基于石墨烯修饰电极的电化学生物传感

doi:10.6023/A13080848

摘要/Abstract

石墨烯是一种具有单原子厚度的二维碳纳米材料，具有大的比表面积、高的导电性和室温电子迁移率，以及优异的机械力学性能. 石墨烯还具有电化学窗口宽，电化学稳定性好，电荷传递电阻小，电催化活性高和电子转移速率快等电化学特性. 化学修饰石墨烯，特别是氧化石墨烯（GO）和还原氧化石墨烯（rGO），可以被宏量、廉价地制备出来. 它们具有可加工性能，可以被组装、加工或复合成具有可控组成和微结构的宏观电极材料. 因此，石墨烯及其化学修饰衍生物是用于电化学生物传感的独特而诱人的电极材料. 例如，GO是一种化学修饰石墨烯，也是石墨烯的重要前驱体；其边缘具有大量的羧基可用于共价固定酶，从而能实现酶电极的生物检测. 在GO上的不可逆蛋白吸附也可以促进蛋白质的直接电子转移以提高其电化学检测性能. 但是，GO大量的含氧官能团破坏了石墨烯本征的共轭结构，降低了其电学性能并限制了其实际应用. GO可以通过化学、电化学、热还原等技术转化成rGO，从而能部分修复其共轭结构，提高其导电性与传感性能. 另一方面，石墨烯是一种零带隙材料；原子掺杂可以调控其能带结构，提高其电催化性能. 石墨烯材料也常常需要通过与其它功能材料的复合进一步改善其可分散与可加工性能，提高其电催化活性和电化学选择性. 本文综述了本征石墨烯（包括GO，rGO和掺杂石墨烯）以及石墨烯与生物分子、高分子、离子液体、金属或金属氧化物纳米粒子等复合材料修饰电极在检测各种生物分子方面的研究进展，并对该研究领域进行了展望.

关键词: 石墨烯, 氧化石墨烯, 生物分子, 电化学检测, 电化学传感

Graphene has a unique atom-thick two-dimensional structure and excellent properties, including high conductivity and electron mobility at room temperature, large specific surface area, and excellent mechanical properties. Graphene also possesses a variety of promising electrochemical properties, such as a wide potential window, low charge-transfer resistance, high electrocatalytic activity and fast electron transfer rate. Furthermore, chemically modified graphene materials, particularly graphene oxide (GO) and reduced graphene oxide (rGO), can be produced in a large scale and at low costs. They have good processability and can be assembled, blended or fabricated into macroscopic electrode materials with controlled compositions and microstructures. Thus, graphene and its chemically modified derivatives are unique and attractive electrode materials for electrochemical biosensing. For example, GO is a chemically modified graphene and an important precursor of graphene. GO sheets have a large amount of carboxyl groups at their edges, which can be used to covalently immobilize enzymes, realizing the detection of biomolecules. GO can also enhance the direct charge transfer of protein because of its irreversible adsorption to protein and abundant catalytic sites. However, the oxygen functional groups of GO heavily destroy the conjugated planes of graphene sheets, decreasing the electrical property and limiting the practical applications of GO. Chemical, electrochemical, or thermal reduction can partly restore the conjugated structure, converting GO to conductive rGO. On the other hand, graphene is a material with zero band gap. Doping graphene with heteroatoms can modulate its band gap and improve its electrocatalytic properties. Graphene materials also frequently have to be blended with other functional materials to improve their dispersibility and processibility, enhance their electrochemical activity and/or selectivity. This review will summarize the recent research achievements in electrochemical biosensing based on the electrodes modified with pristine graphene (e.g. GO, rGO, and doped graphene) or graphene composites with biomolecules, polymers, ionic liquids, metal and metal oxide nanoparticles. A perspective of developments in this research field is also provided.

Key words: graphene, graphene oxide, biomolecules, electrochemical detection, electrochemical sensing

引用此文

于小雯, 盛凯旋, 陈骥, 李春, 石高全. 基于石墨烯修饰电极的电化学生物传感[J]. 化学学报, 2014, 72(3): 319-332.

Yu Xiaowen, Sheng Kaixuan, Chen Ji, Li Chun, Shi Gaoquan. Electrochemical Biosensing Based on Graphene Modified Electrodes[J]. Acta Chimica Sinica, 2014, 72(3): 319-332.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306, 666.

