乙醇-水混合溶液中1-苯基-3-甲基-4-苯甲酰基吡唑酮-5对Nd(Ⅲ), Eu(Ⅲ),Ho(Ⅲ)的萃取及其机理

在乙醇－水混合溶液中，1－苯基－3－甲基－4－苯甲酰基吡唑酮－5与Nd(Ⅲ）,Eu(Ⅲ）,Ho(Ⅲ）等及乙醇形成了萃合物，使萃取分配比明显提高。利用斜率法研究了萃取机理。借助红外（IR）、元素分析、热分析（TG－DTA）等手段对萃合物进行了表征。     

钴－5－（4－硝基苯偶氮）－8－（4－甲苯磺酰氨基）－喹啉配合物的极谱波研究

钴（Ⅱ）在ＨＡｃ－ＮａＮＯ＿２－吐温－８０－ＮＰＴＳＱ体系中有一灵敏的阴极极化导数波，其峰电位－１．００Ｖ（ｖｓ．ＳＣＥ），钴浓度在４．０×１０￣（－９）～３．０×１０￣（－７）ｇ／ｍＬ范围内与峰电流有良好的线性关系。本文讨论了测定钴（Ⅱ）的最佳实验条件，对极谱波的性质进行了初步探讨，并作了维生素Ｂ＿（１２）中钴的测定，测定结果的相对标准偏差为３．７４％，回收率为９６～１０８％。     

Cu（Ⅱ）与L－氨基酸和5＇－嘌呤核苷酸配合物的SOD活性

Ｃｕ（Ⅱ）与Ｌ－氨基酸和５＇－嘌呤核苷酸配合物的ＳＯＤ活性邵昌平，赵丽华，刘宇新，郭和夫（中国科学院大连化学物理研究所，大连１１６０２３）关键词Ｃｕ（Ⅱ）－氨基酸配合物，Ｃｕ（Ⅱ）－氨基酸－核苷酸配合物，ＳＯＤ活性．１．前言在已发现的三种超氧化物歧化...     

介质对配合物稳定性的影响──Ⅶ．Cu（CTS）~（2－）－NaCl_4－C_2H_5OH－H_2O体系

用分光光度法于２９３±１Ｋ温度下测定了由二价阳离子Ｃｕ（２＋）和高价阴离子（ＣＴＳ）（４－）（３，６－二磺酸根－１，８－二羟基萘酚）形成配阴离子Ｃｕ（ＣＴＳ）（２－）在乙醇－水混合溶剂中的稳定常数随离子强度的变化．溶剂中乙醇的重量百分数分别为０、１０、２０、３０、４０和５０；每个混合溶剂中的离子强度均为０．１－３．０ｍｏｌ·ｄｍ（－３）．分别用推广的Ｄｅｂｙｅ－Ｈｕｃｋｅｌ方程［１］和Ｐｉｔｚｅｒ方程［２］计算了配离子的热力学稳定常数．发现对本体系Ｄｅｂｙｅ－Ｈｕｃｋｅｌ方程完全不能适用，而基于Ｐｉｔｚｅｒ方程的多项式逼近法［３］则可得到满意的结果．简单讨论了介质效应和配位反应的标准迁移自由能．     

镉（Ⅱ）－2－（2－苯并噻唑偶氮）－5－二甲氨基苯甲酸配合物的吸附伏安法研究及应用

镉（Ⅱ）－２－（２－苯并噻唑偶氮）－５－二甲氨基苯甲酸配合物的吸附伏安法研究及应用徐素君，施清照，张培敏，吴念慈（杭州大学化学系３１００２８）关键词：２－（２－苯并噻唑偶氮）－５－二甲氨基苯甲酸（ＢＴＡＭＢ），镉，吸附伏安法杂环偶氮试剂的极谱性质及其...     

