反相胶束增稳荧光法测定兔血浆中痕量盐酸水檗碱的研究

本文研究了气溶胶（ＡＯＴ）／环已烷／水反相胶束介质中中草药有效成分盐酸小檗碱的荧光性质，并将该法应用于兔血浆中痕量盐酸小壁碱的测定。该法的线性范围为１．０×１０－７～３×１０＾－５（ｇ／ｍｌ），检出限为８．３×１０＾－８（ｇ／ｍｌ），相对标准偏差为１．１％。     

时间分辨荧光免疫分析法直接测定雌二醇

合成了雌二醇抗原,并获得了雌二醇单克隆抗体,通过酶联免疫吸附法测得效价为１．０×１０＾７。使用洗脱增强－时间分辨荧光免疫分析法测定了血清中的雌二醇,浓度范围为１．０×１０＾－２－１．０×１０＾３μｇ／Ｌ,最低检出限为５．６ｎｇ／Ｌ,批内ＲＳＤ％小于３．７％,批间ＲＳＤ％小于７．５％。将测定结果 放射免疫分析法作了比较。     

流动注射化学发光法测定甲氨蝶呤

研究了甲醛增强高锰酸钾与甲氨蝶呤的化学发光反应，由此建立了一种测定甲氨蝶呤的流动性注射化学发光分析法，方法的检出限为３．４×１０＾－９ｇ／ｍＬ，相对标准偏差为１．１％（２．０×１０＾－６ｇ／ｍＬ甲氨蝶呤，ｎ＝１１）线性范围为１．０×１０＾－８～１．０×１０＾－５ｇ／ｍＬ。该法已用于甲氨蝶呤针剂及片剂中甲氨蝶呤含量的测定。     

催化动力学吸光光度法测定污水中痕量汞

研究了亚铁氰化钾－硫脲－硫酸测定痕量汞的催化显析体系。检出限为３ｎｇ．ｍｌ＾－１，Ｈｇ（Ⅱ）浓度在０－１．０μｇ／２５ｍｌ范围内遵守比耳定律，摩尔吸光系数为６．６×１０＾５，回收率为９９．０％－１１０．３％，相对标准偏差２．７７％，方法可直接测定污水中纳克量的Ｈｇ（Ⅱ），结果令人满意。     

以偶合反应流动注射化学发光法测定铅

基于Ｐｂ（Ⅱ）能置换出Ｆｅ（Ⅱ）－ＥＤＴＡ络合物中的Ｆｅ（Ⅱ）和Ｆｅ（Ⅱ）－鲁米诺－溶解氧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铅的新方法。本方法线性范围１×１０＾－７￣１×１０＾－５ｇ／ｍＬ，相对标准偏差为２．５％（ｎ＝１１，Ｃ＝１０＾－６ｇ／ｍＬ），检出限为２×１０＾－８ｇ／ｍＬ。用于污水中铅的测定，结果令人满意。     

催化动力学垂直光路光度法测定痕量铜

建立了痕量铜的催化动力学垂直光路光度测定法，铜含量在０～３．０ｎｇ／２５０μｌ范围内符合比耳定律，工作曲线的回归方程为：△Ａ＝０．５３４Ｃ（ｃｕ＾２＋，ｎｇ），＋０．０１８（ｒ＝０．９９９９），检出限为１．５×１０＾－１１ｇ．ｍｌ＾－１（△Ａ＝０．０２，ｔ＝２ｍｉｎ）由曲线斜率法求得的表观摩尔吸光系数为１．２×１０＾７，方法用于氮三乙酸及标准水样中铜的测定，加标回收率在９２％～９８％，相对标准偏差     

无机还原剂与光泽精化学发光反应的研究：Ⅱ.钼（Ⅲ）—光泽精化学发光反应

本利用流动注射技术研究了Ｊｏｎｅｓ柱产生的钼（Ⅲ）与光泽精的化学发光反应。建立了痕量相的流动注射化学发光分析法。方法的检出限是１×１０＾－＾１＾１ｇ／ｍｌ；校准曲线的线性范围是１×１０＾－＾１＾０－１×１０＾－＾６ｇ／ｍｌ；相对标准偏差为２．０％（１×１０＾－＾７ｇ／ｍｌ钼，ｎ＝１１）。此法已用于水样的分析，结果令人满意。本还进行了反应机理的探讨。     

氟化钙增敏石墨炉原子吸收法测定人发和血清样品中痕量钼的研究

石墨炉原子吸收法测定生物样品中痕量钼时，用氟化钙作基体改进剂，可使钼的原子吸光度提高５．７倍，其特征量原来的４．２× １０＾－１１ｇ／１％吸收降低到５．１×１０＾－１２ｇ／１％吸收，测定下限为０．５５ｎｇ·ｍＬ＾－１，线性范围为０～１０００ｎｇ· ｍＬ＾－１． 对人发和牛血清标样中痕量钼测定。结果满意。     

头孢噻肟钠的降解及其产物伏安行为的研究

头孢噻肟钠在ＮａＯＨ溶液中降解后，于０．１ｍｏｌ／ＬＮａＯＨ中得一灵敏的吸附伏安原峰，Ｅｐ＝－０．７８Ｖ（νｓＡｇ／ＡｇＣｌ），ｉｐ与头孢噻肟钠浓度在１．０×１０＾－＾９－１．０×１０＾－＾８，１．０×１０＾－＾８－１．０×１０＾－＾７，１．０×１０＾－＾７－１．０×１０＾－＾６ｍｏｌ／Ｌ范围内呈线性关系，检出限为５．０×１０＾－＾１＾０ｍｏｌ／Ｌ。用多种电化学手段研究其降解产物的伏安行为，测定了     

在线分离光度法测定痕量金的研究

本提出了一种泡沫塑料柱在线分离富集／β－环糊精－十二烷基苯磺酸钠溶液在线洗脱／硫代米蚩酮光度法测定痕量金的新方法。方法的检测出限是３×１０＾－＾８ｇＡｕ，线性范围是５×１０＾－＾７－８×１０＾－＾６Ａｕ，对于１．０μｇＡｕ进行１１次测定，相对标准偏差小于３．０％。     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.