乙醇增敏光泽精—H2O2—pb（Ⅱ）化学发光体系的研究及应用

本研究了Ｈ２Ｏ２氧化光泽精发光反应及乙醇的敏化作用，发现加入乙醇可使铅催化Ｈ２Ｏ２氧化光泽精的发光强度有较大幅度的增强；铅量在３×１０＾－７～８×１０＾－５ｇ／ｍＬ范围内与发光强度成正比，方法检出限为０．１０μｇ／ｍＬ；对含４μｇ／ｍＬｐｂ（Ⅱ）１１次重复测定，其ＲＳＤ为２．３％，对３２种常见的阴阳离子进行了干扰实验，表明人有较好的选择性。本法应用于水样及沉积物标样中痕量铅的测定，结果良好。     

Ti（Ⅳ）－F~－－邻硝基苯基荧光酮－氯化十六烷基吡啶四元体系显色反应的研究

本文较详细研究了在Ｈ＿２ＳＯ＿４介质中，Ｔｉ（Ⅳ）－Ｆ￣－－ｏ－ＮＰＦ－ＣＰＣ体系水相光度法测定痕量钛的新方法。四元体系的最大吸收峰在５６５ｎｍ处，表观摩尔吸光系数为２．１×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），Ｓａｎｄｅｌｌ灵敏度为２．２８×１０￣（－４）μｇＴｉ／ｃｍ￣２。钛含量在０～４μｇ／２５ｍＬ范围内遵守比尔定律。方法用于土壤、粮食、牧草、蔬菜和中草药中钛的测定，结果满意。     

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。     

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％。     

meso－四（3，5－二溴－4－羟基苯基）卟啉［T（DBHP）P］二阶导数光度法同时测定废水中锌和铅的研究

本文研究了ｍｅｓｏ－四（３，５－二溴－４－羟基苯基）卟啉与铅，锌显色反应的二阶导数光谱行为，建立了同时测定电镀废水中锌和铅的二阶导数光度法。在硼砂－氢氧化钠碱性介质中，沸水浴上加热３ｍｉｎ，锌、铅的显色反应即可定量完成。比耳定律范围分别为：０～１０μｇ／２５ｍＬＺｎ￣（２＋），０～１０μｇ／２５ｍＬＰｂ￣（２＋）；检出限为：ｃ＿（Ｌ、Ｚｎ）￣（２＋）＝５．６ｎｇ／ｍＬ，ｃ＿（ＬＰｂ）￣（２＋）＝４．０ｎｇ／ｍＬ。     

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。     

新显色剂2－（5－硝基－2－吡啶偶氮）－5－二甲氨基苯胺与钯显色反应的研究及其应用

用新合成的偶氮试剂２－（５－硝基－２－吡啶偶氮）－５－二甲氨基苯胺（５－ＮＯ＿２－ＰＡＤＭＡ）研究了光度法测定他的反应条件。结果表明，在０．４５～１．２ｍｏｌ／Ｌ盐酸介质中，钯与试剂形成稳定的蓝色配合物，其最大吸收波长位于６２１ｎｍ处，表观摩尔吸收系数为９．４×１０￣４Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），配合成的组成为Ｐｄ：５－ＮＯ＿２－ＰＡＤＭＡ＝１：２，钯浓度在０～１０μｇ／１０ｍＬ范围内符合比尔定律。本方法是目前测定钯的高灵敏度和高选择性体系之一。用于含钯分子筛及二次合金管理样－８８中微量钯的测定，结果满意。     

新显色剂N－辛基－N＇－（氨基对苯磺酸钠）硫脲（OPT）与铜（Ⅱ）显色反应的研究和应用

Ｎ－辛基－Ｎ＇－（氨基对苯磺酸钠）硫脲是新合成的一种显色剂，该试剂极易溶于水而形成无色溶液。在ｐＨ３．６～５．２的ＨＡｃ－ＮａＡｃ缓冲体系中，试剂与铜（Ⅱ）形成一种稳定的蓝色水溶性配合物，其组成比为：Ｃｕ（Ⅱ）：ＯＰＴ＝１：３。配合物的最大吸收波长位于３０１．４ｎｍ，表观摩尔吸光系数ε＿（３０１．４）＝１．８２×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。Ｃｕ（Ⅱ）在０～１０μｇ／２５ｍＬ服从比尔定律，相关系数ｒ＝０．９９９６，方法的检出限为３．８５×１０￣（－９）ｇ／ｍＬ。本法灵敏度高，选择性好、操作简单，可直接在水相中测定。将本法用于合金钢和生物制品中微量铜的测定，均获得满意结果。     

Fe（Ⅲ）－TEA－5－Br－PADAP－H_2O_2体系中催化波的研究及其应

在０．２ｍｏｌ·Ｌ￣（－１）ＮＨ＿４Ｃｌ－ＮＨ＿３·Ｈ＿２Ｏ底液中，（ｐＨ为９．２６），得到一个极为灵敏的Ｆｅ（Ⅲ）－ＴＥＡ－５－Ｂｒ－ＰＡＤＡＰ－Ｈ＿２Ｏ＿２配合吸附催化波，其峰电位为－０．７１Ｖ（ｖｓ．ＳＣＥ）。铁浓度在１．８×１０￣（－１０）～５．４×１０￣（－６）ｍｏｌ·Ｌ￣（－１）范围内与二阶导数波高呈线性关系。对该极谱波的性质进行了研究，证明是一种配合吸附催化波，并成功地应用于各类水样，钒催化剂中微量或痕量铁的测定。     

OAP-H2O2-HRP伏安酶联免疫分析新体系测定人血清总甲状腺素

提出邻氨基酚（ＯＡＰ）－Ｈ２Ｏ２－辣根过氧化物酶（ＨＲＰ）发酶联免疫分析新体系并用于人血清中总甲状腺素的测定。本方法以线性扫描二阶导数伏安法检测ＨＲＰ催化Ｈ２Ｏ２氧化ＯＡＰ的产物,用于游离ＨＲＰ和ＨＲＰ标记物的测定,灵敏度的高于经典的ＥＬＩＳＡ显色光度法。测定游离ＨＲＰ的线性范围为１．０×１０＾１２￣４．０×１０＾－９ｇ／ｍＬ,检测限达６．０×１０＾１３ｇ／ｍＬ。本法对总甲状腺素测定的线性范围为１     

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.