二溴对甲偶氮羧光度法测定水中硫酸根

基于二溴对甲偶氮羧与钡离子进行显色反应 ,建立了间接光度法测定硫酸根方法。在磷酸介质中试剂与钡形成蓝色的络合物。在波长 6 0 9nm处测定吸光度 ,εmax=4 .0 8× 10 4 L·mol- 1·cm- 1,线性范围为 0 1.6mg·L- 1。显色体系具有很高的选择性 ,考察了常见离子的干扰情况 ,提供了一种测定硫酸根含量的方法 ,结果满意。     

应用2-(5-硝基-2-吡啶偶氮)-5-二甲氨基苯胺同时测定铑与钯

提出了以 2 - ( 5-硝基 - 2 -吡啶偶氮 ) - 5-二甲氨基苯胺 ( 5- NO2 - PADMA)作为铑、钯同时测定的新光度试剂。钯与试剂可在 0 .3～ 3.9mol/L 的高氨酸介质中形成稳定的配合物 ,其最大吸收位于 62 1 nm处 ;而铑与试剂则在 p H=5.2 5～ 6.75的近中性介质中定量配合 ,配合物一旦形成则很稳定 ,向其中加入强酸酸化该配合物不仅不被分解反而吸收红移、吸光度增大 ,同时二者的吸光度具有良好的加和性。基于二者显色酸度的差异 ,建立了铑、钯同时测定的新方法。方法的灵敏度为 εRh62 0 =1 .39× 1 0 5L·mol-1·cm-1;εPd62 0 =9.4× 1 0 4 L· mol-1·cm-1。铑浓度在 0～ 0 .56、钯浓度在 0～ 1 .4μg·m L-1范围内服从比耳定律。可用于工业样品中微量铑、钯的测定。     

偶氮氯膦Ⅲ吸光光度法测定水中微量钙

探讨了偶氮氯膦Ⅲ吸光光度法测定水中微量钙的最佳测定条件。试验表明,在pH2 80～2.85柠檬酸三钠 盐酸缓冲溶液中,钙离子与偶氮氯膦Ⅲ形成1∶1的配合物,其吸收峰为双峰,最大吸收波长为666nm,水中钙离子含量在0～0.56mg·L-1范围内符合比耳定律,回归方程C=0.0013+2.6382A(mg·L-1),相关系数为0.9999,摩尔吸光系数ε=1.54×104L·mol-1·cm-1,加入EDTA或葡萄糖酸钠等掩蔽剂后,其他金属阳离子在测定条件下对钙离子的测定基本无影响。     

分光光度法快速测定食品中糖精钠含量

基于在硫酸介质中,次甲基蓝与糖精钠反应生成憎水型离子缔合物,且该缔合物可被氯仿定量萃取,提出了分光光度法测定食品中糖精钠含量。在室温下,当0.2 mol.L-1硫酸用量为2.5 mL,0.04 mol.L-1次甲级蓝溶液用量为2 mL时,糖精钠的质量浓度在15 mg.L-1范围内与其吸光度呈线性关系,检出限(3s/k)为0.11 mg.L-1。用此法测定几种食品中糖精钠含量,回收率在100.1%~114.0%之间,相对标准偏差(n=6)均小于5.0%。     

钡(Ⅱ)-偶氮氯膦Ⅲ络合物探针分光光度法测定蛋白质

在pH 1.0～1.5的酸性介质中,蛋白质与Ba(Ⅱ)-偶氮氯膦Ⅲ络合物发生作用,导致络合物溶液褪色,其最大吸收波长处吸光度的降低值与蛋白质的浓度成正比.基于此建立了以Ba(Ⅱ)-偶氮氯膦Ⅲ络合物为光谱探针,分光光度测定蛋白质含量的新方法.该法灵敏度高,选择性好.蛋白质(以牛血清白蛋白为例)的浓度在0～40 mg/L范围内服从比尔定律,表观摩尔吸光系数ε656=6.47×105 L·mol-1·cm-1.生物体内常见物质均不产生干扰,直接应用于人血清样品中蛋白质总量的测定,结果满意.     

