反向流动注射化学发光法测定盐酸乙胺丁醇

基于盐酸乙胺丁醇与高碘酸钾～鲁米诺反应产生很强的化学发光,结合反向流动注射技术,建立了流动注射化学发光法测定盐酸乙胺丁醇的新方法。在优化的实验条件下,该法的线性范围为4.0×10-8～2×10-5g/mL,检出限为8×10-9g/mL,对6.0×10-7g/mL盐酸乙胺丁醇进行11次平行测定,方法的相对标准偏差为1.9%。该法可用于片剂中盐酸乙胺丁醇的测定。     

反向流动注射化学发光法测定五氟利多

基于五氟利多对 KIO4- Luminol体系化学发光有强烈的增敏作用, 结合反向流动注射技术, 首次建立了测定五氟利多的流动注射化学发光的方法; 在优化的实验条件下, 测定五氟利多的线性范围为 4.0× 10- 8～ 1.0× 10- 5 g/mL, 检出限为 9.2× 10- 9 g/mL, 对 4.0× 10- 7 g/mL的五氟利多进行 11次平行测定, 方法的相对标准偏差为 2.1%; 该法用于片剂五氟利多的含量测定, 结果满意.     

铁氰化钾-鲁米诺体系后化学发光行为的研究-流动注射后化学发光法测定可待因

发现了可待因在铁氰化钾鲁米诺化学发光反应体系中的后化学发光反应。优化了反应条件,建立了一种利用后化学发光反应测定可待因的流动注射化学发光新方法。方法的检出限为3×10-8g mL,相对标准偏差为1.9%(1.0×10-6g mL可待因,n=11),线性范围为8.0×10-8～1.0×10-5g mL。此法已用于可待因片剂中可待因的测定,结果与药典方法测定值一致。     

顺序注射化学发光测定非那西汀

根据四价铈在酸性介质中氧化非那西汀产生化学发光，建立了顺序注射化学发光测定非那西汀的方法。该法线性范围为4．0×10－9～1．0×10－6g/mL，检出限为1．0×10－9g／mL，，对5．0×10-8g/mL非那西汀7次平行测定的相对标准偏差为1．2％。不需分离和其它预处理可直接用于药物生产的过程分析。     

铁氰化钾-鲁米诺体系后化学发光反应及其分析应用研究-分子印迹-后化学发光法测定双嘧达莫

研究了双嘧达莫在铁氰化钾-鲁米诺化学发光反应体系中的后化学发光反应, 并在研究其反应的动力学性质、化学发光光谱、荧光光谱以及一些相关问题的基础上, 探讨了反应机理; 合成了双嘧达莫的分子印迹聚合物, 以此聚合物为分子识别物质, 利用铁氰化钾-鲁米诺-双嘧达莫后化学发光体系, 建立了测定双嘧达莫的高选择性分子印迹-后化学发光分析方法. 所建方法的线性范围为1.0×10-8-1.0×10-6 g/mL(r=0.999 2), 检出限为3×10-9 g/mL, 相对标准偏差为2.7%(1.0×10-7 g/mL双嘧达莫, n=11).     

鲁米诺-铁氰化钾-硫酸特布他林化学发光体系的研究

研究发现,铁氰化钾在碱性条件下能氧化鲁米诺产生微弱的化学发光,硫酸特布他林能大大增强该发光强度。在此基础上,结合流动注射技术,建立了一种直接测定硫酸特布他林的流动注射化学发光分析法。该方法的检出限为5.7×10-10g／mL,硫酸特布他林质量浓度在1.0×10-9～1.0×10-7g／mL范围内与发光强度呈良好的线性关系,相对标准偏差为3.3%(硫酸特布他林1.0×10-8g／mL,n＝11)。利用该方法对特布他林片剂和针剂含量的测定,结果令人满意。     

高锰酸钾-亚硫酸钠-氨基比林化学发光体系的研究

采用流动注射技术,研究了高锰酸钾-亚硫酸钠-氨基比林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氨基比林的新方法.方法的检出限为3×10-8 g/mL,线性范围为1.0 ×10-7～8.0×10-5 g/mL.对4.0×10-6 g/mL的氨基比林进行11次平行测定,得方法的相对标准偏差为1.7%.方法用于药剂中氨基比林含量的测定,结果与分光光度法测得值一致.     

偶合反应流动注射化学发光法测定镓

基于Ga(Ⅲ )置换Fe EDTA络合物中Fe 和Fe Luminol O2 产生化学发光的反应 ,建立了置换偶合反应流动注射化学发光测定痕量镓的新方法。方法线性范围为 1.4× 10 - 7～ 1.4× 10 - 5g mL ;检出限为 3×10 - 8g mL ;对 5× 10 - 6 g mL镓标准溶液进行 11次平行测定 ,相对标准偏差为 2 .6 %。方法用于中草药中痕量镓的测定 ,结果满意     

流动注射化学发光法测定安痛定注射液中的氨基比林

在甲醛存在下 ,高锰酸钾与氨基比林能够发生化学发光反应 ,产生很强的化学发光 ,据此采用流动注射技术建立了一种测定氨基比林的化学发光分析法。方法的检出限为 3 .0× 10 -8g/mL ,相对标准偏差为 1.3 % (4 .0× 10 -6g/mL氨基比林 ,n =11) ,线性范围为 1.0× 10 -7～ 8.0× 10 -5g/mL氨基比林。该法已用于安痛定注射液中氨基比林含量的测定。     

流动注射后化学发光法测定异烟肼

本文发现了异烟肼在铁氰化钾-钙黄绿素化学发光反应体系中的后化学发光反应。优化了反应条件,建立了一种利用后化学发光反应测定异烟肼的流动注射化学发光分析法。方法的检出限为6×10-8g/mL, 相对标准偏差为1.8% (2.0×10-6 g/mL 异烟肼,n=11）,线性范围为2.0×10-7~1.0×10-5 g/mL。此法已用于异烟肼片剂中异烟肼含量的测定,结果与药典方法测定值一致。     

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.