二次微分简易示波伏安法用于胃舒平片剂中铝的测定

向3.75×10 -5mol/LCd2 + -4.0×10 -5mol/L芦丁 -0.05mol/LKNO3-0.05mol/LNa2B4O7 中加入Al3 +时 ,二次微分简易示波伏安图上由Cd -芦丁配合物产生的峰高在一定范围内随Al3 + 浓度的增加线性降低 ,据此建立了测定Al3 +的二次微分简易示波伏安法 ;线性范围为1.0×10 -6～6.5×10 -4mol/L ,检出限为6.0×10-7 mol/L ;该法用于胃舒平片剂中铝的测定的相对标准偏差为3.3 %(n=5)。     

钙-茜素红S的示波行为及应用

在0.1 mol/L KOH底液中,研究了Ca2+与ARS形成络合物的示波行为,并根据其在dE/dt-E曲线阴极支-0.83V产生一灵敏切口的示波特性建立了测定葡萄糖酸钙口服液及片剂中钙含量的二次微分简易示波伏安法。当Ca2+浓度在4.0×10-7～1.9×10-5mol/L时.二次微分简易示波伏安图上Ca-ARS的峰高与Ca2+浓度呈线性关系:相关系数为0.9973;检出限为3×10-7mol/L。对2.0×10-6mol/L Ca2+6次测定的RSD为1.2％.     

苯巴比妥的二次微分简易示波伏安法测定

利用苯巴比妥的示波特性 ,分别建立了在0.2mol/LKOH和1.0×10-4mol/LCd2 +-0.1mol/L硼砂底液中直接和间接测定苯巴比妥的二次微分简易示波伏安法 ;直接测定和间接测定的线性范围分别为1.0×10 -5mol/L～1.0×10 -4mol/L和4.0×10 -6mol/L～8.0×10 -5mol/L ;检出限分别为8×10 -6mol/L和2×10 -6mol/L;在直接测定中 ,对6.000×10 -5mol/L苯巴比妥进行10次测定的RSD为4.5 % ;间接测定中 ,对2.000×10 -5mol/L苯巴比妥进行10次测定的RSD为2.6 % ;这一研究表明对于一些在示波分析中灵敏度不高或本身没有示波活性的药物 ,可以利用其与金属离子生成沉淀的方法间接测定 ,从而提高药物测定的灵敏度、拓宽示波分析应用领域     

二次微分简易示波伏安法用于葛根素测定

根据在 0 .1 mol/ L Na OH溶液中 ,葛根素在二次微分简易示波伏安图阴极支-0 .95V ( vs.SCE)产生一灵敏峰的示波特性 ,建立了二次微分简易示波伏安法测定药品中葛根素含量的新方法。线性范围为 2 .5× 1 0 - 6～ 3 .5× 1 0 - 5mol/ L,相关系数为 0 .9985,检出限为 1× 1 0 - 6mol/ L,对 9.0× 1 0 - 6mol/ L葛根素进行 5次测定的RSD为 1 .5%。利用该法测定中药葛根及心可舒片剂中葛根素的回收率分别为 1 0 0 .2 %和 96.9%。     

青霉素 V钾的二次微分简易示波伏安法测定

利用青霉素 V钾在 pH=7的 KH2PO4-Na2HPO4缓冲溶液中产生切口的示波特性 , 提出了一种药片中青霉素 V钾的测定方法 - - 二次微分简易示波伏安法 ; 校正曲线的线性范围为 2.0× 10-5～ 2.0× 10-4 mol/L, 检出限为 8× 10-6 mol/L; 对 7.0× 10-5 mol/L青霉素 V钾 8次测定结果的相对标准偏差为 1.6% ; 实验结果表明该法具有分析速度快、仪器装置简单以及药片中的淀粉等物质不干扰测定的优点 .     

头孢哌酮钠的直接和间接示波测定

在pH4.2HAc -NaAc缓冲溶液中 ,头孢哌酮钠在示波图阴极支 -1.48V(vsSCE)处产生一个灵敏切口 ;而在0.2mol/LNaOH底液中 ,头孢哌酮钠与 β_环糊精(β_CD)形成包结物使 β_CD在示波图上产生的切口变浅。根据这些示波特性 ,建立了测定头孢哌酮钠注射剂中头孢哌酮钠含量的直接和间接二次微分简易示波伏安法。实验结果表明 :直接测定头孢哌酮钠的线性范围为1.2×10 -5～2.2×10 -4mol/L ,检出限为6.0×10 -6mol/L ,对3.000×10 -5mol/L进行5次测定的RSD为2.1 % ;而间接测定的线性范围为2.0×10 -6～9.0×10 -5mol/L ,检出限8.0×10 -7mol/L ,对2.500×10 -6mol/L进行5次测定的RSD为2.7 %。与直接法相比较 ,间接测定头孢哌酮钠的检出限更低而线性范围更宽     

二次微分简易示波伏安法测定痕量镍

用二次微分简易示波伏安法测定了金刚石酸洗废液中的痕量镍 .结果表明 :在 0 .2 0mol/ L NH4 Ac- 0 .0 0 5mol/ L KNO3- 0 .0 2 %丁二酮肟中 ,Ni2 浓度在 3× 10 -7～ 3.5× 10 -6mol/ L范围内与峰高呈线性关系 ,回归方程为 Y=0 .3583 1.365× 10 5c( Ni2 ) ( mol/ L) ,相关系数 r=0 .9970 ,检测下限为 6× 10 -8mol/ L.该法简单、快速、灵敏     

葡萄酒中白藜芦醇的二次微分简易示波伏安法测定

在 0.2 mol/L KOH介质中 ,用二次微分简易示波伏安法测定了葡萄酒中的白藜芦醇含量。校正曲线的线性范围为 2× 10－ 6～ 5× 10－ 5 mol/L,检出限为 1× 10－ 6 mol/L。对 2.5× 10－ 5 mol/L白藜芦醇测定的相对标准偏差为 1.9％（ n=6）。与其它技术相比较,该法具有仪器简单、操作简便、分析速度快的优点。     

示波伏安法测定碘酸钾碘盐中碘

在0.2 mol.L-1NaOH底液中,碘酸钾在示波图阴极支-0.6 V和-1.6 V(vs.SCE)处产生两个切口。其中-1.6 V处切口较为灵敏、稳定,根据这些示波特性,建立了测定碘酸钾碘盐中碘含量的二次微分简易示波伏安法。其二次微分简易示波伏安峰峰高随碘酸钾浓度增大在一定范围内线性增长,线性范围为3.5×10-6~6.4×10-5mol.L-1,回归方程为h(V)=141.40+1.03×106c(mol.L-1),相关系数为0.999 1,检出限为1.0×10-6mol.L-1。对5.0×10-6mol.L-1碘酸钾5次测定的RSD为2.2%,回收率为100.3%。方法仪器简单、快速、无需通氮除氧。     

二次微分简易示波伏安法用于叶酸测定的研究

在0.2mol/LNa2B4O7 底液 ,用二次微分简易示波伏安法测定了叶酸片中叶酸含量。通过对校正曲线进行平方处理 ,明显改善了校正曲线的线性关系 ,扩大了测定的线性范围。实验结果表明 :在叶酸浓度为2.0×10-6～4.2×10-5 mol/L范围内 ,校正曲线相关系数从平方处理前的0.9883提高到平方处理后的0.9993 ,检出限为9×10-7 mol/L。样品测定的相对误差为2.0 %,测定的平均回收率为101.2 %。     

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.