2-(5-氟尿嘧啶-1-乙酰基)氨基-1,5-戊二酸二甲酯手性异构体与双链/G-四链体DNA相互作用的电化学研究

以自组装法制得的双链DNA(ds-DNA)和G-四链体DNA(G4-DNA)修饰的金电极为工作电极, 以 为电活性指示剂, 采用循环伏安法和微分脉冲伏安法研究了R和S型2-(5-氟尿嘧啶-1-乙酰基)氨基-1,5-戊二酸二甲酯(简称为(R)-5FUGlu和(S)-5FUGlu)与ds-DNA和G4-DNA相互作用. 实验结果表明: (1)与5-氟尿嘧啶(5-FU)相反, (R)-5FUGlu或(S)-5FUGlu导致 在Au/ds-DNA和Au/G4-DNA修饰电极上的峰电位呈现负移行为|(2)随着5-FU, (R)-或(S)-5FUGlu浓度的增加, 在上述修饰电极上的峰电流均呈现下降现象, 且峰电流的下降值△I_p的倒数与药物浓度的倒数呈现良好的线性关系|(3)运用Langmuir公式计算获得5-FU, (S)-5FUGlu和(R)-5FUGlu与ds-DNA的结合常数分别为6.16×10³, 0.42×10³和0.58×10³ L•mol^－1, 而与G4-DNA 的结合常数分别为0.78×10³, 2.60×10³和5.29×10³ L•mol^－1|(4) (R)-5FUGlu和(S)-5FUGlu在浓度为10^－4, 10^－6, 10^－8 mol•L^－1时对HL-60肿瘤细胞生长的抑制率分别为55.8和2.8, 12.8和1.5以及5.9和0.6, 这与(R)-5FUGlu比(S)-5FUGlu分子具有更强的靶向结合G4-DNA能力相吻合.     

石墨烯/铁氰化钴复合膜修饰玻碳电极同时测定对苯二酚、邻苯二酚和间苯二酚

采用滴涂法和电沉积法制备了石墨烯/铁氰化钴复合膜修饰玻碳电极. 用扫描电镜对该纳米复合膜进行了表征.用循环伏安法研究了对苯二酚(HQ)、邻苯二酚(CT)和间苯二酚(RS)在修饰电极上的电化学行为. 实验结果表明, 相对于裸玻碳电极和石墨烯修饰电极, HQ, CT 和RS 在石墨烯/铁氰化钴修饰电极上的氧化峰电流显著提高. 利用差分脉冲伏安法测定, HQ, CT 和RS 分别在1.0×10^－6～1.5×10^－4 mol/L, 1.0×10^－6～2.0×10^－4 mol/L 和3.5×10^－6～2.5×10^－4 mol/L浓度范围内与氧化峰电流呈良好的线性关系, 相关系数分别为0.991, 0.993 和0.992. 信噪比为3 时, HQ, CT 和RS 检出限分别为2.0×10^－7, 2.1×10^－7 和3.5×10^－7 mol/L. 将该方法用于水样分析, 回收率为95.6%～106.1%.     

钯/聚苯胺纳米多层膜的制备及对抗坏血酸和多巴胺的催化氧化

采用脉冲电位法(PPSM)结合聚苯胺(PANI)的层层自组装制备了Pd/PANI交替沉积纳米多层膜, 并用于抗坏血酸(AA)和多巴胺(DA)的检测. 实验发现, 多层膜结构形貌及催化性能受前躯体K₂PdCl₆浓度、 脉冲条件及膜厚度等影响. 当K₂PdCl₆浓度为2×10^-3 mol/L, 阴极脉冲电位为-0.3 V, 阶跃次数为17时, 5层Pd/PANI修饰玻碳电极对AA和DA的催化性能最佳; 在0.1 mol/L磷酸盐缓冲液中, AA和DA的氧化峰明显分离[ΔE_p(AA, DA)=160 mV], 其峰电流与浓度分别在5×10^-5～4×10^-4和4×10^-5～1×10^-4 mol/L范围内呈较好线性关系, 实现了对AA和DA的同时测定. 该修饰电极具有良好的抗干扰性和稳定性.     

