利用荷移带的浓度效应测定[5,10,15,20]—四取代基卟啉氯化铁络…

研究了８个新合成的四取代苯基卟啉氯化铁络合物的紫外－可见光谱，对在三氯甲烷溶剂中荷移带约２４０ｎｍ处λｍａｘ随测试溶液浓度增加而红移的规律进行了计算机拟合，拟合修正公式为λｍａｘ＝ｅ＾ａ＋ｂｃ＾ｅ，相关系数达０．９９８，本文用拟合公式对络合物含量进行测定，相对误差为０．０５￣４．９％。本文还对该系列络合物的紫外－可见光谱主要吸收峰作了归属，也研究了取代基效应。     

环丙沙星荷移反应及荧光光谱性质研究

研究了环丙沙星（CPFX）与电子受体2，3－二氰－5，6－二氯－1，4对苯酯（DDQ）之间的荷移反应。实验结果表明：DDQ与CPFX的荷移反应需在丙酮－甲醇（1：4）介质中进行。两者于40℃水浴中恒温30min即可形成1：1络合物，其荧光发射较CPFX有显著的增强。在0．107．2mg/L浓度范围内，荧光强度与质量浓度呈良好线性关系；其检出限为0．1mg/L。本方法用于片剂中环丙沙星的含量测定，其回收率为96．6％－100．2％；标准偏差为1．3％－2．6％。     

某些铁—硫原子族络合物紫外—可见光谱的研究

本文研究了某些铁－硫原子簇络合物紫外－可见光谱２２０－２３０ｎｍ吸收带λｍａｘ的浓度效应；△λｎｍ随络合物结构对称性增加而减小，随浓度基数增大而变大的变化关系。该类型络合物紫外－可见光谱吸收峰的归属，计算了Ｆｅ＾ＩＩ分裂能△值；配体上的取代基效应，以用在二氯甲烷等溶剂中的溶剂效应。     

铁镍镀层中铁镍组成的紫外-可见分光光度分析法

用紫外－可见分光光度法分析了电沉积在导电玻璃上的NiFe合金镀层，三价铁与EDTA和H2O2形成稳定的深紫色三元络合物；在氨性溶液中，当有氧化剂存在时，镍与丁二酮肟形成酒红色的络合物，用吸收光度法可分别在519nm和538nm波长处测定铁、镍的含量，对Fe和Ni的相对标准偏差分别为0．95％和1．2％，适用含量范围分别为1－50mg/L和0．5－20mg/L；对实际样品的测定结果与XPS分析的一致，该法也适用于其他样品中铁、镍含量的测定。     

镉（Ⅱ）—7—碘—8—羟基喹啉—5—磺酸络合物吸附波的研究

在ｐＨ４．３的ＨＡｃ－ＮａＡｃ介质中，Ｃｄ（Ⅱ）与７－碘－８－羟基喹啉－５－磺酸（７－Ｉ－Ｈ２ＱＳ）生成络合物。有二苯胍存在下，于－０．６８Ｖ（ｖｓ．ＳＣＥ）产生一灵敏的极谱波，峰电流与Ｃｄ（Ⅱ）浓度在８．９×１０－９～２．２×１０－６ｍｏｌ／Ｌ浓度范围内呈线性关系。通过对该极谱波性质及反应机理的研究，证实其为络合物吸附波，络合比为１∶１，络合物带负电荷。方法用于铜矿中镉的测定，结果满意     

2-羟基-3-羧基-5-磺酸基苯重氮氨基偶氮苯与汞的显色反应及其应用

研究了2－羟基－3－羧基－5－磺酸基苯重氮氨基偶氮苯（HCSDAA）与汞（Ⅱ）的显色反应。在乳化剂OP存在下和pH10．0～10．5的缓冲介质中，汞（Ⅱ）与HCSDAA形成1：2的红色络合物，其最大吸收波长是522nm，对比度为91nm，表观摩尔吸光系数为1．63×105L·mol－1·cm－1。汞（Ⅱ）在0～0．55mg／L范围内服从比尔定律。本方法操作简便，选择性较好，直接用于头发和废水的分析，6次测定的相对标准偏差分别为2．1％和27％，平均值与双硫腙法一致，回收率分别是94．8％～101．6％和98．7％～103．0％。     

