三维石墨烯/多壁碳纳米管修饰电极的制备及对甲巯咪唑的测定
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摘要
通过滴涂法制备了3DGR/MWCNTs/GCE修饰电极,用电化学交流阻抗(EIS)对其进行表征。以循环伏安法(CV)、恒电位库伦分析法(CPC)、线性扫描伏安法(LSV)和计时电量法(CC)研究了甲巯咪唑的电化学行为。结果表明:在pH 2.6的B-R缓冲溶液中,甲巯咪唑在3DGR/MWCNTs/GCE修饰电极上是受扩散控制的双电子和双质子转移的氧化还原过程,扩散系数D=3.461 4×10-6 cm2/s、电极有效面积A=0.061 8cm2.在1.0×10-6～1.0×10-4mol/L浓度范围内,还原峰电流与甲巯咪唑的浓度呈良好线性关系,方法检出限为5.94×10-7 mol/L.
The 3DGR/MWCNTs/GCE electrode was prepared by a drop-coating method,and was characterized by electrochemical impedance spectroscopy(EIS).The electrochemical behavior of methimazole was studied by cyclic voltammetry(CV),constant potential coulometry(CPC),linear sweep voltammetry(LSV)and chronocoulometry(CC).The experimental results showed that the reaction of methimazole at3DGR/MWCNTs/GCE was redox with two electrodes and two protons transfer,and controlled by diffusion in the B-R buffer solution at pH 2.6.The diffusion coefficient(D)was 3.461 4×10-6 cm2/s,the effective area of electrode(A)was 0.061 8cm2.The methimazole content and reduction peak current showed a good linear relationship in the range of 1.0×10-6～1.0×10-4 mol/L,and the detection limit was5.94×10-7 mol/L.
The 3DGR/MWCNTs/GCE electrode was prepared by a drop-coating method,and was characterized by electrochemical impedance spectroscopy(EIS).The electrochemical behavior of methimazole was studied by cyclic voltammetry(CV),constant potential coulometry(CPC),linear sweep voltammetry(LSV)and chronocoulometry(CC).The experimental results showed that the reaction of methimazole at3DGR/MWCNTs/GCE was redox with two electrodes and two protons transfer,and controlled by diffusion in the B-R buffer solution at pH 2.6.The diffusion coefficient(D)was 3.461 4×10-6 cm2/s,the effective area of electrode(A)was 0.061 8cm2.The methimazole content and reduction peak current showed a good linear relationship in the range of 1.0×10-6～1.0×10-4 mol/L,and the detection limit was5.94×10-7 mol/L.
引文
[1]左云艳.观察甲巯咪唑对甲状腺吸碘率的影响[J].世界最新医学信息文摘,2017,17:89-89.DOI:10.19613/j.cnki.1671-3141.2017.62.071.Zuo Y Y.Observation of the Effect of Methimazole on Iodine Uptake Rate of Thyroid Gland[J].World Latest Med Info,2017,17:89-89.DOI:10.19613/j.cnki.1671-3141.2017.62.071.
[2] Nakamura H,Noh J Y,Itoh K,et al.Comparison of Methimazole and Propylthiouracil in Patients with Hyperthyroidism Caused by Graves’Disease[J].J Clin Endocr Metab,2007,92:2157-2162.DOI:10.1210/jc.2006-2135.
[3] Genter M B.Evaluation of Olfactory and Auditory System Effects of the Antihyperthyroid Drug Carbimazole in the LongEvans Rat[J].J Biochem Mol Toxic,1998,12:305-314.DOI:10.1002/(SICI)1099-0461(1998)12:5<305::AID-JBT7>3.0.CO;2-P.
[4] Ku s'mierek K,Bald E.Determination of Methimazole in Urine by Liquid Chromatography[J].Talanta,2007,71:2121-2125.DOI:10.1016/j.talanta.2006.08.019.
[5] Hollosi L,Kettrup A,Schramm K W.MMSPE-RP-HPLC Method for the Simultaneous Determination of Methimazole and Selected Metabolites in Fish Homogenates[J].J Pharmaceuti Biomed,2004,36:921-924.DOI:1 10.1016/j.jpba.2004.08.028.
[6] De W K,Be Brabander H F,Impens S,et al.Determination of Mercaptobenzimidazol and other Thyreostat Residues in Thyroid Tissue and Meat using High-performance Liquid Chromatography-mass Spectrometry[J].J Chromatogr A,2001,912:311-317.DOI:10.1016/S0021-9673(01)00563-5.
[7] Batjoens P,De Brabander H F,De W K.Rapid and High-performance Analysis of Thyreostatic Drug Residues in Urine Using Gas Chromatography-mass Spectrometry[J].J Chromatogr A,1996,750:127-132.DOI:10.1016/0021-9673(96)00406-2.
[8] Zakrzewski R.Determination of Methimazole in Urine with the Iodine-azide Detection System following Its Separation by Reversed-phase High-performance Liquid Chromatography[J].J Chromatogr B,2008,869:67-74.DOI:10.1016/j.jchromb.2008.05.021.
