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。     

不同电极上血红素对青蒿素的电催化还原

 在含20%乙醇的Britton-Robinson缓冲液介质(pH=7.2)中,采用循环伏安法在玻碳电极和银电极上比较了血红素对青蒿素还原的催化作用. 由于血红素和青蒿素加合物的形成及血红素中Fe2+的催化作用,青蒿素在玻碳电极和银电极上的还原过电位分别降低了0.32和0.09 V,还原活化能分别降低了62.1和17.6 kJ/mol. 还比较了血红素和配合物EDTA-Fe3+对青蒿素的催化还原效果,结果表明,EDTA-Fe2+的催化作用远低于血红素. 进一步证实了血红素在青蒿素的药理研究中起着关键作用.     

谷胱甘肽、表面活性剂共存体系对青蒿素过氧键稳定性的影响

青蒿素的过氧桥键是其抗疟作用的关键部位。采用循环伏安法研究了谷胱甘肽、表面活性剂共存体系对青蒿素过氧键稳定性的影响。实验表明,当青蒿素浓度为1.0mmol/L,谷胱甘肽浓度≥2.0×10-5mol/L时,加入阳离子表面活性剂(1.0×10-5mol/L,DBDAB),在体系中形成了谷胱甘肽-青蒿素-DBDAB三元加合物,该加合物在-0.88V电位下还原,其还原峰电位比游离青蒿素的还原峰电位负移了240mV,其还原反应活化能升高了46·3kJ/moL,使青蒿素的过氧键更趋稳定;而阴离子表面活性剂对体系没有影响。进一步探讨了该三元加合物形成的电极机理。     

肉豆蔻酸-双层类脂膜修饰玻碳电极研究氯化血红素的电化学行为

报道了氯化血红素在肉豆蔻酸-双层类脂膜修饰玻碳电极上的电化学行为。在0.1~-0.7 V(vs.Ag/AgCl)电位范围内,扫描速率为40 mV/s时,氯化血红素在-0.4 V处产生很灵敏的还原峰电流。于pH7.50.01 mol/L KH2PO4-Na2HPO4底液中,该氧化峰电流与氯化血红素浓度在7.32×10-9~1.57×10-6mol/L范围内呈良好线性关系。该电极可作为检测氯化血红素的新型的高灵敏度电化学生物传感器。     

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。     

多孔氧化汞阴极动力学的研究

本文推导出微溶性活性物质多孔电极动力学方程式.将对多孔氧化汞电极进行慢速(5mV/s)线性电位扫描阴极还原的结果与上述方程式加以比较,我们认为30%KOH溶液的多孔红色氧化汞电极的阴极还原是由溶解在碱溶液中的Hg(Ⅱ)_ap在电极中的电子导电基体表面上进行的,但将红色氧化汞换为黄色氧化汞、掺银的氧化汞或掺铊的氧化汞,则除了按上述机理进行外,在过电位大于约0.1V时,有可能按固态阴极还原机理进行.     

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.OV(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E_(1/2)=0.012V,电子转移系数α=0.66,表观标准电极反应速率常数k_s~’=6.34×10~(-6)cm/s,扩散系数D=4.3×10~(-6)cm~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.     

纳米银/石墨烯修饰电极测定青蒿素

本文建立一种新型的青蒿素传感器。首先,在玻碳电极上滴涂氧化石墨,通过电化学方法将氧化石墨还原为石墨烯,然后,在石墨烯上沉积纳米银得到石墨烯/纳米银修饰电极,它作为检测青蒿素的电化学传感器。用此电极对青蒿素进行测定,并通过循环伏安法、差分脉冲伏安法、交流阻抗法等研究其电化学行为。该修饰电极在测定青蒿素溶液时,表现出较正的还原电位和较大的峰电流等优势;对其实验条件如电解质溶液的p H、应用电势等进行了探查,该电化学传感器在青蒿素溶液浓度范围为1.0×10-8~3.0×10-5mol/L时与其还原峰电流呈现良好的线性关系,最低检出限为1.2×10-9mol/L(S/N=3)。此外,对该传感器的稳定性和重现性等也进行了研究,获得令人满意的结果。     

氯化血红素在纳米氧化锌碳糊修饰电极上的电化学行为

以H2C2O4·2H2O和Zn(Ac)2·2H2O为前驱体制备纳米ZnO粉体,用透射电子显微镜、X射线衍射光谱表征了其形貌及晶体结构,并将其用于制备纳米ZnO-碳糊电极,采用循环伏安法和微分脉冲伏安法研究了氯化血红素在电极上的电化学行为。 与商品ZnO颗粒-碳糊电极和裸碳糊电极相比,氯化血红素在纳米ZnO-碳糊电极上的还原峰峰电位正移,还原峰峰电流明显增加,表现出明显电催化性能。 实验表明,在pH=9.18磷酸盐缓冲液中,-0.30 V富集30 s后,氯化血红素在-0.440 V处有1个灵敏的还原峰,可用于氯化血红素的电化学分析。 在优化条件下,该还原峰峰电流与氯化血红素浓度在3.1×10-9~3.1×10-7 mol/L内有线性关系,检出限为1.53×10-9 mol/L(S/N=3)。 将该修饰电极用于红桃K生血剂中氯化血红素测定,结果满意。     

