头孢环己烯降解产物荧光性质的研究及分析应用

本文详细研究了头孢环己烯（先锋Ⅵ）在酸、碱介质中的降解反应，通过降解产生的荧光产物建立了酸、碱降解荧光分析法。方法检出限分别是０．７６ｎｇ／ｍｌ（酸降解）和１／１ｎｇ／ｍｌ（碱降解），线性范围皆为０￣０．１０μｇ／ｍｌ，精密度和准确度是酸降解荧光分析优于碱降解。酸降解荧光分析应用于血清和尿样中头孢环己烯测定，结果令人满意。     

流动注射光纤荧光探针动力学法测定铁的研究

研究了８－苯胺基－１－萘磺酸作为表面活性剂胶束荧光探针的性质，并将其用作动力学分析的荧光指示剂。建立了以铁（Ⅲ）催化过氧化氢氧化ＡＮＳ－Ｂｒｉｊ３５体系荧光猝灭反应为基础，用流动注射和光导纤维技术测定痕量铁的动力学分析新方法，该法线性范围为５－３００ｎｇ／ｍＬ，检测下限为２ｎｇ／ｍＬ，绝对检出量为０．２ｎｇ，对２０ｎｇ／ｍＬ铁（Ⅲ）进行１１次测定相对标准偏差为０．２７％，可直接用于人发、纯铝和铝合     

流动注射光纤动力学荧光法测定锰──锰－二元荧光配合物－高碘酸钠体系

对二元荧光配合物作为动力学反应指示剂的可行性进行了考察，以８－羟基喹啉－５－磺酸铝－高碘酸钠为指示反应，建立起流动注射光导纤维光谱技术测定痕量锰（Ⅱ）的动力学荧光分析新体系。此法线性范围为５～２００ｎｇ／ｍＬ，检出限为１ｎｇ／ｍＬ，对５０ｎｇ／ｍＬ锰（Ⅱ）进行１１次测定的相对标准偏差为０．５％，分析速度为４５样次／ｈ。     

流动注射光纤动力学荧光法测定锰—锰—二元荧光配合物—高碘…

对二元荧光配合物作为动力学反应指示剂的可行性进行了考察，以８－羟基喹啉－５－磺酸铝高碘酸钠为指示反应，建立起流动注射光导纤维光谱技术测定痕量锰（Ⅱ）的动力学荧光分析新体系，此法线性范围为５－２００ｎｇ／ｍＬ，检出了为１ｎｇ／ｍＬ锰（Ⅱ）进行１１次测定的相对标准偏差为０．５％。分析速度为４５样次／ｈ。     

痕量钨钼联合测定的研究

研究了十六烷基三甲基溴化铵（ＣＴＭＡＢ）对钼（Ⅵ）－桑木色素（ｍｏｒｉｎ）络合物荧光的增敏作用。建立了Ｍｏ（Ⅵ）－ｍｏｒｉｎ－ＣＴＭＡＢ体系荧光法测定Ｍｏ（Ⅵ）的新方法，并以酸效应实现了对钨和钼的联合测定。测定Ｍｏ（Ⅵ）的线性范围为０．０１～０．４μｇ／ｍＬ，检出限为０．５ｎｇ／ｍＬ。本法用于直接测定豆类及牛血清中的钼和温泉水中钨和钼的联合测定，得到满意的结果。     

一种在线液—液萃取微型多用分相器的设计和应用：IV.流动注射液— …

设计了在线液－液萃取多用重分布相器及相应流动注射流路系统与ＩＣＰ－ＡＥＳ法联用。具有良好的分析性能，通过对矿石中某些重稀土元素在硝酸介质中被ＴＢＰ萃取的应用研究表明钇，镱，铒的检出限（３σ）分别为６．８ｎｇ／ｍＬ，０．２ｎｇ／ｍＬ和１．５ｎｇ／ｍＬ，精密度（ＲＳＤ％）分别为０．２４，０．４７和１．８，进样频率为２５－３０个／ｈ。     

流动注射停流荧光动力学分析法测定痕量铁的研究

利用自行组装的流动注射停流荧光动力学分析装置，研究了铁（Ⅲ）与３，５－二溴水杨基荧光酮的荧光动力学反应性质，提出了一种快速，简便，精确地测定痕量铁的新方法，其线性范围为０．０２０－０．２５０μｇ／ｍＬ，线性相关系数为０．９９９，检测限为１０ｎｇ／ｍＬ，以０．２００μｇ／ｍＬ的铁（Ⅲ）作精度试验，Ｒ．Ｓ．Ｄ％＝２．１％（ｎ＝１１）。该方法已成功地用于铝合金及桃树叶中痕量铁的测定，结果分别与ＩＣＰ法和     

以新指示反应高敏催化光度测定痕量钌

钌（Ｒｕ￣Ⅲ）对高碘酸钾氧化无色孔雀绿的显色体系有催化作用，借此催化光度测Ｒｕ￣Ⅲ，灵敏度高。在２０～３０℃下３０～６０ｍｉｎ内，以１ｃｍ吸收池内测得吸光度０．１为可准确测极限，则可测最低浓度为０．０８ｎｇ·ｍＬ￣（－１），若表示为间接摩尔吸光系数则 ＝２．０×１０￣８ｍｏｌ￣（－１）·Ｌ·ｃｍ￣（－１）。工作曲线线性范围为０．０４～０．３６ｎｇ／ｍＬ（室温约为２６℃）．其它贵金属如Ｏｓ￣Ⅷ、Ｒｈ￣Ⅲ、Ａｕ￣Ⅲ、Ａｇ￣Ⅰ、Ｐｄ￣Ⅱ、Ｐｔ￣Ⅳ等至少可允许分别存在２００ｎｇ／ｍＬ、１ｎｇ／ｍＬ、２００ｎｇ／ｍＬ、３０００ｎｇ／ｍＬ、２５ｎｇ／ｍＬ和５ｎｇ／ｍＬ。测定了含所有贵金属和某些其它常见金属人工混合液中的痕量Ｒｕ￣Ⅲ，不含Ｉｒ￣Ⅳ时回收率为９８．５％～１０１．０％，含２．３倍于Ｒｕ￣Ⅳ重量的ｌｒ￣Ⅳ时回收率为１０１．５％～１１２％。     

新试剂5－氟偶氮胂Ⅰ荧光法测定铝的研究

本文报道了新试剂５－氟偶氮胂Ⅰ（５－ＦＡｓＡ－Ⅰ）的合成方法，研究了荧光光度法测定铝的反应条件。Ａｌ（Ⅲ）与试剂在ｐＨ５．６０ＨＡｃ－ＮａＡｃ缓冲介质中形成１＋１红色配合物并呈现荧光，λｅｘ／λｅｍ＝３４８．６／３９１．４ｎｍ，线性范围为０～０．２μｇ／ｍＬ，检测限为３．０ｎｇ／ｍＬ。用于分析茶叶样品中的铝，结果满意。     

导数—同步荧光光谱法同时测定三种B族维生素的研究

研究了维生素Ｂ１的氧化产物（硫色素）、维生素Ｂ２和Ｂ６混合物体系的导数－同步荧光光度谱，提出了混合物体系荧光光谱被分辨开的同时测定方法，该法可不经分离直接测定复合维生素片剂中维生素Ｂ１，Ｂ２及Ｂ６，其线性范围均为０－１．０μｇ／ｍＬ，检出限分别为０．５、１．５及４．０ｎｇ／ｍＬ。     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。