[9] Economou A,Tzanavaras P D,Notou M,et al.Determination of Methimazole and Carbimazole by Flow-injection with Chemiluminescence Detection Based on the Inhibition of The Cu(Ⅱ)-catalysed Luminol-hydrogen Peroxide Reaction[J].Anal Chim Acta,2004,505:129-133.DOI:10.1016/S0003-2670(03)00176-4.
[10] Liu X,Yuan H,Pang D,et al.Resonance Light Scattering Spectroscopy Study of Interaction between Gold Colloid and Thiamazole and Its Analytical Application[J].Spectrochim Acta A,2004,60:385-389.DOI:10.1016/S1386-1425(03)00235-X.
[11] Dong F,Hu K,Han H,et al.A Novel Method for Methimazole Determination Using CdSe Quantum Dots as Fluorescence Probes[J].Microchim Acta,2009,165:195-201.DOI:10.1007/s00604-008-0120-4.
[12] Wang A,Zhang L,Zhang S,et al.Determination of Thiols Following Their Separation by CZE with Amperometric Detection at a Carbon Electrode[J].J Pharmaceut Biomed,2000,23:429-436.DOI:10.1016/S0731-7085(00)00326-5.
[13] Shahrokhian S,Ghalkhani M.Voltammetric Determination of Methimazole Using a Carbon Paste Electrode Modified with a Schiff Base Complex of Cobalt[J].Electroanal,2010,20:1061-1066.DOI:10.1002/elan.200704149.
[14] Molero L,Faundez M,Valle M A D,et al.Electrochemistry of Methimazole on Fluorine-doped Tin Oxide Electrodes and Its Square-wave Voltammetric Determination in Pharmaceutical Formulations[J].Electrochim Acta,2013,88:871-876.DOI:10.1016/j.electacta.2012.10.142.
[15] Li Y,Wang X,Yang Q,et al.Ultra-fine CuO Nanoparticles Embedded in Three-dimensional Graphene Network Nanostructure for High-performance Flexible Supercapacitors[J].Electrochim Acta,2017,243:63-70.DOI:10.1016/j.electacta.2017.02.167.
[16] Wu Y,Zhou A,Yang H,et al.3DGraphene-Nitrogen Doped Carbon Nanotubes Network Modified Electrode as Sensing Materials for the Determination of Urapidil[J].Materials,2018,11:322-12.DOI:10.3390/ma11020322.
[17]岳伟超.石墨烯、碳纳米管及纳米金复合材料修饰电极的制备及其应用研究[D].南宁:广西大学,2014.Yue W C.Preparation and Application of Graphene,Carbon Nanotubes and Nano-Gold Composite Modified Electrodes[D].Nanning:Guangxi University,2014:26-26.
[18] Laviron E.General Expression of the Linear Potential Sweep Voltammogram in the Case of Diffusionless Electrochemical Systems[J].J Electroanal Chem,1979,101:19-28.DOI:10.1016/S0022-0728(79)80075-3.
[19] Patil R H,Hegde R N,Nandibewoor S T.Electro-oxidation and Determination of Antihistamine Drug,Cetirizine Dihydrochloride at Glassy Carbon Electrode Modified with Multi-walled Carbon Nanotubes[J].Colloid Surface B,2011,83:133-138.DOI:10.1016/j.colsurfb.2010.11.008.
[20] Dang X,Hu C,Shen D,et al.A Novel Electrochemical Method for Determination of Cis-jasmone Based on Enhancement Effect of Cetyltrimethylammonium Bromide[J].J Electroanal Chem,2011,657:39-45.DOI:10.1016/j.jelechem.2011.03.006.
[21] Dorraji P S,Jalali F.Sensitive Amperometric Determination of Methimazole Based on the Electrocatalytic Effect of Rutin/Multi-walled Carbon Nanotube Film[J].Bioelectrochem,2015,101:66-74.DOI:10.1016/j.bioelechem.2014.07.009.
[2] Nakamura H,Noh J Y,Itoh K,et al.Comparison of Methimazole and Propylthiouracil in Patients with Hyperthyroidism Caused by Graves’Disease[J].J Clin Endocr Metab,2007,92:2157-2162.DOI:10.1210/jc.2006-2135.
[3] Genter M B.Evaluation of Olfactory and Auditory System Effects of the Antihyperthyroid Drug Carbimazole in the LongEvans Rat[J].J Biochem Mol Toxic,1998,12:305-314.DOI:10.1002/(SICI)1099-0461(1998)12:5<305::AID-JBT7>3.0.CO;2-P.
[4] Ku s'mierek K,Bald E.Determination of Methimazole in Urine by Liquid Chromatography[J].Talanta,2007,71:2121-2125.DOI:10.1016/j.talanta.2006.08.019.
