催化动力学电位法测定痕量亚硝酸根

基于稀硫酸介质中，亚硝酸根对溴酸钾氧化碘化钾有催化作用，用碘离子选择电跟踪I^-，建立了测定痕量亚硝酸根的催化动力学电位法。在适宜条件下，该指示反应为一级反应，反应速度可用电位的变化（ΔE）表示。当时间固定时，ΔE与亚硝酸根浓度在0－0．12mg/L范围内呈线性关系，检出限为2．0μg/L。该法用于水样中痕量亚硝酸根的测定，结果满意。     

催化动力学极谱法测定痕量亚硝酸根

在硫酸介质中，痕量亚硝酸根对溴酸钾氧化酸性铬深蓝的反应有极强的催化作用，研究了最佳反应条件，发现在氨缓冲溶液中酸性铬深蓝具有良好的极谱峰，以极变法监测催化反应过程中酸性铬深蓝浓度的变化，建立了催化动力学极谱法测定痕量亚硝酸根的方法，方法的线性范围为0．20－1．34μg.ml^-1，检出限为0．088μg.ml^-1，应用于雪水，雨水中痕量亚硝酸根的测定，结果满意。     

溴酸钾氧化酸性品红催化光度法测定亚硝酸根

研究了在强酸介质中亚硝酸根催化溴钾氧化酸性品红的褪色反应及其动力学条件，建立了高灵敏测定痕量亚硝酸根的新催化光度法。方法灵敏度为３．７×１０＾－１１ｇ／ｃｍ＾２亚硝酸态氮，线性范围为０．０６－０．４２μｇ／１０ｍＬ，用于测定唾液及硝钾中亚硝酸根。     

溴酸钾氧化吡口罗红G催化动力学光度法测定痕量NO-2

研究了在磷酸介质中亚硝酸根催化溴酸钾氧化吡口罗红Ｇ而使其褪色，建立了催化动力学光度法测定痕量亚硝酸根的新方法，测定范围为０．２～２０μｇ／ｍＬ，检出限为０．２ｎｇ／ｍＬ，用于食品和水样中的亚硝酸根测定获得满意结果     

溴酸钾氧化吡罗红G催化动力学光度法测定痕量NO2^—

研究了在磷酸介质中亚硝酸根催化溴酸钾氧化吡罗红Ｇ而使褪色，建立了催化动力学光度法测定痕量亚硝酸根的新方法，测定范围为０．２－２０μｇ／ｍＬ，检出限为０．２ｎｇ／ｍｌ，用于食品和水样中的亚硝酸根测定获得满意结果。     

高碘酸钾氧化酚藏花红褪色催化动力学光度法测定食品中的痕量亚硝酸根

基于在硫酸介质中,亚硝酸根对高碘酸钾氧化酚藏花红褪色反应具有较强的催化作用,建立了测定痕量亚硝酸根的催化动力学光度法。线性范围为0．12～1．22mg/L,相关系数为0．9990,检出限为0．016mg／L。用于食品中痕量亚硝酸根的测定,测定结果的相对标准偏差为2、6％～4．2％,回收率为97％．103％。     

基于水杨基荧光酮的催化动力学荧光熄灭测定痕量亚硝酸根

以溴酸钾与水杨基荧光酮的氧化-还原反应为指示反应,以水杨基荧光酮荧光变化为测定依据,系统研究了亚硝酸根催化荧光熄灭反应的动力学条件,建立了水杨基荧光酮催化动力学荧光熄灭法测定自来水中痕量亚硝酸根的方法。用固定时间法得到了良好的工作曲线lgF0／F= 1．305 c-0．017 5,线性范围为0．1～0．5μg／25 mL,线性相关系数为0．999 0。该方法的检出限为1．6μg·L-1。水样测定结果的相对标准偏差为3．7％,加标回收率为95％~106％。     

亚硝酸根的催化光度法测定

本法基于甲酸介质中，亚硝酸根对溴酸钾氧化甲基橙褪色的催化效应，用正交法确定最佳测定条件。本法测定亚硝酸根的线性范围为０～０．２０μｇ／ｍＬ灵敏度为２．８３×１０－１０ｇ／ｍＬ。用于测定水样中的亚硝酸根，结果良好。     

二甲酚橙催化光度法测定亚硝酸根的研究

基于硫酸介质中亚硝酸根催化溴酸钾氧化二甲酚橙的褪色反应 ,建立了测定痕量亚硝酸根的新方法 ,并探讨了动力学条件 ,测定了反应的表观速率常数( k=1 .32× 1 0 -3 S-1)和表观活化能 ( Ea=35 .0 2 k J/mol)。方法的测定范围为 0～ 0 .1 8μg/m L,检出限为 1 .1 ng/m L。方法已用于水中及水基产品中亚硝酸根的测定     

断续流动注射-催化原子荧光光谱法测定碘

基于碘对亚砷酸-硫酸铈的催化反应，断续流动进样，用氢化物发生．原子荧光光谱法直接测定As(Ⅲ）的浓度变化，建立了微量碘间接测定的方法。在实验条件下，碘离子的线性范围为0．80μg/L；相对标准偏差为2．3％；检测限为4μg/L．加标回收率为92．5％-98．2％。测定结果与硫氰酸铁-亚硝酸催化动力学法相比具有很好的一致性。     

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.