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1.
核黄素丁酸酯在汞电极上的吸附伏安特性及其反应速率常数的测定 总被引:8,自引:0,他引:8
循环伏安法表明,在NaOH底液中核黄素丁酸酯(riboflavine tetrabutyrate,RT)在汞电极上有一对氧化还原峰,其峰电位Epc=Epa=-0.64V(vs.Ag/AgCl)。本文用多种电化学手段对RT的吸附特性进行了较详细的研究。吸附粒子为RT中性分子,测得RT在汞电极上的饱和吸附量为5.42×10-11mol/cm2,每个RT分子所占电极面积为3.06nm2,RT在悬汞电极上的吸附符合Frumkin等温式。测得吸附系数β=4.6×105,吸引因素γ= 1. 10,吸附自由能△G°=- 32. 30 kJ/mol。本文还用循环伏安法研究了RT的电极反应动力学性质,测定了其在汞电极上的反应速率常数。 相似文献
2.
鸟嘌呤—铜配合物在汞电极表面上的电吸附性的研究 总被引:1,自引:0,他引:1
在0.02mol/L NaHCO3-0.05mol/La2SO4介质中、用极谱法和伏安法研究表明,铜-乌嘌呤配合物在汞电极表面上的吸附服从Langmuir吸附,测得其饱和吸附量Γm=1.1×10^-10mol/cm^2,吸附系数β=4.7×10^4,吸咐自由能△G°=-36.6kJ/mol。在8×10^-6mol/L Cu^2+离子存在下,可用示差脉冲阴极吸附溶出法测定8×10^-10~1×10^ 相似文献
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在HAc-NaAc底液中,卡可西灵在汞电极上有两个还原峰,第一峰峰电位Epc1=0.04V(vs.Ag/AgCl),为2电子转移的可逆过程;第二峰峰电位Epc2=-0.39V,为4电子转移的不可逆过程,第二峰具有明显的吸附性。本文探讨了该吸附特性,认为吸附型体为中性分子,属于不可逆吸附体系。测得其电极反应动力学参数αnα和卡可西灵在汞电极上的饱和吸附量,估计了每个卡可西灵分子所占的面积,建立了测定 相似文献
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报道了测定痕量镉的一种新方法.在0.01mol/LHAc-0.01mol/LNaAc-1.2×10-5mol/L乙醛酸缩氨基硫脲(GATSC)体系中,Cd-GATSC产生一灵敏的吸附还原波,波的峰电位是-0.43V(vs·SCE),峰电流与镉的浓度在1.0×10-8~8.0×10-7mol/L范围内成直线关系.此法用于测定水中痕量镉,结果令人满意。 相似文献
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在PH=4.0的0.3mol/L的HAc-NaAc介质中,钼(Ⅵ)-向红菲罗啉体系在悬汞电极上,于-0.58V电位处得到钼(Ⅵ)-向红菲罗啉络合物的吸附还原波,其1.5次微分伏安图的峰峰值epp与Mo(Ⅵ)在3.0×10^-10--1.2×10^-7mol/L浓度范围内呈良好的线性关系;检测限可达8×10^-11mol/LMo(Ⅵ)。方法用于豆类样品微量钼的测定,结果较邹。 相似文献
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托美汀的吸附伏安法研究 总被引:2,自引:0,他引:2
在0.2mol/L NH3-NH4Cl底液中,托美汀在悬汞电极上有一灵敏的还原峰。峰电位为Epc=-1.48V,该峰具有明显的吸附性,峰电流ipc与TOL浓度在4.0×10^-9-7.0×10^-7mol/L范围内呈线性关系;检出限为5.0×10^-10mol/l,用该法测定了片剂TOL的含量,结果良好。 相似文献
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8—氮鸟嘌呤的极谱伏安行为 总被引:4,自引:0,他引:4
用循环伏安法(CV)、电流采样极诸法(SCP,即TAST)、常规脉冲极谱法(NPP)、微分脉冲极谱法(DPP)、线性扫描伏安法(LSV)、Osteryoung方波伏安法(OSWV)和计时库仑法(CC)等电化学技术研究了抗癌药物8-氮鸟嘌呤(8-azaguanine,guanazolo,简称8-AG)的极谱伏安行为.在 0. 1mol/L H2SO4底液中,8-AG有一良好的还原峰,峰电位(Ep)在-0. 95V(vs.Ag/AgCl,下同)附近,8-AG浓度在4×10-6~8×10-4mol/L范围内.峰高与浓度有良好的线性关系,线性相关系数r=0.9999~0.9910,检出限为1× 10-6mol/L.实验证明了该峰具有吸附性.本文提出了电极反应机理,它包括:酸性介质中8-AG的质子化、质子化的8-AG在汞电极上吸附以及完全不可逆的两电子还原过程.同时用量子化学计算方法(全略微分重叠法即CNDO/2)对8-AG和鸟嘌呤的各原子的净电荷以及Wiberg键级进行了计算,从理论上解释了8-AG的电化学还原机理。 相似文献
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阿霉素的吸附伏安法研究 总被引:5,自引:1,他引:4
阿霉素在0.1mol/L HAc-NaAc底液,富集电位-0.20V,富集时间120s,扫速100mV/s等条件下,于悬汞电极上产生一灵敏的吸附伏安还原峰,峰电位为-0.45BV,峰电流与ADM浓度为1.0×1010^-9-4.0×10^-7mol/L范围内呈线性关系,检测限可达5.0×10^-10mol/L。 相似文献
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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%. 相似文献
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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. 相似文献
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Uroš Grošelj Mojca Žorž Amalija Golobič Branko Stanovnik Jurij Svete 《Tetrahedron》2013,69(52):11092-11108
A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives. 相似文献
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The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp3)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp2)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp2)?H and aliphatic 1,5- and 1,6-C(sp3)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp3)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp2)?H insertion. 相似文献
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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. 相似文献
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Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction
Laurent Gavara Thomas Boisse Jean-Pierre Hénichart Adam Daïch Philippe Gautret 《Tetrahedron》2010,66(38):7544-5571
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. 相似文献
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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. 相似文献
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N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%). 相似文献
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Shashikant U. Dighe Surya K. Samanta Shivalinga Kolle Sanjay Batra 《Tetrahedron》2017,73(17):2455-2467
An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y1 and Y2. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones. 相似文献
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In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates. 相似文献