光度法测定有机溶剂中微量水

对于水的分析,国内外普遍使用卡尔·费休法[1 ] 。该方法的适用范围较宽,能够满足多种液体及固体化合物中水的测试要求,但试剂耗费大,毒性较强,容易造成环境污染。7,7,8,8 四氰基对二次甲基苯醌(TCNQ) [2 ] 是一种很强的平面性电子接受体,可与富电子有机物反应形成荷移络合物。水能与TCNQ结合形成兰绿色络合物。本文探讨有机溶剂中TCNQ与水的反应,利用该反应测定醇中微量水的条件。方法简便、快速,重现性好,结果令人满意。1　实验部分1 .1　主要仪器与试剂UV 2 4 0 1PC型紫外可见光光度计(日本岛津) ;HHS·2 1 Ni型电恒温水浴(北京…     

纤维素在新的非水有机溶剂体系中的均相衍生作用研究

本文首先回顾了纤维素衍生化反应和非衍生化反应的有机溶剂,特别是偶极非质子含氧碱性溶剂体系,扼要介绍了纤维素在这两类溶剂中的均相酰化、烷基化和接枝共聚反应的现状。然后,着重叙述作者利用 N_2O_4/DMF 衍生化反应溶剂体系进行纤维素酰化反应合成阴离子酯类(硫酸酯、磷酸酯)的最新研究成果。最后讨论了纤维素在新的有机溶剂体系中的均相衍生作用的优缺点,强调指出羟基位置的取代反应选择性控制的可能性和后处理步骤对决定产物性质的重要作用。     

有机溶剂中微量水的荷移光谱法测定

研究了氯冉酸与有机溶剂中水的反应，确定了反应条件，氯冉酸与水的络合物的最大吸收波长为530nm。在乙醇、甲醇，正丙醇，异丙醇、正丁醇，正庚醇，正己醇溶剂中，水的含量分别在0－5％（V／V）或0－8％（V／V）范围内呈线性关系，相关系数为0．998或0．999；该方法重现性好，灵敏度高，操作简单，用于测定乙醇中微量水的含量，与标准值相符；加入回收法测得甲醇中水的回收率分别为98％－103％，结果令人满意。     

非离子型微乳液介质-天竺牡丹紫催化光度法测定水及土壤中微量锰

研究了以微乳液作为介质,在pH4．5HAc-NaAc缓冲溶液中,用氨三乙酸作活化剂,锰催化高碘酸钾氧化天竺牡丹紫褪色的新指示反应。在580nm处,检出限达到3．8ng/L,线性范围为0．4-5．6μg/L。该法用于土壤及水中微量锰的测定,相对标准偏差小于3．6％,加标回收率在95％-107％范围内,取得了令人满意的结果。     

面粉中微量水的分光光度法测定

氯冉酸可以与醇中的水发生荷移反应，形成的水合物的最大吸收波长为530nm。在甲醇中，水的含量在0％-8．0％(V/V)范围内与吸光度呈线性关系；在乙醇、正丙醇、正丁醇、正庚醇和正己醇中测定水的线性范围为0％．6．0％(V/V)。方法灵敏度高，检测下限为0．13％(V/V)；重现性好，重复实验相对标准偏差小于2％。反应迅速，操作简便。用拟订的方法测定面粉及乙醇中的微量水，结果与标准值相符，回收率为98％-102％。     

靛蓝胭脂红-高碘酸钾-草酸钠催化光度法测定钢中微量钒

研究了在1 mol/L磷酸介质中，钒(V)对KIO4氧化靛蓝胭脂红褪色反应的催化作用及草酸钠的活化作用，建立了一种测定钒的方法。无草酸钠时该体系为准零级反应，表观活化能为76.7 kJ/mol，在22℃时钒量在0～5mg/L范围内与?A呈线性，检出限为0.1　mg/L。在草酸钠存在下则为准一级反应，表观活化能为60.1 kJ/mol，钒量在0～mg/L范围内与1g(A0/A)呈线性，检出限为0.02mg/L。提高介质酸度，可显著降低反应温度。在NaF及尿素存在下，大多数常见离子无干扰。本法简便快速，选择性和灵敏度较高，用于钢中微量钒的直接测定，结果满意。     

有机溶剂中微量水分的测定

绕丹宁与水在有机溶剂中发生诱导荷移反应,产生吸收光谱移动且吸收峰增大。基于此,优化了实验条件,建立了一种快速、简便、灵敏的测定有机溶剂中微量水分的新方法。甲醇、醋酸溶剂中的水分含量分别在3％-10％（φ）、0～4％（φ）范围及乙醇、1-丙醇、丙酮、乙酸乙酯溶剂中水分含量在0～5％（φ）范围内与吸光度（A）呈线性关系。其相关系数分别是0．9992、0．9996、0．9992、0．9982、0．9990和0．9995。使用本方法测定了灯用酒精中水分含量,结果令人满意。     

