催化动力学光度法测定人发中的痕量铜

在NH3.H2O介质中,微量Cu(Ⅱ)能显著催化过硫酸铵氧化溴百里酚蓝的褪色反应。研究了该褪色反应的最佳反应条件,建立了催化动力学测定铜的新分析方法。本法测定铜的线性范围在0.00~0.08μg.mL-1。回收率在97.5%~99.0%之间,RSD为0.6%~1.6%,检出限为4.8×10-8g.L-1。用于人发中痕量Cu(Ⅱ)的测定,结果满意。     

萃取催化光度法测定粉煤中的微量铜

在NH3·H2O NH4Cl缓冲溶液(pH9.2)中,微量铜(Ⅱ)对过氧化氢氧化等色染料离子对(TBF(BRB)2)褪色反应具有催化作用,催化程度与Cu(Ⅱ)浓度在0 25μg/L～3 50μg/L范围内呈线性关系,用萃取平衡控制反应时间和水中有机染料浓度,建立了一种测定Cu(Ⅱ)的萃取催化光度法的新方法。方法的检出限为0 11μg/L,该法已应用于粉灰中微量铜的测定。     

KBrO_3-邻氨基酚体系催化动力学光度法测定微量Cu(Ⅱ)

在pH为4.5的HAc-NaAc缓冲溶液介质中,Cu(Ⅱ)能催化KBrO_3氧化邻氨基酚而显色,据此建立了测定微量Cu(Ⅱ)的新方法。方法的测定波长为430nm,反应温度为60℃时控制反应时间为6min,Cu(Ⅱ)在0.10~1.2μg/mL范围内吸光度与Cu(Ⅱ)的浓度呈良好的线性关系,相关系数r为0.9971。方法用于测定冶炼厂电解银废液中铜含量,相对标准偏差为2.49%(n=6),加标回收率在91.6%~99.4%之间。     

KBrO3-耐尔蓝A体系催化光度法测定痕量钒

研究了在H2SO4介质中,柠檬酸存在下,痕量V（Ⅴ）催化KBrO3氧化耐尔蓝A的褪色反应,通过测定640 nm波长下催化体系和非催化体系的吸光度,建立了催化光度法测定痕量V（Ⅴ）的新方法。方法的线性范围为0.00020-0.0040μg/mL,检出限为7.1×10^-12g/mL。已用于自来水和大米中痕量钒的测定。     

催化光度法测定微量铜

铜是人体内多种酶的活性成分,以人体的新陈代谢有重要调节作用[1]。因此研究铜的分析方法一直引起人们的关注。关于动力学分析法测定Cu(Ⅱ）已有不少文献报道[2-4],但大多是利用铜催化H2O氧化有机染料褪色为指示反应。罗丹明B具有较大的摩尔吸光系数,用于催化动力学分析其测定灵敏度比一般指示剂更高。本研究发现在硫酸介质中Cu( Ⅱ）对溴酸钾氧化罗丹明B的褪色反应有着强烈的催化作用,据此建立了一种新的催化光度测定微量铜离子的反应体系,可用于一些含铜物质的鉴定。     

催化动力学褪色光度法测定痕量铜

用催化动力学方法测定微量铜,早在20世纪初已有报道,所用的催化反应体系各不相同。也有用催化褪色反应的动力学方法测定痕量铜（Ⅱ）。本试验结果发现,在空气中,铜（Ⅱ）对钛（Ⅲ）氧化褪色反应有催化作用。     

催化荧光法测定痕量铜—Cu（Ⅱ）—藏红T—H2O2体系

本文研究了在氨性介质中,铜(Ⅱ)催化过氧化氢氧化藏红T褪色,使荧光减弱的指示反应。建立了催化荧光法测定痕量铜的新方法。铜量在0.1～2ng/mL范围内呈线性关系。应用于食品中痕量铜的测定,结果满意。     

催化动力学法测定超痕量铜的研究

催化动力学法测定微量铜(Ⅱ)已有报道。作者发现了铜(Ⅱ)在氨水介质中催化过氧化氢氧化澳酚红褪色的指示反应: 溴酚红+H_2O_2+NH_3·H_2O→(铜)(Ⅱ)无色产物其反应速度log(A_o)/A与C_(Cu(Ⅱ))值在一定范围内呈线性关系。本实验研究了新的催化褪色反应及其影响反应速度的因素,建立了测定超痕量铜。(Ⅱ)的新方法。本方法具有突出的优点:①灵敏度高;②具有专属性,无须进行分离富集,可直接测定生物样品等,而且操作简便快速;③分析结果的准确度高,便于推广,使用。     

双波长双指示剂催化光度法测定铜的研究

研究了在pH 4.0的HAc～NaAc缓冲介质中,利用痕量铜(Ⅱ)催化过氧化氢氧化罗丹明B和亚甲基蓝褪色的指示反应,通过测量540 nm和660 nm下,催化体系和非催化体系吸光度的变化,建立了双波长双指示剂催化动力学光度法测定痕量铜的新方法.方法的线性范围为0.00080～0.048μg/mL,检出限为4.0×10~(-11) g/mL.方法可用于水中铜的测定.     

催化动力学光度法测定痕量铜的研究

本文研究了在氨水介质中铜（Ⅱ）催化过氧化氢氧化亮黄的褪色反应及其动力学条件，建立了一种超高灵敏、高选择性的测定环境试样中痕量铜的新方法，可测定０．００４～０．５μｇ／２５ｍＬ范围内的铜（Ⅱ）。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.