含氮配体过渡金属络正离子与[Ni（cdc）2]^2—加合物的电子光谱和电导？…

研究了１０个含氮配体的过渡金属络正离子与「Ｎｉ（ｃｄｃ）２」＾２－加合物在溶液２和固体状态下的电子光谱和溶液电导率,发现电导率（Ω＾－１·ｃｍ＾２·ｍｏｌ＾－１）和加合物在ＨＣｌ介质中π－π跃迁带Ｖｍａｘ（ｃｍ＾－１）值呈一致变化关系。对吸收峰作出了归属,指定了负离子的ＭＬＣＴ带,并指出极性溶剂使ＭＬＣＴ带蓝移,ππ跃迁带红移。     

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。     

[5,10,15,20]—四取代苯基卟啉氯化锰配合物紫外—可见光谱…

测定了１８个新合成的四代苯基卟啉氯化锰的紫外－可见光谱，对主要吸收峰作了归属，指定了ＣＴ带，研究了样品在四氢呋喃溶剂中２２０ｎｍ附近吸收带的浓度效应和在四氢呋喃、三氯甲烷、二氯甲烷、乙醇中的溶剂效应及取代基效应。结果表明，除ｏ－Ｍｅ，ｐ－Ｉ取代苯基卟啉锰外，２２０ｎｍ附近吸收带随测试溶浓度增加，λｍａｘ红移；随测定溶剂极性（Ｐ值）增加，λｍａｘ蓝移。     

［5，10，15，20］－四取代苯基卟啉氯化锰配合物紫外－可见光谱的研究

测定了１８个新合成的四取代苯基卟啉氯化锰的紫外－可见光谱，对主要吸收峰作了归属，指定了ＣＴ带，研究了样品在四氢呋喃溶剂中２２０ｎｍ附近吸收带的浓度效应和在四氢呋喃、三氯甲烷、二氯甲烷、乙醇中的溶剂效应及取代基效应。结果表明，除ｏ－Ｍｅ、ｐ－Ⅰ取代苯基卟啉锰外，２２０ｎｍ附近吸收带随测试溶液浓度增加，λ_（ｍａｘ）红移；随测定溶剂极性（ｐ值）增加，λ_（ｍａｘ）蓝移。     

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。     

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合物的含量

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，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。     

超声射流冷却丁二酮的激光诱导荧光激发谱

在超声射流条件下获得了丁二酮在４３２－４５１ｎｍ波段的激光诱导荧光激发谱。在前人标识为０＾００带谱峰的红端观察到３个很弱的谱峰分别位于０,８７,９７ｃｍ＾－１处（以２２１８２ｃｍ＾－１为０ｃｍ＾－１）。在８７和９７ｃｍ＾－１附近精细扫描,观测到８７和９７ｃｍ＾－１谱峰的联道分裂分别为１．０５观和１．６８ｃｍ＾－１,与理论计算的分裂值符合得很好人 而确定了Ｓ１←Ｓ０跃迁０＾００带的位置在２２１８２ｃ     

磺基水杨酸紫外导数分光光度法测定微量铁

在不同ｐＨ下铁－磺基水杨酸形成组成比不同的配合物，其紫外吸收光谱也不同，在ｐＨ５～７的六次甲基四胺－盐酸介质中形成１：２配合物，最大吸收波长λｍａｘ２４８ｎｍ表观摩尔吸光系数ε＝２．９×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１比可见光区的灵敏度高１０倍，用三阶导数光谱法测定化学试剂中微量铁，结果与邻二氮菲法一致，相对标准偏差１．２％。     

用钼酸盐和罗丹明B连续光度法测定铈和钪

聚乙烯醇存在下，铈或钪钼杂多酸与罗丹明Ｂ（ＲＢ）形成离子缔合物，最大吸收均位于５７０ｎｍ，摩尔吸光系数分别为１．１６×１０＾６和５．６２×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，ｃｍ＾－１，０－１．２μｇ／２５ｍＬＣｅ和０－２．０μｇ／ｍＬＳｃ服从比耳定律，检测限１．５ｎｇ／ｍＬＣｅ（ｎ＝１０）和１．１ｎｇ／ｍＬＳｃ（ｎ＝９）。缔合物的摩尔比为Ｃｅ：ｍＯ：ＲＢ＝１：６：３和 Ｓｃ：Ｍｏ：ＲＢ＝１：１     

