液相色谱法测定血浆中三环类抗忧郁药物

用高效液相色谱法测定了血浆中４种三环类抗忧郁药物：卡马西平、氯氮平、多虑平和阿米替林。方法采用Ｃ_（１８）色谱柱分离,二极管阵列检测器检测,流动相为甲醇：０．５ｍｏｌ／Ｌ三乙胺－０．５ｍｏｌ／Ｌ冰醋酸的水溶液（９０：１０,Ｖ／Ｖ;ｐＨ７．５）。标准曲线的线性范围为０～１０ｍｇ／Ｌ,相关系数在０．９９以上。方法的最小检出浓度为１０～４０μｇ／Ｌ血浆。血中药物经溶剂萃取后,药物的回收率为７３．６７％～９８．２４％,血中杂质不影响药物的检测。方法简便、快速,适用于临床中毒样品的分析。     

鲁米诺-双氧水-铬(Ⅲ)化学发光体系测定化探样品中痕量砷

用鲁米诺－双氧水－铬（Ⅲ）化学发光体系结合巯基棉对Ａｓ（Ⅲ）的富集分离，建立了快速的测定化探样品中痕量砷的新方法，检测线性范围为１．０×１０－４～１．０×１０１ｍｇ／Ｌ，检出限为３．４×１０－５ｍｇ／Ｌ。用于实际化探样品测定，相对标准偏差为５．５％～９．０％。     

反相高效液相色谱法测定雷公藤提取物中雷公藤甲素含量

应用反相高效液相色谱法检测了雷公藤提取物中雷公藤甲素的含量。样品经洗脱提取后,以Ｃ１８化学键合硅胶为固定相,乙腈－水（４０∶６０,Ｖ／Ｖ）为流动相,用２１０ｎｍ波长定量检测。测定结果表明,雷公藤甲素浓度在０．２５～４．００ｍｇ／Ｌ范围内线性良好,最低进样检测浓度为０．１ｍｇ／Ｌ。批内（ｎ＝５）及批间（ｎ＝５）测定相对标准偏差分别为１．９％～６．５％和２．７％～７．８％,回收率为８９．８％～９２．０％。     

测定玻璃体和房水中维拉帕米含量的高效液相色谱法

研究了用ＨＰＬＣ 测定兔眼玻璃体和房水中维拉帕米含量的方法。用丙咪嗪为内标， 采用Ｓｐｈｅｒｉｃａｌ Ｃ１８色谱柱分离， 以甲醇－ ０ ．０４ ｍｏｌ／Ｌ 醋酸铵－ 乙腈－ 二乙胺（ 体积比１ ∶１ ∶０ ．５ ∶０ ．０２） 为流动相， 检测波长为２７８ｎｍ 。样品用正己烷－ 异丁醇提取后进样， 分析速度快。 样品及内标的保留时间分别为４ ．６３ ｍｉｎ 及９ ．２３ ｍｉｎ ； 线性范围为２ ．５ ～１００ ｍｇ／Ｌ， 相关系数ｒ 为０ ．９９９ ７ 。方法的回收率为１００ ．３ ％ （ ｎ ＝ ５） ，ＲＳＤ 为３ ．６３％ ， 日内ＲＳＤ 为０ ．５ ％ ～３ ．６１ ％ ， 日间ＲＳＤ 为３ ．７５ ％ ～４ ．８０ ％ ， 最低检测质量浓度为０．２５ ｍｇ／ Ｌ。 应用该法测定了创伤家兔玻璃体和房水中维拉帕米浓度的变化。     

高效液相色谱法测定吲哚美辛控释胶囊的血药浓度和生物利用度

采用ＯＤＳ柱,甲醇－稀磷酸溶液（７６２４）为流动相,２６０ｎｍ为检测波长,建立了测定血浆中吲哚美辛浓度的高效液相色谱法,并测定了吲哚美辛控释胶囊炎痛康的血药浓度。结果表明,血浆中吲哚美辛浓度在０．１２５～５．０ｍｇ／Ｌ范围内线性关系良好（ｒ＝０．９９９６）,检测限６２．５μｇ／Ｌ（Ｓ／Ｎ＝３１）,平均回收率为１００．４％,日内和日间ＲＳＤ均小于５％。１１位受试者单剂量口服炎痛康后的相对生物利用度为１０２．３８％。     

