溴酸钾二甲酚橙体系-顺序注射-催化光度法测定痕量钒

在酸性介质条件下,钒(Ⅳ)能显著催化溴酸钾对二甲酚橙的氧化褪色反应。据此建立了测定痕量钒(Ⅳ)的顺序注射催化光度法。方法的线性范围为0.5⁵0ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%50ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%¹08%。     

高效液相色谱法测定高纯度苯肼

建立了高纯度苯肼的高效液相色谱测定方法。在流动相中加入抗氧剂和色谱改性剂(M),很好解决了苯肼色谱峰拖尾问题,可准确测定高纯苯肼中杂质含量。优化条件是:Agilent hc-C18色谱柱(150×4.6mm,5μm);流动相为甲醇-水(体积比40∶60)其中所含抗氧剂、色谱改性剂(M)、K2HPO4-KH2PO4浓度均为0.02mol/L;流速1.0mL/min;进样量20μL;检测波长272nm。高纯苯肼中所含杂质苯胺、苯酚以及联苯胺,在5~120μg/mL范围内均具有良好的线性关系,相关系数r>0.9993。     

固定化酶流动注射化学发光法测定尿酸

本文制备了高活性和长寿命固定化尿酸酶,并用流动注射化学发光分析在线测定了人血清和尿中尿酸含量。线性范围为40～1000ng/mL,检测下限为16ng/mL,对200ng/mL尿酸测定,相对标准偏差为2.6％。尿和血清中其它物质均无干扰,血清取样量只需50μL,每次测定时间少于1min。     

荧光法测定尿中的富马酸比索洛尔

建立了直接测定尿中富马酸比索洛尔的荧光分光光度法。荧光强度与富马酸比索洛尔含量在100－1000ng/mL范围内呈线性关系。检测限20ng/mL。对浓度100ng/mL与500ng/mL的标准溶液进行测定,其回收率分别为95．6％和99．6％,相对标准偏差为5．6％和2．3％,可用于 尿中富马酸比索洛尔含量的测定。     

催化光度法测定粮食中的痕量锰

研究了测定痕量锰的新催化光度法,方法基于氨三乙酸为活化剂,锰（Ⅱ）催化高碘酸钾氧化溴酚蓝的反应。测定锰的线性范围为0．4－10ng/mL,检出限为0．082ng/mL,对于4.0ng/mL Mn(Ⅱ）的测定,相对标准偏差为3．4％（n=9),其方法已用于粮食中锰的测定。     

化学修饰探针原子吸收光谱法测定无机锡（Ⅳ）

本文描述了用化学修饰探针原子吸收法测定水中无机锡(Ⅳ)的最佳测定条件,并测定了自来水和矿泉水中的无机锡(Ⅳ)。水样经盐酸酸化后直接测定,测定样品的最低检测限为0.4 ng/mL,线性范围是0.4～20 ng/mL。4 ng/mL的锡(Ⅳ)试样,11次测定结果的相对标准偏差为5.7%。     

微波消解-原子荧光光谱法测定皮革中砷和汞

建立了皮革中砷和汞的微波消解-原子荧光光谱测定方法。在优化的实验条件下,砷、汞含量分别在0.60～150ng/mL和0.10～20ng/mL范围内线性良好。砷、汞检出限分别为0.22ng/mL和0.04ng/mL。方法测定砷的回收率为96.0%～104%,汞的回收率为95.0%～110%。方法准确、灵敏、快速、可应用于皮革样品中砷和汞的同时测定。     

硫胺素-亚硝酸根体系的荧光性质研究及应用

研究了在碱性溶液中硫胺素（VB1）与亚硝酸根的荧光反应,建立了荧光光度法测定硫胺素的新方法。方法线性范围为1．28－324ng/mL,检出限0．52ng/mL,对15个浓度为100ng/mL的硫胺素溶液进行测定,相对标准偏差为1．4％。应用于药物中硫胺素的测定,回收率在96．5％－101．8％之间。     

溴酸钾-二甲酚橙体系-顺序注射-催化光度法测定痕量钒

在酸性介质条件下,钒(Ⅳ)能显著催化溴酸钾对二甲酚橙的氧化褪色反应。据此建立了测定痕量钒(Ⅳ)的顺序注射催化光度法。方法的线性范围为0.5~50ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%~108%。     

激光热透镜光谱分析法同时测定铜、钴和镍研究

基于2-(5-NO2-吡啶-2-偶氮)-1-羟基-8-氨基萘-3，6-二磺酸与铜(Ⅱ)、钴(Ⅱ)和镍(Ⅱ)反应酸度的差异及热透镜信号强度的加和性，建立了激光热透镜光谱法同时测定铜、钴和镍的新方法。测定铜、钴和镍的线性范围依次为0～200ng/mL、0～200ng/mL和0～100ng/mL，检出限依次为2ng/mL，2．5ng/mL和1ng/mL。方法已用于合成样品及人发样中铜、钴和镍的同时测定。     

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.