高碘酸钾-酸性品红-NTA-DDMAA体系催化光度法测定良量锰

报道了以氨三乙酸为活化剂，以Ｎ－十二烷基二甲基铵基乙酸（ＤＤＭＡＡ）为增敏剂，高碘酸钾氧化酸性品红催化光度法测定痕量锰的新方法，在ＤＤＭＡＡ存在下，灵敏度提高了７倍（Ｍｎ２＋量为１．２～２．４μｇ／Ｌ）和１４倍（Ｍｎ２＋量为２．４～５．２μｇ／Ｌ），相对标准偏差为２．０％，检出限为１．４×１０－７ｇ／Ｌ，可用于茶叶中锰的测定。     

高压液相色谱法测定肿瘤患者血清中假尿苷的含量

建立了血清中假尿苷含量的高效液相色谱测定法。结果表明，假尿苷在０３７５～１２μｍｏｌ／Ｌ范围内线性关系良好。最低检测量为００１５μｍｏｌ／Ｌ，回收率为９２７％，日内和日间相对标准偏差（ＲＳＤ）分别为４２％和４７％。用该法测定正常人及肝癌、肺癌、食管癌患者血清中假尿苷含量发现，３种肿瘤患者血清中假尿苷含量明显高于正常人（Ｐ＜００５），说明血清假尿苷可作为诊断恶性肿瘤的一种标志物。     

阿斯美胶囊中四种组分的高效液相色谱分析

建立了反相高效液相色谱法测定阿斯美胶囊中氨茶碱、盐酸甲氧非那明、马来酸氯苯那敏及那可汀四种组分的含量。色谱柱为ＳｐｈｅｒｉｓｏｒｂＣ８，５μｍ，２００ｃｍ×４０ｍｍＩＤ，流动相为体积分数０５％的三乙胺溶液（磷酸调节ｐＨ５５）＋乙腈＋甲醇（５５０＋３６８＋８２），检测波长为２６４ｎｍ，线性范围分别为：氨茶碱３１２５～２５０ｍｇ／Ｌ，γ＝０９９９６，盐酸甲氧非那明１５６２５～１２５０ｍｇ／Ｌ，γ＝１００００，马来酸氯苯那敏２５～２００ｍｇ／Ｌ，γ＝０９９９９，那可汀８７５～７００ｍｇ／Ｌ，γ＝０９９９９；回收率（ｎ＝３）分别为１０１２％，１００８％，９９９％，９９５％；精密度：日内平均ＲＳＤ（ｎ＝６）分别为０７％，０４％，０４％，０６％；日间平均ＲＳＤ（ｎ＝３）分别为１０％，１０％，１１％，１２％。     

锑（锡）－Ferron－Se（Ⅳ）络合吸附催化波研究及应用

在ｐＨ１．８的Ｈ＿２ＳＯ＿４－ＮａＡｃ缓冲溶液中，用单扫示波极谱法，Ｓｂ（Ⅲ）或者Ｓｎ（Ⅳ）－７－碘－８－羟基喹啉－５－磺酸－Ｓｅ（Ⅳ）体系可产生灵敏的络合吸附催化波。锑、锡浓度分别在０．４～２００μｇ／Ｌ和０．８～１８０μｇ／Ｌ范围内与峰高呈线性关系，检测限分别为０．２μｇ／Ｌ和０．４μｇ／Ｌ，并用于工业废水、地下水和天然水中痕量锑和锡的测定。同时对电活性络合物的组成、极谱波的性质和电极过程机理也作了讨论和研究。     

用ICP—MS测定高纯氧化镝中痕量稀土元素

考察了源于基体镝的多原子离子干扰。研究了基体对待测稀土杂质信号的影响，采用Ｔｌ内标能基本上补偿基体影响。建立了直接测定高纯氧化镝中痕量稀土杂质的电感耦合等离子体－质谱法。检测限为００１３～００８８μｇ／Ｌ，平均回收率为９２３％～１０１４％，相对标准偏差为２７％～９２％。方法简便、快速、灵敏。     