聚茜素红功能化碳纳米管修饰电极对多巴胺和抗坏血酸的电化学研究

采用电聚合方法将茜素红非共价修饰到碳纳米管上,制备了聚茜素红/碳纳米管修饰电极.以多巴胺(DA)和抗坏血酸(AA)为模型化合物,研究该修饰电极的电催化作用.结果表明:电聚合法使茜素红牢固地修饰到碳纳米管上,能显著提高电极的灵敏度和分子识别性能.DA和AA的氧化峰位分离达240 mV.在AA的存在下,DA的差分脉冲伏安法峰电流在1×10-7～1×10-5 mol/L范围内呈良好的线性关系,检测下限达1×10-7 mol/L.     

聚茜素红膜修饰电极控制电位扫描法分别测定多巴胺和抗坏血酸

研究了聚茜素红膜修饰电极(PARE)的制备及其对多巴胺(DA)和抗坏血酸(AA)的电催化性能,结果表明,在PARE上DA和AA具有不同的循环伏安行为,前者表现为一个准可逆过程,后者则为不可逆过程,并且二者的氧化峰电位分开近200mV.因此可通过控制不同的电位范围进行分步扫描,实现了对同一体系中DA和AA的分别测定,DA的还原峰电流和AA的氧化峰电流分别在8.0×10^-6～4.0×10^-3mol/L和4.0×10^-5～2.0×10^-2mol/L范围内与各自的浓度呈线性关系;检测限分别为8.0×10^-7mol/L和1.0×10^-5mol/L.同时与导数伏安法一步测定进行比较,结果令人满意.     

芦丁修饰电极研究多巴胺的电化学响应

通过循环伏安法(CV)制备了芦丁修饰电极,研究多巴胺(DA)在修饰电极上的电化学行为.结果表明,芦丁修饰膜对DA的氧化有明显的催化作用,并且可以消除抗坏血酸(AA)对DA测定的干扰.DA的浓度在1.0×10-7～9.5×10-6 mol/L范围内与其氧化峰电流呈线性关系,相关系数为0.9996,检出限为1.0×10-8 mol/L.将该修饰电极用于注射液样品中DA的测定,结果表明该修饰电极可用于实际样品分析.     

聚2,6-吡啶二甲酸/多壁碳纳米管修饰电极的电催化性能

研制了一种聚2,6-吡啶二甲酸/多壁碳纳米管(PPDA/MCNT)复合修饰电极。该电极以中性KC l溶液为底液,在玻碳电极上以多壁碳纳米管(MCNT)作掺杂剂,通过电聚合2,6-吡啶二甲酸(PDA)而制得。该修饰电极对多巴胺(DA)有很强的电催化氧化作用。在磷酸盐缓冲液(pH 7.2)中,与碳纳米管修饰电极相比,DA的氧化峰电位降低约30 mV。利用线性扫描伏安法(LSV)测定,DA在9.0×10-8~8.0×10-6mol/L浓度范围内,其峰高与浓度呈线性关系;检出限为5.0×10-8mol/L,并可避免AA、UA对测定产生干扰。     

应用单壁碳纳米管修饰纳米碳纤维电极同时测定多巴胺和抗坏血酸

采用滴涂法制备了单壁碳纳米管修饰的纳米碳纤维电极,研究了多巴胺(DA)、抗坏血酸(AA)及其混合溶液在修饰前后电极上的电化学行为。在20 mmol/L Tris-HCl(pH 7.4)缓冲溶液中,修饰电极对DA和AA具有很好的电催化作用。采用差示脉冲伏安法对DA与AA混合溶液氧化峰电流与浓度的关系进行定量分析,DA和AA的氧化峰电流在1.0×10-7~5.0×10-5mol/L和1.0×10-5~1.0×10-3mol/L范围内与浓度呈线性关系,其线性回归方程及相关系数分别为Ip=0.0012c+4×10-9,r=0.9907;Ip=10-5c+7×10-10,r=0.9974,两种物质的检测限分别达到8.0×10-9mol/L和2×10-6mol/L。     