PVB-联吡啶钌氧敏感膜荧光光度法对非水溶剂中微量溶解氧的测定

以聚乙烯醇缩丁醛(PVB)为共聚前驱体,联吡啶钌([Ru(bpy)3]Cl2·6H2O)为氧荧光指示剂,制备了一种新型氧敏感膜,据此建立了采用流动注射荧光光度法测定非水溶剂中微量溶解氧的新方法.在涂膜液中联吡啶钌浓度为1 mmol/L,涂膜液用量为2.5 mL,20 ℃下放置24 h,40 ℃恒温干燥48 h时,制备的氧敏感膜(膜厚0.5 mm)对氧响应的灵敏度最高.当激发波长为465 nm,溶液流速为1.0 mL/min时,该敏感膜对氧有较快的响应时间、良好的响应可逆性、较好的稳定性.对1,2-丙二醇和PEG-400中溶解氧的测定结果表明,两者的Stern-Volmer曲线的线性范围分别为0 ～69.12 mg/L和0 ～109.54 mg/L,检出限分别为4.25 mg/L和0.56 mg/L,RSD(n=6)分别为2.0%和1.8%.     

荧光分光光度法研究酶在非水相体系中的转酯化反应活性

以4-肼基-7-硝基-2,1,3-苯并氧杂二唑肼为荧光底物,乙烯基羧酸酯、伯醇为转酯化反应底物通过荧光分光光度法比较了几种能以固体聚合物为底物的商品化酶制剂在有机溶剂中催化转酯化反应的性质.该方法使用微量溶剂和底物进行反应,测定快捷,具有很高的直观性.实验所用4种酶制剂均可在异辛烷、甲苯和乙腈中催化转酯化反应,催化能力是脂肪酶LPL-3>蛋白酶Alcalase 3.0 T>蛋白酶subtilisin Carhberg>蛋白酶bacillolysin,但有机溶剂的疏水性对转酯化反应影响较大,疏水性高的有机溶剂比较适合做酶催化转酯化反应的溶剂.和月桂酸乙烯酯相比,小分子的丙酸乙烯酯更有利于酶催化转酯化反应的进行.     

非水毛细管电泳进展

 毛细管电泳通常是在以水为溶剂的缓冲溶液中进行的,事实上以纯有机溶剂替代水介质同样可以完成特殊样品的电泳分离,且存在诸多优点。以所建立的非水毛细管电泳方法为核心,总结了该方法中有机溶剂、电解质的选择原则及溶质-添加剂相互作用模式,并综述了它在无机离子、中性物质、有机酸等化合物分离分析中的应用。71篇。     

Biothermal Analysis Performed In Organic Solvents

Abstract

A thermal assay probe (enzyme thermistor) was used to study the performance of enzymic analyses by immobilized enzymes in organic solvents and in mixtures of organic solvents and aqueous buffer. It was found that rather small amounts of alcohols (around 5 %, v/v) in the buffer approximately doubled the registered temperature changes for glucose oxidase and catalase, mainly by increasing the total enthalpy change of the reaction. the heat production for peroxidase catalyzed reactions was as much as 45 times higher in toluene compared to buffer. the advantage of increased substrate solubility in organic solvents was demonstrated by operating a lipase column in cyclohexane. All enzymes studied showed good stability in the organic solvents used.     

Determination of Sulfur in Trace Amounts

Abstract

An absolute method for the determination of trace amounts of sulfur in water and organic matrices is described. The method involves decomposition of organic samples in an oxygen bomb or oxidation of water samples with hydrogen peroxide. The resultant sulfates are reduced and distilled as hydrogen sulfide by the action of stannous phosphate in anhydrous phosphoric acid. The evolved hydrogen sulfide is absorbed in zinc acetate solution, converted to methylene blue and measured spectrophotometrically at 665 mm. The range is from 2 to 40 μg of sulfur using 1 cm cells.     

共轭尺寸和表面氧化协同触发的红色荧光碳点用于有机溶剂中痕量水的检测

以邻苯二胺和盐酸多巴胺为前体,利用磷酸调节反应体系的pH值(pH=7, 3, 1),制备了荧光逐渐红移的碳点(CDs):CDs-7(绿光)、 CDs-3(橙光)和CDs-1(红光).通过透射电子显微镜(TEM)、拉曼光谱(Raman)、傅里叶变换红外光谱(FTIR)、 X射线电子能谱(XPS)、紫外-可见吸收光谱和荧光衰减曲线分析表明,反应体系pH值的减小促进了前体碳化交联,导致sp2共轭域尺寸和石墨化程度增加,从而使CDs的荧光红移.另外,酸性环境有利于使CDs表面氧化形成羧基,促进CDs荧光红移的同时改善了量子效率(QY).利用CDs-1量子产率高(14.8%)和发光的溶剂依赖特性,将其作为荧光探针分别检测了乙醇(EtOH)、 N,N-二甲基甲酰胺(DMF)和1,4-二氧六环(DIO)中的痕量水,检出限分别为0.86%, 0.123%和0.023%,表明CDs-1在痕量水的检测方面具有应用潜力.     

