钯（Ⅱ）－二溴羟基苯基荧光酮－溴化十六烷基三甲铵体系分光光度法的研究

在ｐＨ６．１～６．７的磷酸盐介质中，钯（Ⅱ）与二溴羟基苯基荧光酮－溴化十六烷基三甲铵于室温下反应，生成水溶性和稳定性皆佳的紫色三元配合物，最大吸收波长为６００ｎｍ，对比度为７０ｎｍ，表现摩尔吸光系数为９．４８×１０￣４Ｌ．ｍｏｌ￣（－１）’ｃｍ￣（－１），桑德尔灵敏度为１．１２×１０￣（－３）μｇ．ｃｍ￣（－２），钯含量在０～７．０μｇ／１０ｍＬ范围内服从比尔定律。据此提出了一个灵敏、简便分光光度法测定钯的新方法，用于合成试样和贵金属合金中微量钯的测定，结果满意。     

无机还原剂与光泽精化学发光反应的研究Ⅲ．钒（Ⅱ）－光泽精体系的化学发光反应

本文采用装有Ｊｏｎｅｓ柱的流动注射系统，研究了钒（Ⅱ）－光泽精体系的化学发光反应。在此基础上建立了痕量钒测定的新方法。方法的检出限３×１０￣（－１０）ｇ·ｍＬ￣（－１）；对于１．０×１０￣（－７）ｇ·ｍＬ￣（－１）钒标准溶液测定的相对标准偏差为２％（ｎ＝１１）；线性范围１．０×１０￣（－９）～９．０×１０￣（－５）ｇ·ｍＬ￣（－１），相关系数大于０．９９８０。该方法已用于水样中痕量钒的测定。对于反应机理，本文也进行了探讨。     

还原剂与鲁米诺化学发光反应的研究（Ⅳ）──痕量铀的流动注射－化学发光测定

本文利用流动注射系统研究了由Ｊｏｎｅｓ柱产生的铀（Ⅲ）与鲁米诺之间的化学发光反应，建立了痕量铀的化学发光测定法。方法的检出限是３×１０￣（－１０）ｇ／ｍＬ铀。校准曲线的线性范围是１×１０￣（－９）～４×１０￣（－６）ｇ／ｍＬ铀，相对标准偏差为２％（测定２×１０￣（－９）ｇ／ｍＬ铀，ｎ＝１１）。对于反应机理进行了初步研究。     

硅钼杂多阴离子薄膜修饰电极线性扫描伏安法测定黑液中可溶性硅

本文报导了以玻碳电极为基体的１：１２硅钼杂多阴离子薄膜化学修铈电极的制备及其电化学特性。并应用于导数伏安法测定。在４．０×１０￣（－３）ｍ０ｌ／Ｌ（ＮＨ＿４）＿６ＭＯ＿７Ｏ＿（２４）－６．８×１０￣（－２）ｍｏｌ／ＬＮａ＿３Ｃｉｔ－０．４８ｍｏｌ／ＬＮＨＯ＿３体系中，硅浓度在８．３×１０￣（－７）～１．７×１０￣（－３）ｍｏｌ／Ｌ范围内与峰电流呈良好线性关系，检测限为８．０×１０￣（－７）ｍｏｌ／Ｌ。对可溶性硅（以ＳｉＯ＿２计）为２４５．０５ｍｇ／Ｌ的黑液，稀释１０倍后，取２．００ｍＬ平行测定９次，ＲＳＤ为０．５８％，加标回收率在９７．３％～１０４．４％间。     

催化光度法测定痕量α，α′－联吡啶

基于α，α′－联吡啶对Ｈ＿２Ｏ＿２氧化靛红的褪色反应的催化作用，本文建立了测定α，α′－联吡啶的新催化光度法，灵敏度为２．２５×１０￣（－９）ｍｏｌ·Ｌ￣（－１），测定范围为０～４×１０￣（－８）ｍｏｌ／２５ｍＬ。     

亚硝酸根－品红－8－羟基喹啉吸附波的研究及痕量亚硝酸根的测定

在醚性介质中，碱性染料品红与亚硝醚粮重氦化，然后在碱性介质中与８－羟基喹啉偶联生成偶氮化合物。该偶氮化合物于电位－０．７０Ｖ（ｖｓ．ＳＣＥ）处有一灵敏的极谱波，波高与亚硝酸根浓度在７×１０￣（－９）～５×１０￣（－６）ｇ／ｍＬ范围内呈线性关系，检测限为５×１０￣（－９）ｇ／ｍＬ。该方法用于人唾液中亚硝醚根的测定，结果满意。     

荧光法测定补骨脂素和异补骨脂素

以溴代十六烷基三甲胺（ＣＴＭＡＢ）为胶束试剂，β－环糊精（β－ＣＤ）为包含试剂，在优化实验条件下，用荧光光度法测定了补骨脂中补骨脂素和异补骨脂素．线性范围分别为２×１０－９～８×１０－６ｇ／ｍＬ，２×１０－９～８×１０－７ｇ／ｍＬ；检出限分别为２．６７×１０－１１ｇ／ｍＬ和１．１５×１０－１１ｇ／ｍＬ．     

无机偶合流动注射化学发光法测定锑（Ⅲ）

将锑（Ⅲ）对铬（Ⅵ）氧化Ｉ＾－产生Ｉ２的诱导作用和Ｉ２氧化鲁米诺化学发光反应相偶合，建立了一种流动注射化学发光测定痕量锑的新方法。本方法线性范围１×１０＾－９￣１×１０＾５ｇ／ｍＬ；ＲＳＤ〈４％（ｎ＝１１，Ｃ＝７×１０＾－９ｇ／ｍＬ）；检出限为１×１０＾－１０ｇ／ｍＬ。本法用于矿样中锑的测定，结果令人满意。     

无机还原剂与光泽精化学发光反应的研究：Ⅲ.钒（Ⅱ）—光泽精体系的化…

本采用装有Ｊｏｎｅｓ柱的流动注射系统，研究了钒（Ⅱ）－光泽精体系的化学发光反应。在此基础上建立了痕量钒测定的新方法。方法的检出限３×１０＾－１０ｇ·ｍＬ＾－１；对于１．０×１０＾－７ｇ·ｍＬ＾－１钒标准溶液测定的相对标准偏差为２％（ｎ＝１１）；线性范围１．０×１０＾－９￣９．０×１０＾－５ｇ·ｍＬ＾－１，相关系数大于０．９９８０。该方法已用于水样中痕量钒的测定。对于反应机理，本也进行了探讨。     

催化－导数分光光度法测定石蜡中的痕量锰

本文提出催化－导数分光光度法的原理，并将此原理用于锰（Ⅱ）在碱性介质（ｐＨ值９．８）中催化过氧化氢氧化钙红（ＣＲ）褪色￣［１］的反应，成功地测定了石蜡中的痕量锰。本文还详细地考查了萃取分离干扰离子的条件。其表现摩尔吸光系数为７．４×１０￣７Ｌ．ｍｏｌ￣（－１）．ｃｍ￣（－１），最低检测限为２．５ｎｇ／２５ｍＬ，该法的灵敏度为一般催化法对应反应体系的５．９倍。     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.