[5] Hollosi L,Kettrup A,Schramm K W.MMSPE-RP-HPLC Method for the Simultaneous Determination of Methimazole and Selected Metabolites in Fish Homogenates[J].J Pharmaceuti Biomed,2004,36:921-924.DOI:1 10.1016/j.jpba.2004.08.028.
[6] De W K,Be Brabander H F,Impens S,et al.Determination of Mercaptobenzimidazol and other Thyreostat Residues in Thyroid Tissue and Meat using High-performance Liquid Chromatography-mass Spectrometry[J].J Chromatogr A,2001,912:311-317.DOI:10.1016/S0021-9673(01)00563-5.
[7] Batjoens P,De Brabander H F,De W K.Rapid and High-performance Analysis of Thyreostatic Drug Residues in Urine Using Gas Chromatography-mass Spectrometry[J].J Chromatogr A,1996,750:127-132.DOI:10.1016/0021-9673(96)00406-2.
[8] Zakrzewski R.Determination of Methimazole in Urine with the Iodine-azide Detection System following Its Separation by Reversed-phase High-performance Liquid Chromatography[J].J Chromatogr B,2008,869:67-74.DOI:10.1016/j.jchromb.2008.05.021.
[9] Economou A,Tzanavaras P D,Notou M,et al.Determination of Methimazole and Carbimazole by Flow-injection with Chemiluminescence Detection Based on the Inhibition of The Cu(Ⅱ)-catalysed Luminol-hydrogen Peroxide Reaction[J].Anal Chim Acta,2004,505:129-133.DOI:10.1016/S0003-2670(03)00176-4.
[10] Liu X,Yuan H,Pang D,et al.Resonance Light Scattering Spectroscopy Study of Interaction between Gold Colloid and Thiamazole and Its Analytical Application[J].Spectrochim Acta A,2004,60:385-389.DOI:10.1016/S1386-1425(03)00235-X.
[11] Dong F,Hu K,Han H,et al.A Novel Method for Methimazole Determination Using CdSe Quantum Dots as Fluorescence Probes[J].Microchim Acta,2009,165:195-201.DOI:10.1007/s00604-008-0120-4.
[12] Wang A,Zhang L,Zhang S,et al.Determination of Thiols Following Their Separation by CZE with Amperometric Detection at a Carbon Electrode[J].J Pharmaceut Biomed,2000,23:429-436.DOI:10.1016/S0731-7085(00)00326-5.
[13] Shahrokhian S,Ghalkhani M.Voltammetric Determination of Methimazole Using a Carbon Paste Electrode Modified with a Schiff Base Complex of Cobalt[J].Electroanal,2010,20:1061-1066.DOI:10.1002/elan.200704149.
[14] Molero L,Faundez M,Valle M A D,et al.Electrochemistry of Methimazole on Fluorine-doped Tin Oxide Electrodes and Its Square-wave Voltammetric Determination in Pharmaceutical Formulations[J].Electrochim Acta,2013,88:871-876.DOI:10.1016/j.electacta.2012.10.142.
[15] Li Y,Wang X,Yang Q,et al.Ultra-fine CuO Nanoparticles Embedded in Three-dimensional Graphene Network Nanostructure for High-performance Flexible Supercapacitors[J].Electrochim Acta,2017,243:63-70.DOI:10.1016/j.electacta.2017.02.167.
[16] Wu Y,Zhou A,Yang H,et al.3DGraphene-Nitrogen Doped Carbon Nanotubes Network Modified Electrode as Sensing Materials for the Determination of Urapidil[J].Materials,2018,11:322-12.DOI:10.3390/ma11020322.
[17]岳伟超.石墨烯、碳纳米管及纳米金复合材料修饰电极的制备及其应用研究[D].南宁:广西大学,2014.Yue W C.Preparation and Application of Graphene,Carbon Nanotubes and Nano-Gold Composite Modified Electrodes[D].Nanning:Guangxi University,2014:26-26.
[18] Laviron E.General Expression of the Linear Potential Sweep Voltammogram in the Case of Diffusionless Electrochemical Systems[J].J Electroanal Chem,1979,101:19-28.DOI:10.1016/S0022-0728(79)80075-3.
[19] Patil R H,Hegde R N,Nandibewoor S T.Electro-oxidation and Determination of Antihistamine Drug,Cetirizine Dihydrochloride at Glassy Carbon Electrode Modified with Multi-walled Carbon Nanotubes[J].Colloid Surface B,2011,83:133-138.DOI:10.1016/j.colsurfb.2010.11.008.
[20] Dang X,Hu C,Shen D,et al.A Novel Electrochemical Method for Determination of Cis-jasmone Based on Enhancement Effect of Cetyltrimethylammonium Bromide[J].J Electroanal Chem,2011,657:39-45.DOI:10.1016/j.jelechem.2011.03.006.
[21] Dorraji P S,Jalali F.Sensitive Amperometric Determination of Methimazole Based on the Electrocatalytic Effect of Rutin/Multi-walled Carbon Nanotube Film[J].Bioelectrochem,2015,101:66-74.DOI:10.1016/j.bioelechem.2014.07.009.