修饰铂电极上Cd(Ⅱ)的示波双电位滴定法

制备了镉修饰铂电极, 用循环伏安法表征了Cd(Ⅱ)在该电极上的吸附特性, 探讨了电极的响应机理. 通过优化试验条件, 建立了一种新的测定Cd(Ⅱ)的示波双电位滴定法. 在1.0 mol/L 的六次甲基四胺溶液中(pH＝6.0), 用制备的修饰铂电极作为双指示电极, 以EDTA 标准溶液滴定Cd(Ⅱ), 利用示波器屏幕上荧光点的显著最大位移指示滴定终点.Cd(Ⅱ)在9.0×10^－4～3.5×10^－3 mol/L 时, 回收率为99.8%～100.3%. 该修饰电极具有良好的稳定性和重现性, 在含有1.0×10^－3 mol/L Cd(Ⅱ)的溶液中, 连续13 次测定, 所得终点电位值均在37 mV左右, 其相对标准偏差(RSD)0.02%. 应用该方法测定含镉样品, RSD 值(n＝7)小于0.81%, 回收率为99.71%～100.09%, 测定结果与指示剂法测定值相符.     

聚苯胺纳米纤维修饰石墨箔电极的制备及电化学性能

以石墨箔(GF)为工作电极, 采用循环伏安法(CV), 通过电化学聚合, 制备了聚苯胺(PANI)纳米纤维修饰GF电极(Nano-PANI/GF). 利用红外光谱(FTIR)研究了Nano-PANI/GF修饰电极上聚合物的组成, 利用扫描电镜(SEM)观测了Nano-PANI/GF修饰电极的表面形貌. 利用循环伏安法研究了Nano-PANI/GF修饰电极在0.1 mol/L磷酸盐缓冲溶液(pH=6.9)中的电化学活性, 发现Nano-PANI/GF修饰电极在中性溶液中有良好的电化学活性. Nano-PANI/GF修饰电极对抗坏血酸(AA)电化学氧化的催化作用结果表明, 在0.2 V(vs. SCE)电位下, 在浓度范围1.7~2.0×10³ μmol/L内, 抗坏血酸的氧化电流与浓度呈良好线性关系, 线性方程式为y=0.00013x+0.0031. 修饰电极对抗坏血酸的最低检测限为1.7 μmol/L(S/N=3).     

Simultaneous Determination of Dopamine and Ascorbic Acid Using the Nano‐Gold Self‐Assembled Glassy Carbon Electrode

Electrochemical behavior of dopamine (DA) was investigated at the gold nanoparticles self‐assembled glassy carbon electrode (GNP/LC/GCE), which was fabricated by self‐assembling gold nanoparticles on the surface of L ‐cysteine (LC) modified glassy carbon electrode (GCE) via successive cyclic voltammetry (CV). A pair of well‐defined redox peaks of DA on the GNP/LC/GCE was obtained at E_pa=0.197 V and E_pc=0.146 V, respectively. And the peak separation between DA and AA is about 0.2 V, which is enough for simultaneous determination of DA and AA. The peak currents of DA and AA were proportional with their concentrations in the range of 6.0×10^?8–8.5×10^?5 mol L^?1 and 1.0×10^?6–2.5×10^?3 mol L^?1, with the detection limit of 2.0×10^?8 mol L^?1 and 3.0×10^?7 mol L^?1 (S/N=3), respectively. The modified electrode exhibits an excellent reproducibility, sensibility and stability for simultaneous determination of DA and AA in human serum with satisfactory result.     

Electrochemistry of Nitrogen‐Doped Carbon Nanotubes (CNx) with Different Nitrogen Content and Its Application in Simultaneous Determination of Dihydroxybenzene Isomers

The bamboo‐shaped nitrogen‐doped carbon nanotubes (CN_x) with different nitrogen content were synthesized using Fe‐containing SBA‐15 molecular sieve as catalyst with thermal decomposition. The CN_x nanotubes prepared were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X‐ray diffraction (XRD) and Raman spectroscopy. The results suggest that there are a larger amount of defective sites on CN_x nanotubes surfaces due to the nitrogen doping and CN_x nanotube with higher nitrogen content possesses lower graphitic ordering in the framework. Furthermore the effects of nitrogen content on the electrochemistry of CN_x modified electrodes were investigated by cyclic voltammetry (CV). CN_x modified electrodes exhibit better electrocatalytic activities to the oxidation of hydroquinone. Moreover CN_x with lower nitrogen content is in favor of the electron transfer between dihydroxybenzene and electrode surface, while CN_x with higher nitrogen content possesses high surface adsorptive ability. CN_x modified electrodes can be applied to determine dihydroxybenzene isomers directly and simultaneously by linear sweep voltammetry technique without previous separation.     

