钴/玻碳离子注入修饰电极伏安法测定呋喃妥因的研究

呋喃妥因 (NFT)在 0 .1mol/LHAc NaAc (pH 4 .0 )溶液中于钴 /玻碳 (Co/GC)离子注入修饰电极上产生一灵敏的伏安还原峰 ,峰电位为 - 0 .2 6V(vs.Ag/AgCl) ,峰电流与NFT浓度在 6 .0× 10 -8～ 5 .0× 10 -6mol/L范围内呈线性关系 (r =0 .9987) ,检出限为 1.0× 10 -8mol/L。用线性扫描伏安法和循环伏安法研究了NFT的伏安行为、吸附特性和电极反应机理。测定了电子转移数 (n =4 )、转移系数 (α =0 .5 8)和参与反应的质子数 (X =4 )等电化学参数。结果表明该电极过程为一具有吸附性的不可逆过程。该法用于片剂中NFT含量的测定 ,得到满意的结果。用标准加入法测得该法的回收率为 94 .0 %～ 98.5 %。     

西维来司他的极谱伏安法研究

应用循环伏安法(CV)、线性扫描伏安法(LSV)、控制电位电解库仑法(BE)对西维来司他的电化学行为进行了研究。在0.2mol/LHAc-NaAc(pH=5.6)缓冲液中,对其进行扫描,发现于-1.29V(vs.SCE)处产生一灵敏的还原峰,其峰电流与西维来司他的浓度在1×10-5~2×10-4mol/L范围内呈良好的线性关系(r=0.9976);检出限为2.0×10-6mol/L。对5.0×10-5mol/L西维来司他溶液进行12次平行实验,RSD为0·56%。实验结果表明,西维来司他在极谱电极上有吸附性质,并为此求得了电极反应的电子转移数为4,同时对电极反应机理进行了研究。     

呋喃丹的极谱法测定研究及应用

用循环伏安法(CV)、线性扫描伏安法(LSV)对呋喃丹的极谱伏安行为及其测定进行了研究。在0.2mol/L NH3-NH4Cl底液中(pH 8.8),对其进行扫描,发现于-1.21V(vs.SCE)处产生一灵敏的还原峰,其峰电流与呋喃丹的浓度在5.0×10-6-1.0×10-mol/L范围内呈良好的线性关系(r=0.9995)。对5.0×10-5mol/L呋喃丹溶液进行6次平行实验,RSD为0.2％。实验结果表明,呋喃丹在极谱电极上有吸附性质。同时对电极反应机理进行了研究。该方法对微生物降解呋喃丹进行监测取得满意的结果,96 h内呋喃丹的降解率为98％。     

极谱催化波测定脉络宁口服液中的肉桂酸

应用线性扫描极谱法(LSV)、循环伏安法(CV),在1.0 mol/L HAc-NaAc(pH 4.1)含溶解氧的支持电解质中,对肉桂酸的电化学行为进行了研究。在该支持电解质中于-1.50 V(vs.SCE)处发现肉桂酸产生一灵敏的催化极谱还原峰,其峰电流与肉桂酸的浓度在2.5×10-6~7.5×10-4mol/L范围内呈良好的线性关系(r=0.999 1);检出限为8.0×10-7mol/L,对8.0×10-5mol/L的肉桂酸溶液进行11次平行测定,RSD为1.4%。并采用循环伏安法对肉桂酸的电极反应机理进行了探讨,结果表明该电极反应过程为不可逆过程。该方法已用于测定脉络宁口服液中的肉桂酸。     

硒代胱氨酸在银电极上的电化学行为及其定量分析

研究了硒代胱氨酸 (SeCys)于0.03mol/L的硼砂 -NaOH( pH9.5)介质中在银电极上的电化学行为 ;实验发现在 -0.62V和 -0.68V(vsSCE)处存在一对氧化还原峰 ,其峰电流与硒代胱氨酸浓度具有良好的线性关系 ,由此建立了SeCys的电分析化学测定方法, (1)循环伏安法 ,其线性范围为8.6×10 -9～1.1×10 -7mol/L,检出限为4.3×10 -10mol/L, (2)二次微分线性扫描伏安法 ,其线性范围为2.2×10 -10～1.0×10 -8mol/L,检出限为8.6×10-11mol/L;该法应用于中药黄芪中SeCys含量的测定 ,结果令人满意 ;该文还探讨了硒代胱氨酸在上述条件下的电极反应机理     

