青蒿素及其衍生物电化学性质的研究Ⅱ: 青蒿素在 氯化血红素存在下的还原

用电化学方法研究了青蒿素与氯化血红素之间的相互作用。青蒿素在玻璃碳电极上于-1.08V处发生一个2电子转移的不可逆还原。但是,即使在低至4.0×10^-^8mol/L氯化血红素存在下,青蒿素仍可被催化还原,阴极过电位降低了600mV。配合物EDTA-Fe(Ⅲ)具有类似氯化血红素的催化性质,它降低了QHS阴极过电位590mV。在这个体系中,青蒿素在碳电极上的还原是一个借助于氯化血红素催化的还原过程,氯化血红素的存在降低了青蒿素还原活化能,促进了青蒿素的分解。文中讨论了该反应的还原机理。     

青蒿素及其衍生物电化学性质的研究Ⅱ: 青蒿素在 氯化血红素存在下的还原

用电化学方法研究了青蒿素与氯化血红素之间的相互作用。青蒿素在玻璃碳电极上于-1.08V处发生一个2电子转移的不可逆还原。但是,即使在低至4.0×10^-^8mol/L氯化血红素存在下,青蒿素仍可被催化还原,阴极过电位降低了600mV。配合物EDTA-Fe(Ⅲ)具有类似氯化血红素的催化性质,它降低了QHS阴极过电位590mV。在这个体系中,青蒿素在碳电极上的还原是一个借助于氯化血红素催化的还原过程,氯化血红素的存在降低了青蒿素还原活化能,促进了青蒿素的分解。文中讨论了该反应的还原机理。     

蒽醌/聚吡咯复合膜修饰电极的电化学行为和电催化活性

在水溶液中制备了掺杂蒽醌磺酸盐(AQS)的聚吡咯(PPy)/玻碳复合膜修饰电极,采用循环伏安法和旋转圆盘电极技术研究了该修饰电极在不同pH值溶液中的电化学行为以及在pH=5.5的磷酸盐缓冲溶液中对氧还原反应的电催化性能和动力学.结果表明,与裸玻碳电极相比,PPy膜的存在不仅降低了AQS的反应电位和峰电位差,而且增大了其氧化还原反应的峰电流,H2AQ/HAQ-氧化还原对的电离常数为9.5.AQS/PPy膜修饰电极上氧的还原主要是两电子还原为H2O2的不可逆过程,H2AQ对氧还原反应起主要催化作用,还原过程符合异相氧化还原催化机理.该修饰电极具有良好的电化学重现性.     

水溶液中2,4,6-三溴苯酚在银阴极上的选择性脱卤

采用循环伏安法比较了玻碳、光亮银和粗糙化银电极对2,4,6-三溴苯酚还原脱卤反应的电催化活性, 初步研究了碱性水溶液中2,4,6-三溴苯酚在粗糙化银电极上的还原脱卤历程; 在此基础上, 利用恒电位电解法进一步探索了2,4,6-三溴苯酚在粗糙化银电极上的电还原脱卤历程. 结果表明, 粗糙化银电极对2,4,6-三溴苯酚的选择性还原脱卤反应具有优良的电催化活性, 且其活性优于光亮银和玻碳电极; 2,4,6-三溴苯酚在粗糙化银电极上的还原反应是个逐步脱卤过程, 推测得出其邻位和对位C—Br键的还原断裂所需的活化能非常接近, 而反应中间产物2,4-二溴苯酚的对位C—Br键的还原断裂所需的活化能比邻位要低; 2,4,6-三溴苯酚能实现完全脱卤生成苯酚, 主要路径为2,4,6-三溴苯酚→2,4-二溴苯酚→2-溴苯酚→苯酚.     

