石墨烯/聚苯胺复合膜修饰玻碳电极测定多巴胺
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摘要
采用原位聚合法制备石墨烯/聚苯胺复合物,利用X射线衍射技术和红外光谱进行表征,通过滴涂法制备修饰电极,对多巴胺进行电化学测定。分别对支持电解质、pH值和扫描速率等实验条件进行了优化,建立了测定多巴胺的新方法。实验结果表明,经石墨烯/聚苯胺修饰后的玻碳电极对多巴胺具有很好的催化氧化作用。在0.1mol/L磷酸盐缓冲溶液中(pH值为4.0),多巴胺的线性响应范围为8.0×10-7~5.0×10-3 mol/L,相关系数为0.994,检出限为9.8×10-8 mol/L。该法用于实际样品中多巴胺的测定,回收率为97.1%~103.4%。
The graphene/polyaniline composite is synthesized by using an in situ polymerization procedure,and is characterized by XRD and FTIR.The composite is used to modify bare glass carbon electrode by drop-coating method,then dopamine(DA)is determined utilizing the composite film modified electrode via cyclic voltammetry.The experimental conditions,including the amount of supported electrolyte,pH value and scan rate,are optimized,and a new determination method of DA is established.The results show that the composite film modified electrode performs excellent electrocatalysis in redox behaviors of DA.In0.1mol/L phosphate buffer solution(pH 4.0),the anodic peak current of DA is linear with its concentration in the range of8.0×10-7~5.0×10-3 mol/L with the correlation coefficient of 0.994,and the limit of detection is 9.8×10-8 mol/L.The proposed method is applied to determine DA in hydrochloride injection solution with recoveries of 97.1%~103.4%.
The graphene/polyaniline composite is synthesized by using an in situ polymerization procedure,and is characterized by XRD and FTIR.The composite is used to modify bare glass carbon electrode by drop-coating method,then dopamine(DA)is determined utilizing the composite film modified electrode via cyclic voltammetry.The experimental conditions,including the amount of supported electrolyte,pH value and scan rate,are optimized,and a new determination method of DA is established.The results show that the composite film modified electrode performs excellent electrocatalysis in redox behaviors of DA.In0.1mol/L phosphate buffer solution(pH 4.0),the anodic peak current of DA is linear with its concentration in the range of8.0×10-7~5.0×10-3 mol/L with the correlation coefficient of 0.994,and the limit of detection is 9.8×10-8 mol/L.The proposed method is applied to determine DA in hydrochloride injection solution with recoveries of 97.1%~103.4%.
引文
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[2]王光,刘红缨,朱英,等.氧化石墨掺杂的电化学活性自支撑聚苯胺膜[J].高等学校化学学报,2011,32(2):366-371.WANG Guang,LIU Hongying,ZHU Ying,et al.High electrochemical activities of polyaniline doped with graphene oxide free-standing film[J].Chem J Chinese Universities,2011,32(2):366-371.
[3]李英,赵地顺.导电高分子材料[J].河北科技大学学报,2000,21(2):9-12.LI Ying,ZHAO Dishun.Conductive polymer materials[J].Journal of Hebei University of Science and Technology,2000,21(2):9-12.
[4]张红梅.石墨烯双势垒结构中的输运特性[J].河北科技大学学报,2011,32(6):536-540.ZHANG Hongmei.Transport properties of double-barrier structures in graphene[J].Journal of Hebei University of Science and Technology,2011,32(6):536-540.
[5]LI J,LIU C Y,CHENG C.Electrochemical detection of hydroquinone by graphene and Pt-graphene hybrid material synthesized through a microwave-assisted chemical reduction process[J].Electrochimica Acta,2011,56(6):2712-2716.
[6]胡耀娟,金娟,张卉,等.石墨烯的制备、功能化及在化学中的应用[J].物理化学学报,2010,26(8):2073-2086.HU Yaojuan,JIN Juan,ZHANG Hui,et al.Graphene:Synthesis,functionalization and applications in chemistry[J].Acta Phys Chim Sin,2010,26(8):2073-2086.