L-半胱氨酸自组装膜电极对米吐尔的电催化及其分析应用

研究了米吐尔在L 半胱氨酸自组装膜修饰金电极上的电化学行为。米吐尔在该修饰电极上的CV曲线仅出现一对峰 ,其峰形对称 ,ΔEp =42mV ,氧化还原峰电流之比约等于 1,为可逆反应 ;扩散系数D =2 .2 4× 10 - 6 cm2 ·s- 1 。初步探讨了电催化机理。差分脉冲伏安法测定其氧化峰电流与米吐尔浓度在 5 .0× 10 - 7～ 2 .0× 10 - 5mol/L和 5 .0× 10 - 5～ 1.0× 10 - 3 mol/L范围内分段呈线性关系 ;相关系数分别为 0 .9987和 0 .9972 ;检测限 1.0× 10 - 8mol/L     

舒乐安定在铂离子注入修饰电极上的电化学行为及其应用

舒乐安定在0.1 mol/L NH3-NH4Cl缓冲溶液(pH 9.40)中,用线性扫描伏安法,在Pt/GC离子注入修饰电极上,形成一良好的线性扫描伏安还原峰,峰电位Ep=-0.70V(vs.SCE)。其峰电流与舒乐安定浓度在3.0×10-9-1×107和1×10-7-1.5×10-6mol/L范围内呈线性关系,相关系数均为0.9999,检出限为3.0×10-9mol/L。并用于片剂的测定,回收率在96.5％～98.5％之间,结果是可靠的。用循环伏安法研究了体系的性质。实验表明,电极过程为不可逆吸附。用AES、XPS和SEM等表面分析方法证明,Pt离子确实注入到玻碳基体电极表面,Pt以原子态存在,催化了舒乐安定的还原。     

聚L-白氨酸修饰电极伏安法测定痕量多巴胺的研究

用循环伏安法制备了聚L-白氨酸修饰玻碳电极,研究了多巴胺在聚L-白氨酸修饰玻碳电极上的电化学行为,建立了循环伏安法测定痕量多巴胺的新方法。实验结果表明,在pH 6.0的磷酸盐缓冲溶液中,多巴胺在聚L-白氨酸修饰玻碳电极上产生一对灵敏的氧化还原峰,峰电位分别为Epa=0.281V,Epc=0.170 V(相对Ag/AgCl电极)。峰电流与多巴胺的浓度在5.0×10-8~5.0×10-4mol/L的范围内有线性关系,检出限为5.0×10-9mol/L。对1.0×10-5mol/L多巴胺溶液平行测定9次,其相对标准偏差为4.0%。已用于针剂中多巴胺的测定。     

抗癌药长春新碱及其与微管蛋白相互作用的电化学研究

在 0 0 5mol/LTris,0 15mol/LNaCl溶液中 ,用吸附伏安法研究长春新碱 (VCR) ,其峰电位在 -1 68V (vs .Ag/AgCl) ,峰电流与 1 0× 10 -8～ 2 0× 10 -7mol/LVCR浓度成正比 ,检测限为 7 0× 10 -9mol/L .用常规脉冲极谱法、线性扫描和循环伏安法等研究该体系的电化学行为 .实验表明 ,电极还原过程为具有吸附特征的不可逆过程 .VCR的吸附符合Frumkin吸附等温式 .也研究了VCR与微管蛋白的相互作用 .实验表明 ,VCR与微管蛋白形成一电活性的结合物 ,这一结合物具有吸附性 ,且还原过程也为不可逆过程     

纳米金/双氢氧化物膜修饰电极制备及对肾上腺素的测定

研究了纳米金/双氢氧化物膜修饰玻碳电极(AuNPs/LDHs/GCE)的制备,通过循环伏安法、扫描电镜和电化学阻抗对修饰电极进行了表征;详细讨论了电极的性能,找出了制备该修饰电极的实验条件,并将此电极用于生物体系中肾上腺素(Adrenaline,AD)的电化学测定.在选定的实验条件下,修饰电极在磷酸盐缓冲溶液(pH=7.0)中进行循环伏安扫描时,氧化峰电流和肾上腺素浓度在9.0×10-8～1.0×10-4mol/L范围内呈良好的线性关系,相关系数为0.9982,其检出限(S/N=3)可达3.1×10-8 mol/L.据此建立了一种新的测定肾上腺素的分析方法,可用于实际样品的检测.     

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.