薄层光密度法测定低含量的N－（α－萘基）咔唑和N－（β－萘基）咔唑

测定了光诱导ＳＲＮ１反应生成的Ｎ－（α－萘基）咔唑和Ｎ－（β－萘基）咔唑。光化学反应产物用硅胶板展开，外标法定量，测定波长２８８ｎｍ，斑点的线性范围０～２μｇ，回收率１００．５％，相对标准偏差４．８％，Ｎ－（α－萘基）咔唑含量＜１％，Ｎ－（β－萘基）咔唑含量２．２６％。     

二安替比林基－（3－羟基）苯基甲烷光度法测定痕量钒

合成和鉴定了二安替比林基－（３－羟基）苯基甲烷（ＤＡｍＨＭ），研究了它与Ｖ（ｖ）的显色反应。在磷酸介质中，在Ｍｎ（Ⅱ）和吐温－４０存在下，ＤＡｍＨＭ与Ｖ（Ｖ）生成橙黄色化合物，λ＿（ｍａｘ）＝４８０ｎｍ，ε＝１．０３×１０￣６Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），Ｖ（ｖ）量在０．２～１．２ｕｇ／２５ｍＬ间符合比尔定律，体系灵敏度高，稳定性好，用于中草药中痕量钒的测定，结果满意。     

TritonX-100-盐-水液-固萃取体系分离Co,Cd,Zn

在含有一定浓度硫酸铵的条件下，ＴｒｉｔｏｎＸ－１００水溶液能形成盐水相与聚合物固相。本实验研究了Ｃｏ（Ⅱ）、Ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）、Ｆｅ（Ⅲ）与４－（２－吡啶偶氮）间苯二酚（ＰＡＲ）形成的配合物在ＴｒｉｔｏｎＸ－１００盐水萃取体系液固两相中的分配行为。主要探讨萃取酸度，萃取剂用量和硫酸铵浓度等条件对金属离子萃取率的影响。用控制酸度的方法实现了Ｃｏ（Ⅱ）与Ｃｄ（Ⅱ），Ｃｏ（Ⅱ）与Ｚｎ（Ⅱ）的定量分离。每组金属离子浓度在１∶１０００倍情况下分离互不干扰，结果满意。该法可用于样品的提纯与分离。     

非水溶性新卟啉显色剂T（BHMOP）P与Cd（Ⅱ）显色反应的研究及应用

系统研究了新合成的非水溶性卟啉显色剂ｍｅｓｏ－四（３－溴－４－羟基－５－甲氧基苯基）卟啉，简称Ｔ（ＢＨＭＯＰ）Ｐ，与Ｃｄ（Ⅱ）的显色反应条件。在Ｔｗｅｅｎ－８０存在下，不需任何催化剂，沸水浴１４ｍｉｎ，Ｃｄ（Ⅱ）与Ｔ（ＢＨＭＯＰ）Ｐ形成稳定的绿色配合物，ε（４４２）＝２．２９×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。在混合掩蔽剂存在下，应用于大米、面粉及皮蛋等食品中痕量镉的测定，结果满意。     

μ－4，4＇－联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４＇－联吡啶为桥联配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·２Ｈ＿２Ｏ（１）、［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３］（ｂｐｙ）＿３］（ＣｌＯ＿４）＿６·Ｈ＿２Ｏ（２）和［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ＮＯ＿２－ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·６Ｈ＿２Ｏ（３）。经元素分析、电导、ＩＲ、电子光谱、ＥＳＲ、磁化率等方法进行了表征，推定该配合物具有以４，４＇－联吡啶为扩展桥的结构。利用Ｈｅｉｓｅｎｂｅｒｇ模型求得交换参数Ｊ值为－０．２３ｃｍ－１（１）和－０．９０ｃｍ－１（３），表明配合物中金属离子间仅有很弱的反铁磁交换作用．     

Kinetics and products of ozonation of C.I. Reactive Red 195 in a semi-batch reactor

Textile wastewater shows great threats to the environment if not well pretreated before discharge. A promising technique, ozonation, was applied to remove the color in dye solutions containing C.I. Reactive Red 195 (RR195) in a semi-batch reactor. The decolorization of RR195 by the ozone process followed pseudo-first-order kinetics. Several factors which influenced the efficiency of decolorization were studied and the reaction rate constant (k) obtained with different operational parameters was compared. Our results showed that RR195 was more easily degraded in acidic than in alkaline conditions. The dyeing auxiliaries (sodium carbonate and sodium chloride) that acted as radical scavengers could enhance the decolorization process, and the ozonation time for total color removal lengthened if the initial dye concentration was higher. The analysis of the ozonation products was performed by liquid chromatography-tandem mass spectrometer and a possible degradation pathway was predicted according to the ozonation products and structure of RR195. Our results indicated that ozonation was effective in the color removal of dyes, but further treatment might be necessary since the ozonation products are high toxic.     

