75时,出现明显的正交相和四方相的准同型相界区.测试结果表明:陶瓷具有高介电常数.低介质损耗,良好的温度稳定性;获得了饱和的电滞回线,显示了优良的铁电性能.尤其在x=0.75时各项性能达到最佳,其中介电常数ε_r=1590,介电损耗tan δ=0.017,居里温度T_c=295℃,剩余极化强度P,=28.6 μC·cm~(-1),矫顽场强E_c=0.89 kV·mm~(-1).