[7]YAN J,WEI T,SHAO B,et al.Preparation of a graphene nanosheet/polyaniline composite with high specific capacitance[J].Carbon,2010,48(2):487-493.
[8]SUN C L,LEE H H,YANG J M,et al.The simultaneous electrochemical detection of ascorbic acid,dopamine,and uric acid using graphene/size-selected Pt nanocomposites[J].Biosensors and Bioelectronics,2011,26(8):3450-3455.
[9]PHILLIIPS P E,STUBER G D,HEIEN M L,et al.Subsecond dopamine release promotes cocaine seeking[J].Nature,2003,422(6932):614-618.
[10]CHATRAEI F,ZARE H.A comparative study of the electrochemical characteristic and simultaneous determination of dopamine,acetaminophen,and aspirin at a ruthenium oxide nanoparticles modified glassy carbon electrode versus a bare one[J].Anal Methods,2012,4(9):2940-2947.
[11]林海莲,杨健茂,刘建允,等.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[J].高等学校化学学报,2013,34(5):1099-1105.LIN Hailian,YANG Jianmao,LIU Jianyun,et al.Preparation of palladium nanoparticle/polyaniline multilayer films for the determination of dopamine and ascorbic acid[J].Chem J Chinese Universities,2013,34(5):1099-1105.
[12]郑新宇,周学酬,郑舒燕,等.聚4-氨基丁酸修饰碳纳米管掺杂碳糊电极的制备及其对多巴胺的测定[J].传感技术学报,2013,26(1):7-11.ZHENG Xinyu,ZHOU Xuechou,ZHENG Shuyan,et al.Preparation of poly-4-aminobutyric acid modified carbon nanotube-doped carbon paste electrode and the detection of dopamine[J].Chinese Journal of Sensors and Actuators,2013,26(1):7-11.
[13]ALIPOUR E,MAJIDI M R,SAADATIRAD A,et al.Simultaneous determination of dopamine and uric acid in biological samples on the pretreated pencil graphite electrode[J].Electrochimica Acta,2013,91(28):36-42.
[14]鹿才余,王宗花,张菲菲,等.桑色素/石墨烯修饰电极的制备及对多巴胺的选择性灵敏测定[J].分析测试学报,2012,31(9):1120-1125.LU Caiyu,WANG Zonghua,ZHANG Feifei,et al.Fabrication of morin incorporated graphene modified electrode and its selective and sensitive determination of dopamine[J].Journal of Instrumental Analysis,2012,31(9):1120-1125.
[15]HUMMERS W S,OFFEMAN R E.Preparation of graphitic oxide[J].J Am Chem Soc,1958,80(6):1339.
[16]孙秀新,闫国婷,李伟.原位聚合法在纳米复合材料中的应用[J].河北工业科技,2008,25(5):318-320.SUN Xiuxin,YAN Guoting,LI Wei.Advances in research of in-suit polymerization applied to nano composites[J].Hebei Journal of Industrial Science and Technology,2008,25(5):318-320.
[17]ZHANG K,ZHANG L L,ZHAO X S,et al.Graphene/polyaniline nanofiber composites as supercapactior electrodes[J].Chem Mater,2010,22(4):1392-1401.
[18]李景印,李娜,李昌家,等.S/石墨烯复合材料的水热法制备及其电化学性能研究[J].河北科技大学学报,2013,34(6):530-534.LI Jingyin,LI Na,LI Changjia,et al.Preparation of S/graphene composite by hydrothermal synthesis and study on its electrochemical performance[J].Journal of Hebei University of Science and Technology,2013,34(6):530-534.
[19]王德山.增强型磺酸羧酸复合膜的工业应用研究[J].河北工业科技,2011,28(4):230-232.WANG Deshan.Research in industrial application of enhanced sulfonic acid and carboxylic acid compound membrane[J].Hebei Journal of Indusirial Science and Technology,2011,28(4):230-232.