Isotopic splitting patterns in the 13C NMR spectra of some partially deuterated 1‐aryl‐2‐(phenyldiazenyl)butane‐1,3‐dione and 4‐hydroxy‐3‐(phenyldiazenyl)‐2H‐chromen‐2‐one: evidence for elucidation of tautomeric forms

Nuclear magnetic resonance spectra of synthesized azo dyes derived from aniline derivatives in reaction with benzoylacetone and 4‐hydroxycoumarin were studied in both CDCl₃ and (CD₃)₂SO (two drops of D₂O were added into solutions of dyes). All dyes showed intramolecular hydrogen bonding. Dyes derived from o‐nitro aniline in the reaction with benzoylacetone, and 4‐hydroxycoumarin showed bifurcated intramolecular hydrogen bonds. The solvent‐substrate proton exchange of dyes derived from benzoylacetone and 4‐hydroxycoumarin was examined in the presence of two drops of D₂O. Among ten dye samples, two dyes derived from benzoylacetone did not show deuteration, three dyes showed partial deuteration and five dyes showed full deuteration under similar conditions. For the partially deuterated dyes the β‐isotope effect in ¹³C splitting was investigated and was used for the determination of the predominant tautomeric form. Copyright © 2016 John Wiley & Sons, Ltd.     

固相萃取-高效液相色谱法同时测定调味品中15种工业合成染料

建立了测定调味品中15种工业合成染料的固相萃取-高效液相色谱法(SPE-HPLC)。样品经甲醇-水(1:1, v/v)超声提取、SPE柱净化后用HPLC进行分析,流动相为10 mmol/L乙酸铵溶液(含1%乙酸)和乙腈。实验结果表明15种工业合成染料的分离效果良好,回收率为84.6%～114.2%,相对标准偏差为0.9%～10.3%;检出限为0.05～0.18 mg/kg。该方法操作简单,结果准确,重现性好,可用于同时测定调味品中非法添加的15种工业合成染料。     

磁性金属有机骨架-聚多巴胺的制备并用于水产养殖水样中阳离子染料的萃取检测

利用多巴胺（DA）中的儿茶酚基团能与金属有机骨架晶体（MOFs）中金属离子螯合的原理,以ZIF-67为模板,经DA蚀刻-自聚合形成具有孔洞结构的聚多巴胺（PDA）壳层,制备了磁性-MOFs-PDA（Fe₃O₄@Z67D）新型材料。多种表征手段验证了材料的形貌、结构和性能。新型材料具有亲水性的表面、纳米级的孔径,以及良好的磁响应,被用作磁固相萃取吸附剂。结合高效液相色谱分析手段,建立了萃取检测亚甲蓝（MB）和结晶紫（CV）两种阳离子染料的新方法。在最优的萃取和色谱分析条件下,MB和CV的线性范围分别为0.5~200 μg/L和0.01~50 μg/L,检出限分别为0.04 μg/L和0.008 μg/L,对两种染料的富集因子分别为777和688。新型材料重复使用10次,其萃取性能未见发生变化。该方法成功应用于检测淡水鱼养殖用水中痕量的MB和CV,加标回收率为82.0%~109.0%,RSD低于2.9%。     

C60O结构和电子光谱的理论研究

用ＩＮＤＯ系列方法研究Ｃ６０Ｏ的两种结构：一是桥氧加在２个六元环之间的键上为Ｃ２ｖ构型；另一个是桥氧加在１个五元环和１个六元环之间的键上为Ｃｓ构型。计算表明，从总能量、ＨＯＭＯ－ＬＵＭＯ能级差和光谱性质看，Ｃ６０Ｏ的稳定构型都应是Ｃ２ｖ构型，该Ｃ２ｖ异构体具有环氧结构（桥Ｃ１５－Ｃ３０键长为０．１５１８ｎｍ，键序为０．８７４４），其电子光谱计算结果与实验值较好地符合。     

Decolorization of AZO dyes using catalytic ozonation

Decolorization of C.I. Reactive Red 2 (RR2) and C.I. Acid Orange 6 (AO6) using a catalytic ozonation system was evaluated. The decolorization rates for RR2 and AO6 were accelerated by at least 30% by adding MnO₂ to the O₃ system; additionally, the decolorization rate increased as the MnO₂ dosage and ozone power consumption increased. Enhanced MnO₂ catalytic ozonation was more apparent for AO6 than for RR2.     