2—（2‘吡啶基）—5—甲苯并噻唑及其二氯二乙基锡（Ⅳ）络合物的结构以及抗

X－射线单晶衍射法测定了2－（2'-吡啶基）－5－甲苯并噻唑（I）及其二氯二乙基锡（IV）络合物（2）的结构，晶体（I）属单斜晶系，《空间群为P21／n，晶胞参数a=5.808(2),b=10.283(3),C=18.373(3)A,β=91.48(2)°，Z=4,Dc=1.370g.cm^-3，偏离因子R＝0．047。晶体（2）属单斜晶系，空间群p21/c,晶胞参数a=17.271(2),b=9.411(1),c=14.015(2)A,β122．98（1）°，Z＝4，D＝1．648g.cm^-3，偏因子R－0．047，络合物中Sn-N平均键长已达2．5－A，参考顺铂类药物研究经验，展望了抗肿瘤有机锡络合物发展的前景。     

7-(对甲酰基苯偶氮)-8-羟基喹啉-5-磺酸的合成及其双波长分光光度法测定镓

7－（对甲酰基苯偶氮）－8－羟基喹啉－5－磺酸是一新显色剂。该试剂在微碱性介质中（pH＝7．5）与镓形成黄色络合物。络合物λmax＝392nm，摩尔吸光系数ε392＝2．24×104L·mol-1·cm-1。同时在500nm呈现负峰，用双峰观波长法测定镓ε392～500＝6．89×104L·mol-1·cm－1，灵敏度是单波长法的三倍多．线性范围0～2．0×10－5mol／L。用拟定的方法测定了掺硅的GaAS材料及岩石中的镓，加入回收率为106％～110％；方法的相对标准偏差小于1．6％。     

聚-γ-N(β-丁硫基乙基)胺丙基硅氧烷铂络合物的合成及其催化性能的研究

以丙烯胺和氯乙醇为原料，合成了Ｎ－烯丙基乙醇胺；经过卤化，再与丁硫醇钠反应，制得Ｎ－（β－丁硫基乙基）烯丙胺；经过硅氢化，水解固载，络合Ｋ２ＰｔＣｌ４，得到固定在二氧化硅上的聚－γ－Ｎ（β－丁硫基乙基）胺丙基硅氧烷铂络合物，并用ＸＰＳ研究了其结构．选用１－十二烯、１－癸烯、氯代十一烯、苯基烯丙醚、苯丙烯、环己烯、丁烯腈等７种烯烃为底物，与三乙氧基硅烷进行硅氢加成反应，用铂络合物作为催化剂，考察了铂络合物的催化活性和产物的选择性．表明硅氢化速度随温度的增加而增加．铂络合物在空气中暴露半年不影响其活性，经简单回收可再使用     

流动注射-荧光光纤传感器测定盐酸

将3－羟基－4‘-N,N-二甲氨基黄酮甲基丙烯酸酯与甲基丙烯酸甲酯和丙烯酸丁酯共聚，制备了含荧光基团的高聚物（PFMB），以PFMB为敏感膜研制了一种荧光猝灭型的盐酸光纤传感器。在Fe(Ⅲ）存在下，猝灭效率大大增加，猝灭机制主要包括Fe(Ⅲ）与Cl^-形成络合物的初级内滤效应和该络合物与PFMB形成非荧光复合物两种作用。该传感器可直接用于0．1－6．0mol/L盐酸的测量。与流动注射联用可测量0．1－12．0mol/L的盐酸。传感器具有良好的重现性和可逆性，响应和恢复时间均小于40s，且有较长的使用寿命。     

Optimization of parameters for semiempirical methods. III Extension of PM3 to Be,Mg, Zn,Ga, Ge,As, Se,Cd, In,Sn, Sb,Te, Hg,Tl, Pb,and Bi

Using a recently developed procedure for optimizing parameters for semiempirical methods,¹ PM3 has been extended to a total of 28 elements. Average ΔH_f errors for the newly parameterized elements are Be: 8.6, Mg: 8.4, Zn: 5.8, Ga: 14.9, Ge: 11.4, As: 8.5, Se: 11.1, Cd: 2.6, In: 11.3, Sn: 9.0, Sb: 13.7, Te: 11.3, Hg: 6.8, Tl: 6.5, Pb: 7.4, and Bi: 10.9 kcal/mol. For some elements the paucity of data has resulted in a method, which, while highly accurate, is likely to be only poorly predictive.     

Metal-Directed Formation of Tetra-, Hexa-, Octa-, and Nonanuclear Complexes of Magnesium,Calcium, Manganese,Copper, and Cadmium

Efficacious metal control of self-assembly of dialkylketipinate dianions leads to completely different supramolecular assemblies. The structures of grid 1 , double-decker 2 , triple-decker 3 , and metalla-spherand 4 were characterized by X-ray crystallographic analyses or by NMR spectroscopy.     