锑（锡）—Ferron—Se（Ⅳ）络合吸附催化波研究及应用

在ｐＨ１．８的Ｈ２ＳＯ４－ＮａＡｃ缓冲溶液中，用单扫示波极谱法，Ｓｂ（Ⅲ）或者（Ｓｎ（Ⅳ）－７－碘－８－羟基喹啉－５－磺酸－Ｓｅ（Ⅳ）体系可产生灵敏的络合吸附催化波。锑、锡浓度分别在０．４～２００μｇ／Ｌ和０．８～１８０μｇ／Ｌ范围内与峰高呈线性关系，检测限分别为０．２μｇ／Ｌ和０．４μｇ／Ｌ，并用于工业废水，地下水和天然水中痕量锑和锡的测定，同时对电话性络合物的组成，极谱波的性质和电极过程机理也     

用新荧光试剂7-(2,4-二羟基-5-羧基苯偶氮)-8-羟基喹啉-5-磺酸荧光法测定镁

研究了新荧光试剂７－（２，４－二羟基－５－羧基苯偶氮）－８－羟基喹啉－５－磺酸（ＤＨＣＢＡＱＳ）与镁形成配合物的荧光性能，在ｐＨ９０的硼砂缓冲介质中，试剂与镁形成１∶１配合物，其λｅｘ／λｅｍ＝３５８ｎｍ／５０２ｎｍ。镁（Ⅱ）含量在０～４８０μｇ／Ｌ范围内呈良好线性关系，检测限为３７μｇ／Ｌ，据此建立测定痕量镁的新方法，并应用于矿样及血清中痕量镁（Ⅱ）的测定，结果满意。     

流动注射在线预富集—同步扫描荧光法分析水样中痕量多环芳烃

建立了苯并［ａ］芘和的流动注射在线预富集－同步扫描荧光检测法，方法简便快速。苯并［ａ］芘和的测定下限分别为０２μｇ／Ｌ和００４μｇ／Ｌ。测定的相对标准偏差分别为：７１１％和７５４％。用于实际水样的测定，苯并［ａ］芘的回收率为９０％～１０３３％，为１０３３％～１１６７％，结果满意。     

高碘酸盐氧化亚甲蓝动力学光度法测定痕量锇

以Ｏｓ（Ⅳ）催化高碘酸盐氧化亚甲蓝（ＭＢ）反应为基础提出了测定痕量锇的方法。在９０℃加热１４ｍｉｎ和６６０ｎｍ波长处采用固定时间法测定亚甲蓝吸收的降低,锇浓度在０～３．２μｇ／Ｌ范围呈线性关系,检了限为０．０２μｇ／Ｌ,对１．６μｇ／Ｌ Ｏｓ（Ⅳ）测定的ＲＳＤ为１．５６％（ｎ＝１１）,催化反应对Ｏｓ（Ⅳ）、ＭＢ、ＫＩＯ４和Ｈ２ＳＯ４均为一级反应,催化反应的表观活化能为８７．７２ＫＪ／ｍｏｌ,探讨了     

meso－四（4－甲基－3－磺基苯）卟啉分光光度法测定痕量钯的研究

本文研究了Ｐｄ（Ⅱ）与ｍｅｓｏ－四（４－甲基－３－磺基苯）卟啉（Ｔ（４Ｍ３ＳＰ）Ｐ）的显色反应在表面活性剂十二烷基磺酸钠（ＳＤＳ）和抗坏血酸存在下，ｐＨ４８的ＨＡｃ－ＮａＡｃ介质中，沸水浴加热，Ｐｄ（Ⅱ）与Ｔ（４Ｍ３ＳＰ）Ｐ形成１∶１（Ｍ∶Ｌ）配合物配合物最大吸收波长４１４ｎｍ，表观摩尔吸光系数ε＝２０×１０５Ｌ·ｍｏｌ－１·ｃｍ－１钯量在０－２．２５μｇ／１０μＬ范围内符合比耳定律本法应用于催化剂中痕量钯的测定，结果满意     

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.