血红素LB膜的电化学行为

采用循环伏安法研究了血红素与脑磷脂混合Y型LB（Langmuir-Blodgett）膜在玻碳电极上的电化学行为，结果表明血红素LB膜有良好的电化学活性，在0．1mol/L KCl溶液中有一对氧化还原峰（－0．42V／－0．30V）；将血红素LB膜转移到玻碳电极表面得到的血红素LB膜修饰电极（heme LB-GC）对溶液中溶解氧的电化学还原有良好的催化作用，其催化还原过程具有不可逆电荷传递特性。     

Ce4+/Ce3+-V2+/V3+氧化还原流动电池的可行性研究(Ⅱ)--旋转圆盘(RDE)与旋转环盘(RRDE)法对Ce4+/Ce3+氧化还原体系的研究

用RDE与REDE法研究了Ce4+/Ce3+-V2+/V3+氧化还原流动电池中Ce4+/Ce3+体系的电化学动力学参数,以说明组成该新型氧化还原流动电池的可能性.用RDE法得出在铂电极表面与玻碳电极上均会生成一层氧化膜,对Ce3+的氧化反应产生阻碍作用.但在铂上的氧化膜对Ce4+的还原反应却有催化作用.用Rrde法得出Ce3+在玻碳电极上的氧化与析氧之间存在着竞争,为得到较高的Ce3+氧化效率,应控制氧化电流在2～8 mA@cm-2之间.     

多贝斯在纳米金修饰玻碳电极上的电化学行为与测定

采用循环伏安法将纳米金电沉积于玻碳电极表面,制备了纳米金修饰玻碳电极(NG/GCE).在0.05 mol/L H2SO4溶液中,用循环伏安法研究了多贝斯在NG/GCE上的电化学行为.结果表明,NG/GCE对多贝斯的氧化还原反应有明显的电催化作用.建立了测定多贝斯的新方法,用方波伏安法测得多贝斯的氧化峰电流与其浓度在4....     

烟酰胺辅酶在聚甲苯胺蓝膜修饰的玻碳电极上的电催化氧化

用循环伏安法在玻碳电极上电沉积一层稳定的甲苯胺蓝聚合物膜 ,研究了这层膜在 0 .2mol/L磷酸缓冲溶液 (pH 6 .86 )中的电化学性质 ,并且考察了该膜修饰的玻碳电极对烟酰胺辅酶 (NADH)的电催化作用 ,用旋转圆盘电极测量了NADH在该修饰电极上的催化反应常数。实验发现 ,在该修饰电极上 ,NADH氧化峰电位比未修饰的玻碳电极负移了 4 5 0mV ,且其催化反应速率常数为 3.5× 10 3 L·mol-1·s-1,说明聚甲苯胺蓝膜对NADH有良好的电催化作用     

硫酸双肼屈嗪修饰玻碳电极安培法测定过氧化氢

在1.0 mol/L H2SO4溶液中,在玻碳电极上修饰硫酸双肼屈嗪制得的修饰电极对过氧化氢还原有催化作用.研究了各种实验条件对修饰电极性能的影响.在-0.3 V工作电位下,用安培法测定过氧化氢的响应电流与其浓度在1.94×10-5～1.05×10-s mol·L-1范围内呈线性关系.该修饰电极具有制作简单,使用寿命长...     

芦丁在纳米金修饰玻碳电极上的电化学行为及其测定

采用循环伏安法将纳米金电沉积于玻碳电极表面,制备了纳米金修饰玻碳电极(NG/GCE).在pH3.29的Britton-Robinson(B-R)缓冲溶液中,用循环伏安法研究了芦丁在NG/GCE上的电化学行为.结果表明,NG/GCE对芦丁的氧化还原反应有良好的电催化作用.用方波伏安法测得芦丁的还原峰电流与其浓度在2.0×10-8～2.0×10-6mol/L范围内呈线性关系,检出限为1.0×10-8mol/L(S/N=3).     

Decomposition mechanism of an artemisinin-type compound via hemin-electrocatalysis

The interaction between a typical derivative of artemisinin and hemin was investigated by electrochemical and spectroelectrochemical methods. This derivative can be reduced via hemin-catalysis at the glassy carbon electrode, the cathodic overpotential is decreased by ca. 650 mV. A HPLC method for separating the products of the catalytic reaction was established. They were identified either in H(2)O-CH(3)CN solution or in tetrahydrofuran, respectively. The structures of these products show that the hemin-catalyzed decomposition of an artemisinin-type compound on the glassy carbon or reticulated vitreous carbon electrode can be achieved by both electrochemical reduction and rearrangement. The conclusion that the reaction of artemisinin with hemin is a critical step in the antimalarial mechanism of artemisinin can be drawn.     