催化光度法测定水中痕量铜

采用抗坏血酸还原性铬蓝Ｋ的反应,在２,２’－联吡啶活化下被Ｃｕ＾２＋催化加速,建立了催化光度法测定水中痕量铜的新方法。考察了影响反应速度的最佳条件。探讨了反应机理。方法的测定范围是０．００－１．２ｎｇ／ｍＬ,检出限达１．８＊１０＾－１１ｇ／ｍＬ。方法已经用于蒸馏水,自来水中痕量Ｃｕ＾２＋的测定。     

Micellar Solubilization of Proteins in Aprotic Solvents and their Spectroscopic Characterisation

The quaternary ammonium salt methyl-trioctylammonium chloride enables the transfer of α-chymotrypsin, trypsin, pepsin and glucagone from water to cyclohexane. Reversed micelles, whose polar core solubilizes both protein and water, are probably formed in the apolar phase. The influence of various parameters on the phase transfer (concentration, pH, solvent, temperature, etc.) has been investigated. Absorption, fluorescence and circular dichroism studies of the biopolymers in the cyclohexane system have been carried out. For trypsin and chymotrypsin, the CD. signal in the 200 nm region is very similar in water and in cyclohexane, which suggests that the polypeptide folding is not substantially different in the two phases. The fluorescence quantum yield is always much larger in the cyclohexane phase than in water. The longer wavelength region of the UV. absorption spectrum is slightly red-shifted relative to water, and a band at 225 nm, probably arising from the aromatic chromophore, is apparent in the organic phase. Reasons for these spectral perturbations are discussed. The enzymes transferred from water into cyclohexane phases can be continuously retransferred into a second water phase. The possible relevance of this ‘double transfer’ as a model for the vectorial transport of biopolymers or a separation technique is discussed.     

Development of Microdroplet Generation Method for Organic Solvents Used in Chemical Synthesis

Recently, chemical operations with microfluidic devices, especially droplet-based operations, have attracted considerable attention because they can provide an isolated small-volume reaction field. However, analysis of these operations has been limited mostly to aqueous-phase reactions in water droplets due to device material restrictions. In this study, we have successfully demonstrated droplet formation of five common organic solvents frequently used in chemical synthesis by using a simple silicon/glass-based microfluidic device. When an immiscible liquid with surfactant was used as the continuous phase, the organic solvent formed droplets similar to water-in-oil droplets in the device. In contrast to conventional microfluidic devices composed of resins, which are susceptible to swelling in organic solvents, the developed microfluidic device did not undergo swelling owing to the high chemical resistance of the constituent materials. Therefore, the device has potential applications for various chemical reactions involving organic solvents. Furthermore, this droplet generation device enabled control of droplet size by adjusting the liquid flow rate. The droplet generation method proposed in this work will contribute to the study of organic reactions in microdroplets and will be useful for evaluating scaling effects in various chemical reactions.     

Osmotic Coefficients and Activity Coefficients of Nonaqueous Electrolyte Solutions. Part 2. Lithium Perchlorate in the Aprotic Solvents Acetone, Acetonitrile, Dimethoxyethane, and Dimethylcarbonate

Vapor pressure lowering by the addition of lithium perchlorate to the aprotic solvents acetone (0.02–0.6 m), acetonitrile (0.05–1.2 m), dimethoxyethane (0.02–0.4 m), and dimethylcarbonate (0.03–1.8 m) was measured at 25°C with high precision. The experimental data for the corresponding osmotic coefficients are compared to those obtained from the Pitzer equations and chemical model calculations. Mean activity coefficients are derived from the osmotic coefficients.     

固相微萃取-气相色谱/质谱测定工业废水中痕量有机物的研究

采用固相微萃取(SPME)技术结合气相色谱-质谱(GC/MS)法对石化工业废水中的痕量有机物进行检测和分析。针对废水中存在的几种主要有机物,对影响SPME的参数进行了优化。建立的方法在所测的范围内具有良好的线性(相关系数:0.981.00),检测限达0.329.1 μg/L,重复测定的相对标准偏差小于7%,回收率为78.6%125.1%。采用该方法对某石化工业废水样品中主要存在的25种痕量有机物进行测定,结果表明这是一种简便、准确的分析方法,所测得的结果可为废水的治理提供科学依据。