Thin-layer chromatographic separation of aldrin,dieldrin, γ-hexachlorocyclohexane,malathion, ethyl-parathion,pentachlorophenol, and of chlordane,dieldrin, γ-hexachlorocyclohexane,malathion, ethyl-parathion,and pentachlorophenol from each other

A thin-layer chromatographic method is reported for the separation of aldrin (or chlordane), dieldrin, γ-hexachlorocyclohexane, malathion, ethyl-parathion, and pentachlorophenol from each other. The procedure, however, does not separate aldrin and chlordane from each other although it does separate either pesticide from the other components. The method employs alumina plates with n-hexane:xylene:benzene:toluene:cyclohexane:methyl cyclohexane (50:50:50:50:50:50:) as developing solvent.     

Certification of the mass fractions of Ca,Cu, Cl,I, Fe,K, Mg,P, Pb,N, Na and Zn in skim milk powder

Analyses of milk and milk products are routinely performed by a number of dairy laboratories to control the quality of these products with regard to e.g. nutritional components and potential exposure to toxic elements. In order to improve and control the quality of such analyses the Community Bureau of Reference (BCR) has organized series of certification campaigns to produce reference material of milk certified for a variety of elements and compounds. The increasing demand is such that the stock of some of these materials is now exhausted. Consequently, the BCR decided to produce a new batch of CRM of skim milk powder certified for its contents of Ca, Cu, Cl, I, Fe, K, Mg, P, Pb, N, Na and Zn (CRM 063R). This material was carefully prepared (spray-drying) and its homogeneity and long term stability was verified. This paper presents the certification work performed.     

Stereochemistry of the oxidation of 1, 2, 3, 5, 6, 7, 8, 8a-octahydro-1-naphthoic acids

Summary It was shown that the oxidation of syn- and anti-1,2,3,5,6,7,8,8a-octahydro-1-naphthoic acids with peroxyacetic acid and with osmium tetraoxide proceed stereospecifically from the side opposite to that of the carboxy group. On the other hand, the oxidation of syn-cis-1,2,3,5,6,7,8,8a-octahydro-1, 2-naphthalenedicarboxylic acid goes in both of the possible sterically different directions with formation of isomeric- and-epoxides.     

Prediction of the enthalpy of vapourisation for anhydrides,formates, acetates,propionates, butyrates,esters, and ethers

Four analytical correlations based on the use of the corresponding states principle were used to calculate the enthalpy of vapourisation of fluids. Three of these correlations require as inputs the critical temperature and the acentric factor. The fourth requires a molecular Lennard–Jones parameter and the acentric factor. Results for 184 polar and non-polar fluids grouped into 9 families are compared with the values accepted by the Design Institute for Physical Property (DIPPR) project. Recommendations are given for the use of each model and for the choice of the adequate model for each family of fluids.     

Certification of the contents of As, B, Cd, Cr, Co, Cu, Mn, Hg, Ni, Ti, V and Zn in a natural Moroccan phosphate rock

Summary The preparation and homogeneity tests of a natural Moroccan phosphate rock are described. The experimental procedures leading to the certification of the contents of As, B, Cd, Cr, Co, Cu, Hg, Mn, Ni, Ti, V and Zn are presented. The Pb-content is given as a recommended value. Indicative values are proposed for Ag, Mo, Sb, Se, Th and U. The certification has been carried out in participation with 11 laboratories from different European countries.

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Zertifizierung der Gehalte an As, B, Cd, Cr, Co, Cu, Mn, Hg, Ni, Ti, V und Zn in einem natürlichen Marokkanischen Phosphatgestein

Zusammenfassung Die Aufbereitung und die Homogenitätskontrollen eines natürlichen Marokkanischen Phosphatgesteins werden beschrieben. Die experimentellen Arbeiten, die zur Zertifizierung der genannten Gehalte geführt haben, werden angegeben. Für Blei wird ein empfohlener Wert gegeben. Indikative Werte werden für Ag, Mo, Sb, Se, Th und U vorgeschlagen. Die Zertifizierung wurde in Zusammenarbeit mit 11 Laboratorien aus verschiedenen europäischen Ländern durchgeführt.

     

ICP-AES法测定铝中铁、硅、铜、镓、镁、锌、锰和钛

用 50g L氢氧化钠溶液溶解铝样品 ,硝酸 (1 1 )酸化 ,以ICP AES测定其中铁、硅、铜、镓、镁、锌、锰和钛等 8种杂质元素。