荧光法测定补骨脂素和异补骨脂素

以溴代十六烷基三甲胺（ＣＴＭＡＢ）为胶束试剂，β－环糊精（β－ＣＤ）为包含试剂，在优化实验条件下，用荧光光度法测定了补骨脂中补骨脂素和异补骨脂素．线性范围分别为２×１０－９～８×１０－６ｇ／ｍＬ，２×１０－９～８×１０－７ｇ／ｍＬ；检出限分别为２．６７×１０－１１ｇ／ｍＬ和１．１５×１０－１１ｇ／ｍＬ．     

高锰酸钾—抗坏血酸化学发光体系测定抗坏血酸

本文研究了高锰酸钾－抗坏血酸化学发光体系，建立了测定抗坏血酸的化学发光分析新方法，线性响应的浓度范围为５．０×１０＾－７ｍｏｌ／Ｌ～４．０×１０＾－５ｍｏｌ／Ｌ，检出限为３．０×１０＾－７ｍｏｌ／Ｌ，对２．５×１０＾－６ｍｏｌ／Ｌ抗坏血酸进行１０次平行测定，相对标准偏差为１．６％，考察了２２种物质的干扰情况。用于维生素Ｃ片剂及注射液中抗坏血酸含量测定，结果令人满意。     

高锰酸钾－抗坏血酸化学发光体系测定抗坏血酸

本文研究了高锰酸钾－抗坏血酸化学发光体系，建立了测定抗坏血酸的化学发光分析新方法。线性响应的浓度范围为５．０×１０￣（－７）ｍｏｌ／Ｌ～４．０×１０￣（－５）ｍｏｌ／Ｌ检出限为３．０×１０￣（－７）ｍｏｌ／Ｌ对２．５×１０￣（－６）ｍｏｌ／Ｌ抗坏血酸进行１０次平行测定，相对标准偏差为１．６％。考察了２２种物质的干扰情况。用于维生素Ｃ片剂及注射液中抗坏血酸含量测定，结果令人满意。     

用流动注射法研究巯基化合物-铈(Ⅳ)-氢化可的松的化学发光反应

采用流动注射法研究了巯基化合物－铈（Ⅳ）－氢化可的松（ＨＣＲｓ）体系的化学发光行 为，对影响化学发光强度的诸因素进行试验和探讨，建立了流动注射化学发光法检测谷胱甘 肽（ＧＳＨ），半胱氨酸（Ｃｙｓ）等含巯基化合物的新方法。检测ＧＳＨ和Ｃｙｓ和线性范围分别为 ２．０×１０－６～１０．０×１０－５ｍｏｌ／Ｌ和１．０×１０－６ｍｏｌ／Ｌ～１０．０×１０－５ｍｏｌ／Ｌ；检测限分别为２．０ ×１０－７ｍｏｌ／Ｌ和１．４×１０－６ｍｏｌ／Ｌ（Ｓ／Ｎ＝３）；ＧＳＨ、Ｃｙｓ加入血清中进行回收测定的回收率 为９０％～９５％，相对标准偏差小于４％。     

表面活性剂对镉示波极谱的增敏作用

提出了一个简便测定微量镉的灵敏的示波极谱法，在ｐＨ＝４．０的ＨＡｃ和少量非离子型表面活性剂存在下，Ｃｄ（Ⅱ）产生一灵敏的极谱波，峰电位为－０．６７Ｖ，线性范围为２．０×１０－８ｍｏｌ／Ｌ～４．９×１０－６ｍｏｌ／Ｌ，检出限为５．６×１０－９ｍｏｌ／Ｌ．该法用于废水样及发样的测定，结果良好     

一种基于形成杂多核络合物的荧光增敏效应的研究：Ⅲ.锰（Ⅱ）,钴（…

本研究了Ｍｎ＾２＋和Ｃｏ＾２＋对７－（８－羟基－３，６－二磺基萘偶氮）－８－羟基喹啉－５－磺酸－硼砂反应体系的混合荧光增敏作用。实验条件下，荧光增敏强度满足线性加和关系的范围是：Ｍｎ＾２＋浓度０￣２．９×１０＾－７ｍｏｌ／Ｌ；Ｃｏ＾２＋浓度０￣８．８～１０＾－７ｍｏｌ／Ｌ；总浓度不超过１．０×１０＾－６ｍｏｌ／Ｌ。检出限量为Ｍｎ＾２＋４．５×１０＾－９ｍｏｌ／Ｌ和Ｃｏ＾２＋１．４×１０＾－８ｍｏ     

N—（β—羧丙酰基）异鲁米诺的电致化学发光行为及其机理探讨

本进行了Ｎ－（β－羧丙酰基）异鲁米诺的电致化学发光行为的研究。采用正矩形液脉冲电压，在ＫＯＨ－ＫＣｌ－Ｈ２Ｏ２－（ｐＨ１１．６）介质中，Ｎ－（β－羧丙酰基）异鲁米诺测定的线性范围为４．０×１０＾－１０￣７．０×１０＾－８ｍｏｌ／Ｌ，检出限为２．０×１０＾－１０ｍｏｌ／Ｌ。本对此体系的电致化学发光机理进行了探讨。     

用荧光法研究补骨脂素与异补骨脂素的药代动力学

补骨脂素和异补骨脂素是补骨脂的主要有效成分。为了研究补骨脂素和异补骨脂素的药物代谢动力学,本文采用胶束荧光法对补骨脂素和异补骨脂素在兔体内的血药浓度进行２４ｈ监测,求出系列药动学参数。结果表明：补骨脂素的Ｋａ为３．２２５１ｈ－１,ｔ１／２（α）为 ０．１８４９ｈ,ｔ１／２（β）为１０．７０６５ｈ,Ｔ为０．８２００ｈ,ＡＵＣ为２１．６１０４ｍｇ·ｈ／Ｌ;异补骨脂素的Ｋａ为４．４３２９ｈ－１,ｔ１／２（Ｋａ）为０．１５６４ｈ,ｔ１／２（Ｋｅ）为２．１７７７ｈ,Ｔ为１．０９５５ｈ,ＡＵＣ为７．２４１８ｍｇ·ｈ／Ｌ。     

新化学发光试剂ITCI的合成及其性能研究

合成一种新化学发光试剂异硫氰酸异鲁米诺（ＩＴＣＩ），研究其化学发光及标记酵母ＲＮＡ的性能。标记反应条件温和快速，１克酵母ＲＮＡ可与１．５×１０－５ｍｏｌＩＴＣＩ结合。建立了测定ＩＴＣＩ和ＲＮＡ的化学发光分析方法，线性范围分别为１．０×１０－１０～１．０×１０－７ｍｏｌ／Ｌ和４．０～×１０－９～２．０×１０－７ｇ／ｍＬ，检测限分别为６．６×１０－１１ｍｏｌ／Ｌ和８．０×１０－１０ｇ／ｍＬ。     

乙醇酸菠菜组织电极和马兰组织电极的研究

分别以菠菜和马兰叶为生物催化材料，将其叶浆组织与氧电极相结合，首次制成乙醇酸电极，本研究了这两种电极的响应性能。菠菜组织电极线性范围为５．０×１０＾－６－１．０＾１０＾－４ｍｏｌ／Ｌ；响应时间为３ｍｉｎ；寿命为１０天，马兰组织电极线性范围为２．０×１０＾－６－１．０×１０＾－４ｍｏｌ／Ｌ；响应时间为３ｍｉｎ；寿命至少３０天。这两种电极对底物乙醇酸钠皆有良好的选择性。     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.