流动注射化学发光法测定甲氨蝶呤

研究了甲醛增强高锰酸钾与甲氨蝶呤的化学发光反应，由此建立了一种测定甲氨蝶呤的流动性注射化学发光分析法，方法的检出限为３．４×１０＾－９ｇ／ｍＬ，相对标准偏差为１．１％（２．０×１０＾－６ｇ／ｍＬ甲氨蝶呤，ｎ＝１１）线性范围为１．０×１０＾－８～１．０×１０＾－５ｇ／ｍＬ。该法已用于甲氨蝶呤针剂及片剂中甲氨蝶呤含量的测定。     

高锰酸钾-亚硫酸钠-核黄素化学发光体系的研究

研究了核黄素在酸性条件下与高锰酸钾和亚硫酸钠发生化学发光反应的行为,建立了流动注射化学发光测定核黄素的新方法。核黄素浓度在１．０×１０＾－７－１．０×１０＾－５ｇ／ｍＬ范围内与化学发光强度呈良好的线性关系,检出限为３×１０＾－８ｇ／ｍＬ。对４．。０×１０＾－７ｇ／ｍＬ的核黄素进行１１次平行测定,得方法的相对标准偏差为１．６％。     

空气中肼的流动注射化学发光分析

研究了肼在碱性条件下与鲁米诺和高磺酸钾产生化学发光行为，建立了流动注射化学发光测定痕量肼的新方法。肼的浓度在１．０×１０＾－８－１．０×１０＾－６ｇ／ｍＬ范围内与化学光强度成线性关系；检出限为４×１０＾－９ｇ／ｍＬ；相对标准偏差小于３％。     

流动注射化学发光法测定盐酸异丙嗪

在酸性溶液中，高锰酸钾能氧化盐酸异丙嗪产生化学发光反应，乙二醛的存在可使发光强度增强。据此，采用流动注射技术，建立了一种测定盐酸异丙嗪的化学发光分析分析。方法的检出限为３．５×１０＾－８ｇ／ｍＬ，相对标准偏差为２．８％（１．０×１０＾－６ｇ／ｍＬ盐酸异丙嗪，ｎ＝１１），线性范围为１．０×１０＾－７￣６．０×１０＾－５ｇ／ｍＬ。该法已用于盐酸异丙嗪针剂和片剂中盐酸异丙嗪含量的测定，并与药典标准方法进     

测定钴的化学发光新体系

研究了新吖啶衍生物９，１０－二甲基吖啶氟磺酸盐的化学发光特性。建立了测定Ｃｏ６２＋的化学发光新体系。方法线性范围为１．０×１０＾－１０－１．０×１０＾－７ｇ／ｍＬ；检测限为５．０×１０＾－１１ｇ／ｍＬＣｏ＾２＋。测定５．０×１０＾－９ｇ／ｍＬＣｏ６２＋的相对标准偏差为６．０％。方法选择性好，用于自来水，江水，池塘水中痕量钴的测定，结果令人满意。     

偶合反应化学发光法测定痕量银的研究——K4Fe（CN）6—Luminol体系

将Ａｇ（Ｉ）催化Ｋ４Ｆｅ（ＣＮ）６的水合反应与Ｌｕｍｉｎｏｌ同Ｃｕ（ＣＮ）＾２－４的化学发光反应相偶合，建立起一种新的灵敏测定痕量银的化学发光分析法，在所研究的优化条件下，该法测定银的选择性较好，检测限达到４．０×１０＾－１３ｇ／ｍＬＡｇ线性浓度范围为１．０×１０＾－１２～１．０×１０＾－６ｇ／ｍＬＡｇ对４×１０＾－１１ｇ／ｍＬＡｇ（Ｉ）溶液连续１１次测定的ＲＳＤ≤３．５％，用于环境水和岩矿中银的     

高锰酸钾—连二亚硫酸钠—核黄素化学发光体系的研究

在酸性溶液中，高锰酸钾能氧化核素产生化学发光，连二亚硫酸钠的存在可使发光强度大大增强，采用流动注射技术，建立了测定核黄素的化学发光分析法，方法的检出限为６．２×１０＾－８ｇ／ｋｍＬ，线性范围为２×１０＾－７～１×１０＾－５ｇ／ｍＬ对４．０×１０＾－６ｇ／ｍＬ核黄素进行１１次平行测定，相对标准偏差为１．８％，方法用于针剂和片剂中核黄素测定，与药典标准方法－紫外分光光度法对照，相对误差不大于±２％。     

全固定化试剂流动注射化学发光测定铜

采用离子交换固定法把Ｌｕｍｉｎｏｌ（Ｌｕ），ＣＮ＾－固定在阴离子交换树脂上，串入流动注射系统中，当一定量洗脱剂被注入阴离子交换柱时，洗脱下来的Ｌｕ和ＣＮ＾－与分析物Ｃｕ＾２＋发生化学反应，产生化学发光，实现对Ｃｕ＾２＋的在线检测。本法检出限为１．３×１０＾－９ｇ／ｍＬ，线性范围为４．０×１０＾－９－６．０×１０＾－６ｇ／ｍＬ，ＲＳＤ为３．４％，单次测定在１ｍｉｎ内能完成。已用于井水中铜的测定，结果     

高碘酸钠-过氧化氢-盐酸黄连素化学发光体系的研究

１引言 盐酸黄连素是一种用于治疗肠道感染，毒性低、副作用小的天然药物。对盐酸黄连素的测定，化学发光法未见报道。本文发现，过氧化氢存在下，磷酸介质中盐酸黄连素与高碘酸钠反应产生强的化学发光。据此结合流动注射技术建立了在ＮａＩＯ４－Ｈ３ＰＯ４－Ｈ２Ｏ２－盐酸黄连素体系中测定盐酸黄连素的化学发光新方法。方法的检出限为 ３．８×１０－９ｇ／ｍＬ。线性范围是 １．０× １０－８－ ７．０ ×１０－６ｇ／ｍＬ。相对标准偏差为 ２．３％（ Ｃ８＝ １． ０ ×１０－６ｇ／ｍＬ； ｎ＝１１）。该法与药典方法对照，结果满意。…     

流动注射化学发光法测定吡哌酸

采用流动注射技术，研究了高锰酸钾－亚硫酸钠－吡哌酸体系的化学发光行为，对影响化学发光强度的诸因素进行了实验和探讨，建立了化学发光法测定吡哌酸的新方法。方法的检出限为３×１０~（－８）ｇ／ｍＬ；线性范围为１．０×１０~（－７）～８０×１０~（－５）ｇ／ｍＬ。对４．０×１０～（－６）ｇ／ｍＬ的吡哌酸进行１１次平行测定，得方法的相对标准偏差为１．６％。方法用于药剂中吡哌酸含量的测定，结果与分光光度法测得值一致。     

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.