高效液相色谱法测定人血浆中甲磺酸培氟沙星浓度

建立了一种测定人血浆中甲磺酸培氟沙星的匠相液相色谱方法,用的是ＺｏｒｂａｘＯＤＳＣ＿（１８）柱和用三乙醇胺调节成ｐＨ为３．０的甲醇－０．０４ｍｏｌ／ＬＨ＿３ＰＯ＿４溶液（８０：２０,Ｖ／Ｖ）的流动相,检测在２７６ｎｍ处进行,流量为１ｍＬ／ｍｉｎ,线性范围是６．０１×１０￣（－８）～３．０１×１０￣（－５）ｍｏｌ／Ｌ（γ＝０．９９９８）,检测极限为６．０１×１０￣（－８）ｍｏｌ／Ｌ,平均回收率为９７．５７±３．０４％,日内与日间的ＣＶ分别为３．２９％和５．０８％。     

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％。     

单扫描极谱法连续测定人发中的微量元素锌铁锰铜

本提出在０．１５ｍｏｌ／Ｌ乙二胺－７．５×１０＾－３ｍｏｌ／Ｌ三乙醇胺－２．５×１０＾－２ｍｏｌ／Ｌ硫氰酸钾底液中单扫描极谱法测定锌、铁、锰，续加硫酸（０．３ｍｏｌ／Ｌ）测定铜的方法，峰电位分别为－１．４２Ｖ，－１．６３Ｖ，－１．７１Ｖ，－０．４８Ｖ（ｖｓ．ＳＣＥ），线性范围：０．０５～１．４μｇ／ｍＬＭｎ，０．０４～１μｇ／ｍＬＣｕ，最低检出浓度．０３，０．０５，０．０２，０．０４μｇ／ｍＬＭ     

秋水仙碱在碳糊电极上的吸附伏安行为

秋水仙碱在硫酸溶液中加热水解得分析试液。在０．０５ｍｏｌ／ＬＨ２ＳＯ４底液中，用碳糊电极吸附伏安法测定秋水仙碱，阳性峰电位为０．８２Ｖ（ｖｓ．ＳＣＥ），峰电流与秋水仙碱的浓度在１．０×１０＾－７～１．０×１０＾－４ｍｏｌ／Ｌ范围内呈良好线性关系，检测下限为５．０×１０＾－８ｍｏｌ／Ｌ回收范围为９５．０％～１０３．５％ＲＳＤ为２．８％（ｎ＝１０）。本对反应机理进行了初步探讨。     

孕血和药物中孕酮的单扫极谱法测定

孕酮２，４－二硝基苯腙在单扫描示波极谱仪上，以吡啶－氢氧化钠为底液（ｐＨ２．０）于－０．７４Ｖ（ｖｓ．ＳＣＥ）处可出现一灵敏的吸附催化波，孕酮浓度在１．０×１０＾－８～２．０×１０＾－６ｍｏｌ／Ｌ范围内与该波呈线性关系，检出限为５．０×１０＾－９ｍｏｌ／Ｌ方法用于测定孕血和药物中孕酮含量，获得满意的结果。     

酸性媒染紫-示波计时电位法测定天然水和饮用水中铝

报道酸性媒染紫（ＳＶＲＳ）－示波计时电位法测定天然水及饮用水中铝。在０．８５ｍｏｌ／Ｌ　ＮＨ３·Ｈ２Ｏ－ＮＨ４Ｃｌ－５×１０－５ｍｏｌ／Ｌ ＳＶＢＳ（ｐＨ８．８）底液中,Ａｌ－ＳＶＲＳ络合物在－１．０５Ｖ电位处产生灵敏切口,切口深度与铝浓度成正比,可用于定量分析。线性范围为１×１０－７～６×１０－６ｍｏｌ／Ｌ． ＲＳＤ为５．５％ （ｎ＝１０,２×１０－７ｍｏｌ／Ｌ）,检测限为５×１０－８ｍｏｌ／Ｌ。本法特点为：在碱性条件下,无需加热,无需通氮除氧,无需预富集,大大减少了分析时间。仪器简单,方法灵敏准确,特别适用于天然水和饮料中Ａｌ的分析。对实际水样进行了分析,与ＩＣＰ／ＡＥＳ法所测结果基本一致。     

用碳糊修饰电极测定氨基酸的伏安法研究：Ⅱ.组氨酸在氧化铝修饰碳糊 …

用１０％氧化铝的修饰碳糊电极研究了测定组氨酸的伏安法。在０．０５ｍｏｌ／Ｌ丁二酸－硼砂（ｐＨ＝３．５）底液中在－０．６Ｖ出现一还原峰,结合２．５次微分技术测定组氨酸,在３．２０～１３０μｍｏｌ／Ｌ浓度范围内有良好的线性关系,相对标准偏差为３．４％,检出限为０．４μｍｏｌ／Ｌ。检测灵敏度比文献报道有较大的提高。文中还讨论了电极过程。     

铜（Ⅱ）锌（Ⅱ）—氟哌酸体系电化学行为及示波极谱法研究

铜（Ⅱ）和锌（Ⅱ）分别在０．１ｍｏｌ／ＬＫＨ２ＰＯ４－Ｎａ２ＨＰＯ４缓冲溶液（ｐＨ６．５）和０．２５ｍｏｌ／ＬＮＨ４Ｃｌ溶液中，与氟哌酸形成良好的络合吸附波，峰电位分别为－０．２６Ｖ和－１．２８Ｖ（ｖｓ．ＳＣＥ），络合比分别为１：３和１：２，峰电流与铜（Ⅱ）和锌（Ⅱ）的浓度均在４．０×１０＾－７～５．０×１０＾－６ｎｏｌ／Ｌ范围内呈线性关系，检测限分别为７．０×１０＾－８和５．０×１０＾－８ｍｏｌ     

倒数示波计时电位法同时测定粮食中Cu、Pb含量

在分别含有２ｇ／Ｌ乙二胺与＊１０＾－４ｍｏｌ／Ｌ８－羟基喹啉（Ｏｘｉｎｅ）和０．３ｍｏｌ／Ｌ的氢氧化钠淀粉液中,Ｃｕ＾２＋、Ｐｂ＾２＋具有良好的示波图。其切口电位分别为－０．８５Ｖ,－１２０Ｖ（ｖｓ．ＳＣＥ）,二者相差０．３５Ｖ,能够分辨,可同时测定,本方法应用于大米中Ｃｕ、Ｐｂ含量的同时测定,检出限分别为５．８μｇ／Ｌ（Ｃｕ）、１０．０μｇ／Ｌ（Ｐｂ）,平均回收率为９６．０％、１０２．０％。     

扑尔敏的示波极谱测定

在０．１ｍｏｌ／Ｌ的Ｈａｃ－ＮａＡｃ缓冲溶液中，扑尔敏于—１．３６Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的极谱还原波，导数波高与扑尔敏在２．０×１０~（－６）～８．０×１０~（－５）ｍｏｌ／Ｌ浓度范围内成线性关系，检测下限达６．０×１０~（－７）／ｍｏｌ／Ｌ。对极谱波的性质进行了探讨，并用该法测定了速效伤风胶囊中扑尔敏的含量。     

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.