氯化血红素在纳米氧化锌-碳糊电极上的电化学行为

以H2C2O4·2H2O和Zn(Ac)2·2H2O为前驱体制备纳米ZnO粉体,用透射电子显微镜、X射线衍射光谱表征了其形貌及晶体结构,并将其用于制备纳米ZnO-碳糊电极,采用循环伏安法和微分脉冲伏安法研究了氯化血红素在电极上的电化学行为。与商品ZnO颗粒-碳糊电极和裸碳糊电极相比,氯化血红素在纳米ZnO-碳糊电极上的还原峰峰电位正移,还原峰峰电流明显增加,表现出明显电催化性能。实验表明,在pH=9.18磷酸盐缓冲液中,-0.30V富集30s后,氯化血红素在-0.440V处有1个灵敏的还原峰,可用于氯化血红素的电化学分析。在优化条件下,该还原峰峰电流与氯化血红素浓度在3.1×10-9～3.1×10-7mol/L内有线性关系,检出限为1.53×10-9mol/L(S/N=3)。将该修饰电极用于红桃K生血剂中氯化血红素测定,结果满意。     

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.     

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.     

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.     

血红蛋白在磷脂-月桂酸修饰的玻碳电极上的电化学行为及其分析应用

报道了血红蛋白（Hb）在磷脂-月桂酸修饰的玻碳电极上的电化学行为,在+0. 8～-0.7V (vs. Ag/AgCl)电位范围内,于pH6.0的0.01mol/L的KH_2PO_4- Na_2HPO_4底液中,血红蛋白产生不可逆的还原电流峰。还原峰电流与血红蛋白浓 度在1.25 * 10~(-8)～4.31 * 10~(-7) mol/L范围内呈良好线性关系。该电极可作 为检测血红蛋白的新型的高灵敏度电化学生物传感器。     

基于溶胶-凝胶技术的聚烯丙胺基二茂铁化学修饰电极的组装及其对抗坏血酸的电催化氧化

将聚烯丙胺基二茂铁与聚苯乙烯磺酸盐生成的离子配合物用乙醇溶解后掺杂到溶胶-凝胶中,将此溶液滴涂在玻碳电极表面,制成化学修饰电极.详细地研究了该修饰电极的电化学性能及其稳定性.实验发现,在0.1mol/L磷酸盐缓冲液(pH=2.5)中,该修饰电极对抗坏血酸的电化学氧化具有很好的催化活性和稳定性.     

Electropreparation of Poly(benzophenone‐4) Film Modified Electrode and Its Electrocatalytic Behavior Towards Dopamine,Ascorbic Acid and Nitrite

The oxidation of benzophenone‐4 (2‐hydroxy‐4‐methoxybenzophenone‐5‐sulfonic acid) at glassy carbon electrode gives rise to stable redox active electropolymerized film during repetitive potential cycling between 0 to 1.3 V (Ag/AgCl). Cyclic voltammogram of poly(benzophenone‐4) film shows a redox couple with well‐defined peaks. The redox response of the modified electrode was found to be depending on the pH of the contacting solution. The peak potentials were shifted to a less positive region with increasing pH and the dependence of the peak potential was found to be 51 mV/pH. The electrocatalytic behavior of poly(benzophenone‐4) film modified electrode towards oxidation of dopamine, ascorbic acid and reduction of nitrite was investigated. The oxidation of dopamine and ascorbic acid occurred at less positive potential on poly(benzophenone‐4) film compared to bare glassy carbon electrode. For dopamine, the overpotential was reduced about 180 mV. Feasibility of utilizing poly(benzophenone‐4) film coated electrode in analytical estimation of dopamine, ascorbic acid and nitrite was also demonstrated.     

Electrochemical Detection of Artemisinin Using Cobalt Sulphide/Reduced Graphene Oxide Nanocomposite

Solvothermally synthesized cobalt sulphide/reduced graphene oxide (CoS/rGO) was used to fabricate an electrochemical sensor for detection of artemisinin. Microscopic techniques were used to characterize CoS/rGO nanocomposite. The electrochemical sensor was fabricated by modifying the surface of glassy carbon electrode with CoS/rGO nanocomposite. [Fe(CN)6]^3−/4− was used as a mediator to aid oxidation of artemisinin. Differential pulse voltammetric technique was used for the detection of artemisinin. A linear range of 30–100 μM was used. Experimentally, a detection limit of 0.5 μM was obtained. Therefore, the developed sensor can be used for quality control of artemisinin.     

四种药物中席夫碱基团在玻碳电极上的电化学行为

选择呋喃妥因、盐酸二甲双胍、西咪替丁和醋甲唑胺4种含有席夫碱基团的常见药物,运用电化学循环伏安法对其中的-C=N-基团在玻碳电极上的电化学氧化还原行为进行了研究。呋喃妥因、盐酸二甲双胍和西咪替丁中的席夫碱基团(-CH=N-)在玻碳电极上能够被还原,而且是一个电化学的不可逆过程,其还原电位分别为-0.864V,-1.36...