碳纳米管修饰金电极检测特定序列DNA

利用化学偶联法将末端修饰氨基的寡聚核苷酸固定在表面修饰有羧基化碳纳米管(CNTs-COOH)的金电极表面, 制备新型核酸探针, 可以特异性结合目标单链寡聚核苷酸. 以阿霉素作为嵌合指示剂, 利用示差脉冲法测定杂交的结果. 经过实验条件的优化, 测定DNA浓度在1.0×10^－6～1.0×10^－9 mol/L呈良好的线性关系. 检测限为: 2.54×10^－10 mol/L. 碳纳米管特有的纳米结构对检测结果的放大作用, 提高了该传感器的检测限和灵敏度.     

Electrocatalytic Oxidation of Dopamine by Ferrocene in Lipid Film Cast on a Glassy Carbon Electrode

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Electrocatalytic Oxidation and Determination of Dopamine in the Presence of Ascorbic Acid and Uric Acid at a Poly (4‐(2‐Pyridylazo)‐Resorcinol) Modified Glassy Carbon Electrode

A sensitive and selective electrochemical method for the determination of dopamine (DA) was developed using a 4‐(2‐Pyridylazo)‐Resorcinol (PAR) polymer film modified glassy carbon electrode (GCE). The PAR polymer film modified electrode shows excellent electrocatalytic activity toward the oxidation of DA in a phosphate buffer solution (PBS) (pH 4.0). The linear range of 5.0×10^?6–3.0×10^?5 M and detection limit of 2.0×10^?7 M were observed. Simultaneous detection of AA, DA and UA has also been demonstrated on the modified electrode. This work provides a simple and easy approach to selective detection of DA in the presence of AA and UA.     

Chiral Recognition of Penicillamine Enantiomers Based on DNA‐MWNT Complex Modified Electrode

Double‐stranded DNA and multiwalled carbon nanotube (MWNT) complex modified glassy carbon electrodes (DNA‐MWNT‐GCE) were employed to discriminate penicillamine (PA) enantiomers. Cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and ultraviolet‐visible spectroscopy were used to characterize the enantioselective phenomenon. The results indicated that the binding effect between L ‐PA and DNA‐MWNTs was stronger than that of D ‐PA and DNA‐MWNTs. In addition, the influencing factors of the modified electrodes were systematically investigated. The modified electrodes exhibited a linear response towards PA enantiomers from 1.0×10^?1 to 1.0×10^?8 mol L^?1 and detection limits of 3.1×10^?9 and 3.3×10^?8 mol L^?1 for L ‐PA and D ‐PA, respectively.     

Simultaneous Determination of Ascorbic Acid,Dopamine and Uric Acid at Pt Nanoparticles Decorated Multiwall Carbon Nanotubes Modified GCE

A modified electrode was fabricated by electrochemically deposition of Pt nanoparticles on the multiwall carbon nanotube covered glassy carbon electrode (Pt nanoparticles decorated MWCNT/GCE). A higher catalytic activity was obtained to electrocatalytic oxidation of ascorbic acid, dopamine, and uric acid due to the enhanced peak current and well‐defined peak separations compared with both, bare and MWCNT/GCE. The electrode surfaces were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). Individual and simultaneous determination of AA, DA, and UA were studied by differential pulse voltammetry. The detection limits were individually calculated for ascorbic acid, dopamine, and uric acid as being 1.9×10^?5 M, 2.78×10^?8 M, and 3.2×10^?8 M, respectively. In simultaneous determination, LODs were calculated for AA, DA, and UA, as of 2×10^?5 M, 4.83×10^?8 M, and 3.5×10^?7 M, respectively.     

