溴酸钾氧化荧光素动力学荧光法测定痕量亚硝酸根

基于稀硫酸介质中,亚硝酸根催化溴酸钾氧化荧光素,建立了动力学荧光法测定痕量亚硝酸根的新方法。本方法具有高灵敏度和高选择性,测定亚硝酸根的线性范围为2～80ng/ml,可用于直接测定水样中亚硝酸根。     

吖啶红荧光猝灭法测定痕量亚硝酸根

研究了在稀硫酸介质中亚硝酸根与吖啶红发生的亚硝化反应,建立了测定痕量亚硝酸根的荧光猝灭法。方法的测定范围为0.01～0.70μg·ml-1。方法用于环境水样中痕量亚硝酸根的测定,结果满意。     

催化动力学光度法测定新鲜果蔬中痕量亚硝酸根

基于在稀磷酸介质中亚硝酸根对溴酸钾氧化百里酚蓝褪色反应的催化效应 ,建立了一种测定痕量亚硝酸根的催化光度法。该方法测定亚硝酸根的线性范围为 0～ 6 .5 μg/ 2 5ml,灵敏度为 0 .6 7ng·ml- 1。用于新鲜果蔬样品中痕量亚硝酸根的测定 ,结果满意     

二甲苯蓝FF-十六烷基三甲基溴化铵分光光度法测定痕量亚硝酸根

1 引言亚硝酸根是水质、食品和环境检测的重要指标之一.目前,测定亚硝酸根的方法已有不少,作者发现,在稀盐酸介质中,十六烷基三甲基溴化铵的存在可使二甲苯蓝FF与亚硝酸根的反应灵敏度提高,选择性增强,从而建立了测定亚硝酸根的新方法.     

基于重氮化反应分光光度法测定微量亚硝酸根

1　引　　言亚硝酸根与芳胺或苯甲胺反应因生成致癌物质亚硝胺而引起普遍关注 ,因此 ,分析化学工作者研究了一系列测定的方法。目前 ,光度法测定亚硝酸根的方法除经典的Ｇｒｉｅｓｓ法及其改良法外又有不少报道 ,如催化法、重氮化偶联法和亚硝化法等 ,但基于核固红 (1 氨基 2 ,4 二羟基蒽醌 3 磺酸 )与亚硝酸根发生重氮化反应的光度法测定亚硝酸根的方法未见报道。作者发现 ,在盐酸介质中 ,亚硝酸根的加入使核固红在 5 5 2ｎｍ处的吸收峰明显降低 ,从而建立了光度法测定亚硝酸根的新方法。方法操作简单 ,灵敏度较高 ,重复性好 ,可直接测定…     

橙黄Ⅳ分光光度法测定微量亚硝酸根

亚硝酸根是水质检测和食品分析中重要的测定项目之一。天然水和食品中亚硝酸根的测定主要用分光光度法，较经典方法是基于重氮化偶联反应和亚硝化反应，催化光度法也有不少研究。近年来，亚硝化反应由于方法简便、反应产物具有良好的稳定性和分析性能，重新引起了人们的兴趣。本文研究了在盐酸介质中，橙黄Ⅳ与亚硝酸根的亚硝化反应，建立了以双波长叠加分光光度法测定亚硝酸根的方法。用于环境水和合成水样中微量亚硝酸根的测定，结果满意。     

天青Ⅰ分光光度法测定冷却液中的亚硝酸根

研究了亚硝酸根与染料天青Ⅰ在盐酸介质中的显色反应。结果表明,反应产物的最大吸收波长为442nm,据此拟定了快速简便的分光光度测定冷却液中亚硝酸根的新方法。该方法亚硝酸根浓度在0～200ug/50mL范围内服从比尔定律,用于冷却液中亚硝酸根的测定,结果与KMnO_4容量分析法一致。     

催化光度法测定痕量亚硝酸根

基于稀磷酸介质中亚硝酸根催化溴酸钾氧化靛蓝的褪色反应,建立测定痕量亚硝酸根的方法。方法检出限为1.36×10-6g.L-1,线性范围为0.012~0.08mg.L-1,回收率为98.0%~100.8%。方法已用于水中亚硝酸根的测定,结果满意。     

荧光分光光度法测定痕量亚硝酸根——基于对劳氏紫的荧光猝灭作用

在盐酸介质中亚硝酸根能与劳氏紫发生重氮化偶联反应,基于劳氏紫的荧光强度随亚硝酸根的加入量增加而明显降低的现象,建立了荧光猝灭一荧光分光光度法测定痕量亚硝酸根的方法,线性范围为0.04～0.40 mg·L-1,用于泡菜样品中痕量亚硝酸根的测定,测得回收率在96%～104%之间.     

对氨基苯甲酸荧光猝灭法测定痕量亚硝酸根

亚硝酸根广泛存在于土壤、天然水、食品等物质中,亚硝酸根被人体吸收后,可使体内正常的血红蛋白氧化而失去携氧能力,与胺类及酰胺类化合物反应生成致癌性的亚硝胺类物质,亚硝酸根是环境和食品等检测的重要项目之一。因此,建立高灵敏、高选择性的测定亚硝酸根方法十分重要。由于分子荧光光度法具有灵敏度高,干扰少,试剂低毒等特点,引起了广泛关注。但已报道的此类测定方法除加入荧光化合物外,还需加入其它辅助试剂,使试验相对复杂。文献方法用亚硝酸根直接与藏红T在盐酸介质中发生重氮化反应测定了亚硝酸根。     

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.