鲁米诺—双氧水—铬（Ⅲ）化学发光体系测定化探样品中痕量砷

用鲁米诺－双氧水－铬（Ⅲ）化学发光体系结合巯基棉对Ａｓ（Ⅲ）的富集分离，建立了快速的测定化探样品中痕量砷的新方法，检测线性范围为１．０＊１０＾－４－１．０＊１０＾１ｍｇ／Ｌ，检出限为３．４＊１０＾－５ｍｇ／Ｌ。用于实际化探样吕测定，相对标准偏差为５．５＾－９．０％。     

反相高效液相色谱法测定人血浆中曲尼司特浓度

报道了用反相高效液相色谱法测定人血浆中曲尼司特浓度。以甲醇－磷酸二氢钾缓冲液（６０∶４０，Ｖ／Ｖ；ｐＨ４．２）为流动相，色谱柱采用ＹＷＧ－Ｃ１８不锈钢柱，紫外３３３ｎｍ波长检测，血浆样品经甲醇沉淀蛋白后直接进样测定。血浆浓度在０．６５～４０ｍｇ／Ｌ范围内线性良好，方法的平均回收率为１００．０％±４．１％。血浆最低检测浓度为０．２ｍｇ／Ｌ。对１０名健康志愿者口服２００ｍｇ曲尼司特后不同时间的血药浓度进行了测定。     

反相高效液相色谱法测定人血浆中曲尼司特浓度

 报道了用反相高效液相色谱法测定人血浆中曲尼司特浓度。以甲醇－磷酸二氢钾缓冲液（６０∶４０，Ｖ／Ｖ；ｐＨ４．２）为流动相，色谱柱采用ＹＷＧ－Ｃ１８不锈钢柱，紫外３３３ｎｍ波长检测，血浆样品经甲醇沉淀蛋白后直接进样测定。血浆浓度在０．６５～４０ｍｇ／Ｌ范围内线性良好，方法的平均回收率为１００．０％±４．１％。血浆最低检测浓度为０．２ｍｇ／Ｌ。对１０名健康志愿者口服２００ｍｇ曲尼司特后不同时间的血药浓度进行了测定。     

铜（Ⅰ）—苯骈三氮唑络合吸附波的极谱研究与应用

本文在０．６ｍｏｌ／Ｌ ＮＨ３－ＮＨ４Ｃｌ缓冲溶液（ｐＨ＝９．８）中，Ｃｕ（Ⅱ）在滴汞电极上还原生成Ｃｕ（Ⅰ），可与苯骈三氮唑（ＢＴＡ）络合，产生一灵敏的络合吸附波，Ｅｐ＝－０．７３Ｖ（ｕｓ，ＳＣＥ）。苯骈三氮唑的浓度在０．４０－１０．０ｍｇ／Ｌ范围内与极谱波峰高呈线性关系，检测下限为０．４０ｍｇ／Ｌ，相对标准偏差为１．４％－３．２％；回收率为９７．５％－１０１．５％。     

芦荟大黄素的电化学研究

用单扫示波极谱法研究了芦荟大黄素的电化学行为。在５％Ｎａ２ＣＯ３＋５％ＮａＯＨ（９＋１）底液中，芦荟大黄素于－０．８４Ｖ（Ｐ１）和－０．９７Ｖ（Ｐ２）处产生两个示波极谱峰，利用Ｐ１可测定芦荟大黄素，线性范围为 ０．１１－２４ｍｇ／Ｌ和３．０－２８．６ｍｇ／Ｌ，检测限为０．０６ｍｇ／Ｌ。将该法应用于中药大黄中的芦荟大黄素的测定，结果满意。另外，讨论了芦荟大黄素清除由邻苯三酚自氧化产生的超氧自由基（Ｏ２）的作用。     

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.