Hemin Modified Carbon Fat Electrode for Analyzing Antimalarial Endoperoxide Artemisinin in Artemisia annua

A hemin bulk modified carbon electrode with Adeps neutralis (solid fat) as binder was developed for the determination of antimalarial endoperoxide artemisinin in plant matrix. The hemin modified electrode showed significant catalytic activity for the electrochemical reduction of artemisinin at about ?380 mV vs. Ag/AgCl in phosphate buffer solution of pH 7 by using cyclic and differential pulse voltammetry. Under optimized conditions strict linearity between artemisinin concentration and height of the cathodic catalytic current peak was observed in 4.8×10^?6–7.8×10^?5 M concentration range (R=0.9991) when using differential pulse voltammetry. The detection limit was calculated as 1.4×10^?6 M of artemisinin. The developed electroanalytical device is suitable for the determination of artemisinin in Artemisia annua extracts.     

Artesunate interaction with hemin

Artesunate is an important new antimalarial drug. The interaction of artesunate with hemin was investigated by electrochemical methods and UV spectroelectrochemistry (UV-SEC). Artesunate underwent an entirely irreversible reduction at ca. −1.27 V (vs. Ag/AgCl) on the glassy carbon electrode. Hemin can catalyze the decomposition of artesunate. In the presence of concentration of hemin as low as 2×10⁻⁸ M, the cathodic overpotential of artesunate was reduced ca. 680 mV (E_pc=−0.59 V vs. Ag/AgCl). UV-SEC experiments further confirm this process. UV spectra show that the decomposed products of artesunate have absorption behavior similar to artesunate. These results indicated that artesunate might undergo the identical antimalarial mechanism as its parent compound Qinghaosu, and hemin plays a catalyst role in the process of action of Qinghaosu-type antimalarial drugs.     

青蒿素及其衍生物电化学性质的研究I. 青蒿素在汞电极上的电化学还原

青蒿素及其衍生物代表着一类新型抗疟药。青蒿素分子中过氧基与抗疟活性密切相关。本文采用多种电化学方法研究了青蒿素分子中过氧基在Hg电极上的还原, 还原电位在0.0V(vs.Ag/AgCl)附近, 电极过程为不可逆还原, 反应电子数n=2, 半波电位E1/2=0.012V, 电子转移系数α=0.66, 表观标准电极反应速率常数ks'=6.34×10^-^6cm/s, 扩散系数D=4.3×10^-^6cm^2/s。反应产物在电极表面具有吸附性, 文中提出了可能的电化学反应机理。     

Electrochemical behavior of tryptophan and its derivatives at a glassy carbon electrode modified with hemin

The electrochemical behavior of tryptophan (Trp) and its derivatives, such as indole-3-acetic acid (IAA), 5-hydroxytryptamine (5-HT), 5-hydroxy-indole-3-acetic acid (5-HIAA) and glycyl-tryptophan (Gly-Trp) peptide at a glassy carbon electrode modified with hemin (hemin/GC electrode) by electropolymerization have been investigated in detail. The results showed that the hemin/GC electrode would catalyze the electrochemical oxidation of Trp and its derivatives, based on which a differential pulse voltammetric procedure has been proposed for determination of Trp and its derivatives. Meanwhile, the electrochemical reaction mechanism for these compounds at hemin/GC electrode has been also investigated, and the results indicated that a two electron and two proton transfer was involved in the electrode reaction process.     