双波长光度法测定阿米卡星的研究

在酸性条件下,水溶苯胺蓝(ANB)与硫酸阿米卡星(AMK)反应,生成蓝色离子缔合物,其最大正吸收波长位于682nm,最大负吸收波长位于602nm,正负峰吸光度绝对值之和与AMK的浓度线性相关,AMK的浓度在0～1.8×10-5mol·L-1的范围内遵从朗伯比耳定律,表观摩尔吸光系数为9.50×104L·mol-1·cm-1,由此建立了测定阿米卡星的双波长光度法。方法用于市售药物及人体尿液中阿米卡星含量的测定,结果满意。     

催化动力学光度法测定食品中微量铜的研究

提出了催化动力学吸光光度测定铜的新方法 ,基于在 0 .0 5～ 0 .0 9mol· L-1硫酸介质中和 2 .0× 1 0 -3 mol·L-1氯化十六烷基吡啶存在下 ,Cu( )催化抗坏血酸还原邻甲氧基苯基重氮氨基偶氮苯。用固定时间法在 50 2 nm处监测催化反应。方法的线性范围为 0～ 2 8ng·ml-1,检出限( 3σ)为 0 .66ng· ml-1,摩尔吸光系数为 9.65× 1 0 5L· mol-1· cm-1。除 Fe( )外常见离子都不干扰测定。用 NH4 F掩蔽 Fe( ) ,方法直接应用于多种食品分析 ,结果与二乙基二硫代氨基甲酸钠萃取光度法相同 ,相对标准偏差为 2 .0 %～ 4.4% ( n=6)。非催化反应和催化反应在 3.0～ 8.0 min内为假零级反应 ,活化能分别为 1 56.1和 1 0 3.8k J· mol     

新显色剂2-[2,3,5-三氮唑偶氮]-5-二甲氨基苯甲酸与铜的显色反应研究及应用

合成了 2 [2 ,3,5 三氮唑偶氮 ] 5 二甲氨基苯甲酸 (TZAMB) ,并研究了试剂与铜的显色反应。结果表明 ,在 0 .1mol·L- 1H3PO4 介质中 ,试剂与铜形成紫红色配合物 ,配合物至少稳定2 4h ,最大吸收波长位于 5 75nm处 ,表观摩尔吸收系数为 4 .2 3× 10 4 L·mol- 1·cm- 1,配合物的组成为 ηCu∶ηTZAMB=1∶2 ,铜浓度在 0～ 1.2mg·L- 1范围内服从比耳定律 ,所拟方法已用于镁合金和铝合金中微量铜的测定 ,试验结果与标准值相符 ,RSD为 0 .0 75 %～ 0 .5 1%。     

水溶苯胺蓝吸光光度法测定人血清蛋白

用吸光光度法研究了水溶苯胺蓝(AnB)与牛血清白蛋白(BSA)在Britton-Robinson广泛pH缓冲介质中的结合反应,在最佳试验条件下,以试剂空白为参比,AnB-BSA复合物在600nm波长处的吸光度,与BSA的浓度呈良好的线性关系,BSA的线性范围为1.6×10-8～2.4×107mol.L-1,摩尔吸光系数ε=1.34×106L·mol-1·cm-1,Sandell灵敏度为0.051μg·cm-2,BSA的检出限为1.0×10-8mol·L-1,方法具有灵敏度较高、选择性好等特点,用于人血清样品中蛋白质的测定,与溴甲酚绿方法结果一致。     

流动注射停流法快速测定环境水样中COD

应用流动注射停流分析技术 ,对环境水样中的COD进行测定。采用KMnO4 作氧化剂和光度分析指示剂 ,葡萄糖作基准物质 ,在反应温度为 95℃ ,停流 5min时 ,COD测定范围为 0～10 0mg·L- 1,检出限为 2mg·L- 1,相对标准偏差为 0 .8% (n =9) ,回收率为 85 %～ 95 %。Cl-<15 0mg·L- 1时不干扰测定     

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.