丁基罗丹明B—钼酸盐光度法连续测定铈和钪

在聚乙烯醇（ＰＶＡ）存在下，丁基罗丹明Ｂ（ＢＲＢ）分别与铈钼、钪钼杂多酸络阴离子形成离子缔合物，其最大吸收均位于５７０ｎｍ，表面摩尔吸光度分别为εＣｅ＝３．９６×１０＾６Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，εＳｃ＝４．７１×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，服从比耳定律范围分别为０－２４μｇ／Ｌ Ｃｅ和０－６０μｇ／ＬＳｃ，测定极限为Ｃｅ１．０μｇ／Ｌ（ｎ＝１２）和Ｓｃ１．９μｇ／Ｌ（ｎ＝１０），对     

Role of entropy and autosolvation in dimerization and complexation of C60 by Zn7 metallocavitands

The supramolecular chemistry of bowl-shaped heptazinc metallocavitands templated by Schiff base macrocycles has been investigated. Dimerization thermodynamics were probed by (1)H NMR spectroscopy in benzene-d(6), toluene-d(8), and p-xylene-d(10) and revealed the process to be entropy-driven and enthalpy-opposed in each solvent. Trends in the experimentally determined enthalpy and entropy values are related to the thermodynamics of solvent autosolvation, solvent molecules being released from the monomeric metallocavitand cavity into the bulk solvent upon dimerization. The relationship established between experimentally measured dimerization thermodynamics and autosolvation data successfully predicts the absence of dimerization in CH(2)Cl(2) and CHCl(3) and was used to estimate the number of solvent molecules interacting with the monomeric metallocavitand in solution. Host-guest interactions between heptazinc metallocavitands and fullerene C(60) have also been investigated. Interestingly, metallocavitand-C(60) interactions are only observed in solvents that facilitate entropy-driven dimerization suggesting entropy and solvent autosolvation may be important in explaining concave-convex interactions.     

Optimization of dispersive liquid-liquid microextraction of copper (II) by atomic absorption spectrometry as its oxinate chelate: application to determination of copper in different water samples

In this study a dispersive liquid-liquid microextraction (DLLME) method based on the dispersion of an extraction solvent into aqueous phase in the presence of a dispersive solvent was investigated for the preconcentration of Cu(2+) ions. 8-Hydroxy quinoline was used as a chelating agent prior to extraction. Flame atomic absorption spectrometry using an acetylene-air flame was used for quantitation of the analyte after preconcentration. The effect of various experimental parameters on the extraction was investigated using two optimization methods, one variable at a time and central composite design. The experimental design was performed at five levels of the operating parameters. Nearly the same results for optimization were obtained using both methods: sample size 5 mL; volume of dispersive solvent 1.5 mL; dispersive solvent methanol; extracting solvent chloroform; extracting solvent volume 250 microL; 8-hydroxy quinoline concentration and salt amount do not affect significantly the extraction. Under the optimum conditions the calibration graph was linear over the range 50-2000 muicro L(-1). The relative standard deviation was 5.1% for six repeated determinations at a concentration of 500 microg L(-1). The limit of detection (S/N=3) was 3 microg L(-1).     

Spectrophotometric determination of water in organic solvents with solvatochromic dyes

The correlation between the absorbance at a fixed wave-length of a betaine dye in an organic solvent and the water content of the same solvent has been investigated. The betaine dyes investigated are 2,4,6-triphenyl-N-(3,5-diphenyl-4-hydroxyphenyl)pyiidinium betaine (I), 1-methyl-8-hydroxyquinolinium betaine (II), 1-methyl-6-hydroxyquinolinium betaine (III) and 2-methyl-5-isoquinolinium betaine (IV), and the organic solvents are ethanol, isopropanol, acetone, dioxan, acetonitrile and pyridine. The possibility of determining a trace amount of water in an organic solvent is demonstrated. The sensitivity of the method depends on solvent and dye but for example, 0.06 mg of water in 1 ml of acetonitrile can be detected with III with an ordinary spectrophotometer. The limitations of practical applications are discussed.     