铁铂核壳纳米粒子修饰玻碳电极制备及对亚硝酸盐还原的电催化性能

通过循环伏安法（CV）在玻碳（GC）电极表面电沉积出分布较为均匀的纳米Fe粒子,制得纳米Fe粒子修饰的GC（纳米Fe/GC）电极,再经“电荷置换”制得具有Fe核Pt壳结构的纳米粒子修饰的（纳米PtFe/GC）电极。 SEM结果显示,纳米Fe/GC和纳米PtFe/GC表面粒子的形貌均呈立方体形,分布较为均匀,粒径在60 nm左右。 纳米PtFe/GC电极对亚硝酸盐的还原具有很高的电催化活性。 3种电极的电催化活性顺序依次为：纳米Fe/GC＜纳米Pt/GC＜纳米PtFe/GC。 相对于纳米Pt/GC电极,纳米PtFe/GC电极的起始还原电位（Ei）正移了0.14 V,还原峰电流（ip）增大了3倍。     

Molecular Basis of Artemisinin Derivatives Inhibition of Myeloid Differentiation Protein 2 by Combined in Silico and Experimental Study

Artemisinin (also known as Qinghaosu), an active component of the Qinghao extract, is widely used as antimalarial drug. Previous studies reveal that artemisinin and its derivatives also have effective anti-inflammatory and immunomodulatory properties, but the direct molecular target remains unknown. Recently, several reports mentioned that myeloid differentiation factor 2 (MD-2, also known as lymphocyte antigen 96) may be the endogenous target of artemisinin in the inhibition of lipopolysaccharide signaling. However, the exact interaction between artemisinin and MD-2 is still not fully understood. Here, experimental and computational methods were employed to elucidate the relationship between the artemisinin and its inhibition mechanism. Experimental results showed that artemether exhibit higher anti-inflammatory activity performance than artemisinin and artesunate. Molecular docking results showed that artemisinin, artesunate, and artemether had similar binding poses, and all complexes remained stable throughout the whole molecular dynamics simulations, whereas the binding of artemisinin and its derivatives to MD-2 decreased the TLR4(Toll-Like Receptor 4)/MD-2 stability. Moreover, artemether exhibited lower binding energy as compared to artemisinin and artesunate, which is in good agreement with the experimental results. Leu61, Leu78, and Ile117 are indeed key residues that contribute to the binding free energy. Binding free energy analysis further confirmed that hydrophobic interactions were critical to maintain the binding mode of artemisinin and its derivatives with MD-2.     

Stereolability of dihydroartemisinin, an antimalarial drug: a comprehensive kinetic investigation. Part 2

Artemisinin or qinghaosu has now largely given way to the more potent dihydroartemisinin (DHA, 1) and its derivatives in the treatment of drug-resistant malaria, in combination with other classical antimalarial drugs. DHA is obtained by NaBH(4) reduction of artemisinin and contains a stereochemically labile center at C-10, which provided two lactol hemiacetal interconverting epimers, namely 1α and 1β. In the solid state, the drug consists exclusively of the β-epimer; however, upon dissolution, the two epimers equilibrate, reaching different solvent-dependent ratios with different rates. Such equilibration also occurs in vivo, irrespective of the isomeric purity at which the drug would have been administered. The aim of this study was then to achieve an in-depth understanding of the kinetic features of the α/β equilibration. To this purpose, free energy activation barriers (ΔG(?)) of the interconversion were determined as a function of both general and specific acid and base catalysts, ionic strength, and temperature in different solvents by dynamic HPLC (DHPLC). In hydro-organic media, the dependence of ΔG(?) on temperature led to the evaluation of the related enthalpic and entropic contributions. Theoretical calculations suggested that the rate-determining step of the interconversion is not the ring-opening of the cyclic hemiacetal but the previous reversible deprotonation of the individual epimers (base-catalyzed mechanism). The whole findings may contribute to shed some light on the mechanism of action and/or bioavailability of the drug at the molecular level.     

Pt-Ru/GC电极对甲醇电催化氧化的研究

利用循环伏安法制备了Pt-Ru/GC电极并用于对甲醇的电催化氧化研究,考察了Pt、Ru原子比、沉积电位下限和沉积量对电极催化性能的影响,研究了电极催化性能的稳定性。结果表明Ru的加入对电极催化性能具有明显的改善作用,对甲醇的氧化电位范围明显变宽,氧化电流明显增大,电极的稳定性明显高于Pt/GC电极。在Pt、Ru原子比为1:1、沉积电位下限为-0.2V、沉积量为40r的条件下,Pt-Ru/GC电极对甲醇电催化氧化的性能最好。