Selective Electrochemical Determination of Dopamine with Molecularly Imprinted Poly(Carbazole‐co‐Aniline) Electrode Decorated with Gold Nanoparticles

Dopamine (DA) is a significant neurotransmitter in the central nervous system, coexisting with uric acid (UA) and ascorbic acid (AA). UA and AA are easily oxidizable compounds having potentials close to that of DA for electrochemical analysis, resulting in overlapping voltammetric response. In this work, a novel molecularly imprinted (MI) electrochemical sensor was proposed for selective determination of DA (in the presence of up to 80‐fold excess of UA and AA), relying on gold nanoparticles (Au_nano)‐decorated glassy carbon (GC) electrode coated with poly(carbazole (Cz)‐co‐aniline (ANI)) copolymer film incorporating DA as template (DA imprinted‐GC/P(Cz‐co‐ANI)‐Au_nano electrode, DA‐MIP‐Au_nano electrode). The DA recognizing sensor electrode showed great electroactivity for analyte oxidation in 0.2 mol L^?1 pH 7 phosphate buffer. Square wave voltammetry (SWV) was performed within 10^?4–10^?5 mol L^?1 of DA, of which the oxidation peak potential was observed at 0.16 V. The limit of detection (LOD) and limit of quantification (LOQ) were 2.0×10^?6 and 6.7×10^?6 mol L^?1, respectively. Binary and ternary synthetic mixtures of DA‐UA, DA‐AA and DA‐UA‐AA yielded excellent recoveries for DA. Additionally, DA was quantitatively recovered from a real sample of bovine serum spiked with DA, and determined in concentrated dopamine injection solution. The developed SWV method was statistically validated against a literature potentiodynamic method using a caffeic acid modified‐GC electrode.     

Electrocatalytic Oxidation of Dopamine and Ascorbic Acid on Carbon Paste Electrode Modified with Nanosized Cobalt Phthalocyanine Particles: Simultaneous Determination in the Presence of CTAB

Metallophthalocyanine (MPc) and its derivatives are well known as electrocatalysts to catalyze oxidation or reduction of some species, such as cysteine, nitric oxide. Their nanosized particles may display the potential optics, electronic, catalytic and structural properties. In this paper, carbon paste electrodes modified with nanosized cobalt phthalocyanine particles (denoted as Nano‐CoPc‐CPE) are fabricated. The electrocatalytic oxidation of dopamine (DA) and ascorbic acid (AA) on the Nano‐CoPc‐CPE was investigated by means of cyclic voltammetry. Nano‐CoPc particles perform good electrocatalytic activity to DA and AA. The anodic peak potentials of DA and AA were separated with good sensitivity in the presence of cetyltrimethylammonium bromide (CTAB). The DA and AA can be simultaneously determined by using differential pulse voltammetry. On optimal conditions, the good linear response to DA and AA was observed in the range of 3.0×10^?6–1.0×10^?4 M and 5.0×10^?6–3.0×10^?4 M with the correlation coefficient of 0.9983 and 0.9978, respectively. Moreover, 100‐fold AA did not interfere in the determination of DA. This method has been used to simultaneously determine DA and AA concentration in mixed drug samples with satisfactory results.     

Selective detection of dopamine with poly(diphenylamine sulfonic acid) modified electrode in the presence of ascorbic acid

A glassy carbon electrode was modified with electropolymerized film of diphenylamine sulfonic acid (DPASA). Electropolymerization was performed by cyclic voltammetry in 0.1 M KCl solution. The modified electrode showed an excellent electrocatalytic effect towards oxidation of dopamine (DA) and ascorbic acid (AA). Electrostatic interaction between the negatively charged poly(DPASA) film and either cationic DA species or anionic AA species favorably contributed to the redox response of DA and AA. Anodic peaks of DA and AA in their mixture were well separated by ca 168 and −11.8 mV. The proposed modified electrode was utilized for selective determination of dopamine in the concentration range of 5.0 × 10^t7–2.0 × 10⁻⁵ M in the presence of high concentration of ascorbic acid. Detection limit was 6.5 × 10⁻⁹ M.