离子液体体系中1－丁烯二聚反应的研究

 研究了在强酸性AlCl3／Et2AlCl／［BMIM］Cl型离子液体体系中过渡金属化合物对1－丁烯二聚反应的催化作用．结果表明，［BMIM］Cl对强酸性AlCl3／Et2AlCl催化剂催化1－丁烯高聚反应有明显的阻聚作用，并显著提高了1－丁烯二聚的选择性．在过渡金属化合物中，含镍化合物对1－丁烯二聚反应有最好的催化效果．在最佳反应条件下，1－丁烯的转化率可达95．1％，二聚产物C8烯的选择性为85．8％．同时，对1－丁烯二聚反应的机理进行了初步探讨．     

Reversible thermoresponsive behavior of poly(2-chloroethyl vinyl ether-<Emphasis Type="Italic">alt</Emphasis>-maleic anhydride) in mixed solvent of tetrahydrofuran/hexane

Poly(2-chloroethyl vinyl ether-alt-maleic anhydride) can exhibit lower critical solution temperature-type phase behavior reversibly by tuning the solvent composition in mixed solvent of tetrahydrofuran (THF) and hexane. The effect of solvent composition and polymer concentration on cloud point of polymer solution was investigated. The cloud point temperature for high molecular weight polymer was lower than that for lower molecular weight polymer. High resolution ¹H NMR spectra in mixed solvent of THF-d ₈ and hexane were also measured for comprehending thermoresponsive behavior of polymer solution in molecular level; however, any discontinuous change in the NMR signals around the cloud point could not be recognized.     

非水相中固定化脂肪酶催化性能的研究

以离子交换树脂为载体,用离子交换吸附法固定化脂肪酶,对影响固定化过程的各种因素进行了考察,确定了最优条件。得到的固定化酶催化合成月桂酸月桂醇酯,考查了在不同lgP值有机溶剂中的催化反应,异辛烷为最佳反应介质,最佳水含量为8％,最佳酸醇摩尔比为1：2,最适催化温度为55℃,得到的活化能Eα为19．00kJ／mol。     

含O-, S-, N-和C-2,3-不饱和糖苷的合成

以3,4,6-三-O-乙酰基-D-葡萄烯糖为原料,(NH₄)₂S₂O₈为催化剂,利用Ferrier重排反应制得一系列含O-, S-,N-和C-2,3-不饱和糖苷,其结构经¹H NMR, IR和MS（ESI）确证。考察了催化剂及其用量,溶剂和温度对产率的影响。结果表明：在最优条件［反应温度80 ℃,乙腈为溶剂,(NH₄)₂S₂O₈为催化剂(1 eq.)］下,3a产率高达83%。     

稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能

以工业生产中碱法溶硅剩余的稻壳残渣为碳源,采用硫酸磺化法制备稻壳碳基固体酸催化剂,考察了其催化木糖脱水制备糠醛的性能.采用红外光谱、元素分析及表面酸浓度测定等手段对催化剂进行了表征.对固体酸催化剂的制备条件进行了优化,所得催化剂的表面酸浓度可达1.03 mmol/g.以木糖脱水制备糠醛为模型反应,考察了溶剂类别、反应温度和反应时间对固体酸催化剂催化性能的影响.实验结果表明,以二甲基亚砜(DMSO)为反应溶剂效果优于水,并且随着反应温度的升高和反应时间的延长,反应产率逐渐增加,最高可达75.8%.此外,还对催化剂的循环性能进行了研究,探讨了其失活原因和再生方法.     

Anion-exchange behaviour of several elements in hydrobromic acid-organic solvent media

The anion-exchange behaviour of 19 elements in hydrobromic acid-organic solvent media has been investigated. The batch distribution coefficients of the metal ions were determined in these systems employing the strongly basic anion-exchange resin Dowex 1, x 8. Organic solvents used were methanol, ethanol, n-propanol, isopropanol, methyl glycol, acetone, tetrahydrofuran and acetic acid. The most suitable conditions for some quantitative separations based on these equilibrium studies are indicated and discussed.