Stripping voltammetric determination of silver(I) at carbon paste electrode modified with 3-amino-2-mercapto quinazolin-4(3H)-one

A differential pulse anodic stripping voltammetric method was developed for the determination of Ag(I) at a 3-amino-2-mercapto quinazolin-4(3H)-one modified carbon paste electrode. The analysis procedure consisted of an open circuit accumulation step in stirred sample solution for 12 min. This was followed by medium exchange to a clean solution where the accumulated Ag(I) was reduced for 15 s in −0.6 V. Subsequently an anodic potential scan was effected from −0.2 to +0.2 V to obtain the voltammetric peak. The detection limit of silver(I) was 0.4 μg L⁻¹ and R.S.D. for 10, 100 and 200 μg L⁻¹ silver(I) were 2.4, 1.8 and 1.3%, respectively. The calibration curve was linear for 0.9-300 μg L⁻¹ silver(I). Many coexisting ions had little or no effect on the determination of silver(I). The procedure was applied to determination of silver(I) in X-ray photographic films and natural waters. In X-ray photographic film samples, the results have compared to those obtained by atomic absorption spectroscopy.     

Potentiometric determination of silver(I), palladium(II) and gold(III) in mixtures by use of an iodide-selective electrode

Two procedures are proposed for the potentiometric determination of Ag(I), Pd(II) and Au(III) in binary mixtures, by titration with potassium iodide solution, and use of a commercial iodide electrode as sensor. In the first procedure, two aliquots of the mixture are titrated, at pH 2.0 ± 0.2 and 9.0 ± 0.2, adjusted with dilute sulphuric acid and ammonia solution. At pH 2.0, the titrant reacts with both metals, whereas at pH 9.0, Ag(I) is the only reactant. The second procedure utilizes titration of two aliquots of the mixture in the presence and absence of a selective masking agent. The methods have been applied to the determination of these metals in some jewellery alloys.     

KBrO3-KBr紫外分光光度法测定痕量苯酚

研究了在盐酸介质中以 KBrO3-KBr 紫外分光光度法测定痕量苯酚的条件,在浓度为 0.6mol/L HCl,3×10-5mol/L KBrO3,5×10-4mol/L KBr,6×10-4mol/L KI 溶液中测定苯酚时,线性范围为 0.10～2.5mg/L,表观摩尔吸光系数为 1.89×104L·mol-1·cm-1,Sandell 指数为 4.98μg/cm2.本法已用于测定废水中苯酚.     

Study on the Catalytic Effects of Ruthenium on the Oxidation of Basic Dyes by Kio4 and its Analytical Applications

ABSTRACT

Three sensitive catalytic spectrophotometric methods have been developed for the determination of ruthenium(III), based on its catalytic effects on the oxidation reactions of three basic dyes: nile blue (NB), butyl rhodamine B (BRB) and methylene blue (MB), by KIO⁴ in acidic medium at 90±0.5 °C. The above reactions are followed spectrophotometrically by measuring the decrease in the absorbance at 630 nm, 555 nm and 670 nm for the catalytic reactions of NB, BRB and MB, respectively. The working curves for the three recommended reaction-rate methods are linear in the concentration range over 0.0080-1.2 and 0.0080-0.72 μg/L for NB and BRB methods, and 0.0-1.2 and 1.2-5.6 μg/L for MB method. Almost no foreign ion interfered in the determination at less than 10-fold concentration of Ru(III). The methods are highly sensitive, more selective and very stable, and have been successfully applied for the determination of trace amount of ruthenium in some ore and metallurgy products. The kinetic parameters and the catalytic reaction mechanism have also been studied.