[2] Geim, A. K.; Novoselov, K. S. Nat. Mater. 2007, 6, 183.

[3] Alwarappan, S.; Erdem, A.; Liu, C.; Li, C.-Z. J. Phys. Chem. C 2009, 113, 8853.

[4] Lee, C.; Wei, X.; Kysar, J. W.; Hone, J. Science 2008, 321, 385.

[5] Stoller, M. D.; Park, S.; Zhu, Y.; An, J.; Ruoff, R. S. Nano Lett. 2008, 8, 3498.

[6] Huang, X.; Zeng, Z.; Fan, Z.; Liu, J.; Zhang, H. Adv. Mater. 2012, 24, 5979.

[7] Huang, C.; Li, C.; Shi, G. Energy Environ. Sci. 2012, 5, 8848.

[8] Yang, W.; Ratinac, K. R.; Ringer, S. P.; Thordarson, P.; Gooding, J. J.; Braet, F. Angew. Chem., Int. Ed. 2010, 49, 2114.

[9] Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80, 1339.

[10] Zuo, X.; He, S.; Li, D.; Peng, C.; Huang, Q.; Song, S.; Fan, C. Langmuir 2010, 26, 1936.

[11] Zhou, M.; Zhai, Y.; Dong, S. Anal. Chem. 2009, 81, 5603.

[12] Liu, Y.; Dong, X.; Chen, P. Chem. Soc. Rev. 2012, 41, 2283.

[13] Si, Y.; Samulski, E. T. Nano Lett. 2008, 8, 1679.

[14] Artiles, M. S.; Rout, C. S.; Fisher, T. S. Adv. Drug Delivery Rev. 2011, 63, 1352.

[15] Wu, J.-F.; Xu, M.-Q.; Zhao, G.-C. Electrochem. Commun. 2010, 12, 175.

[16] Zeng, Q.; Cheng, J.-S.; Liu, X.-F.; Bai, H.-T.; Jiang, J.-H. Biosens. Bioelectron. 2011, 26, 3456.

[17] Zhang, Q.; Yang, S.; Zhang, J.; Zhang, L.; Kang, P.; Li, J.; Xu, J.; Zhou, H.; Song, X.-M. Nat. Nanotechnol. 2011, 22, 494010.

[18] Wu, S.; He, Q.; Tan, C.; Wang, Y.; Zhang, H. Small 2013, 9, 1160.

[19] Ratinac, K. R.; Yang, W.; Gooding, J. J.; Thordarson, P.; Braet, F. Electroanalysis 2011, 23, 803.

[20] Kuila, T.; Bose, S.; Khanra, P.; Mishra, A. K.; Kim, N. H.; Lee, J. H. Biosens. Bioelectron. 2011, 26, 4637.

[21] Gan, T.; Hu, S. Microchim. Acta 2011, 175, 1.

[22] Shao, Y.; Wang, J.; Wu, H.; Liu, J.; Aksay, I. A.; Lin, Y. Electroanalysis 2010, 22, 1027.

[23] Pumera, M.; Ambrosi, A.; Bonanni, A.; Chng, E. L. K.; Poh, H. L. Trac-trend. Anal. Chem. 2010, 29, 954.

[24] Pumera, M. Chem. Soc. Rev. 2010, 39, 4146.

[25] Chen, D.; Tang, L.; Li, J. Chem. Soc. Rev. 2010, 39, 3157.

[26] Brownson, D. A.; Banks, C. E. Analyst 2010, 135, 2768.

[27] Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. Chem. Soc. Rev. 2010, 39, 228.

[28] Liu, Y.; Yu, D.; Zeng, C.; Miao, Z.; Dai, L. Langmuir 2010, 26, 6158.

[29] Vincent, K. A.; Li, X.; Blanford, C. F.; Belsey, N. A.; Weiner, J. H.; Armstrong, F. A. Nat. Chem. Biol. 2007, 3, 761.

[30] Kang, X.; Wang, J.; Wu, H.; Liu, J.; Aksay, I. A.; Lin, Y. Talanta 2010, 81, 754.

[31] Muti, M.; Sharma, S.; Erdem, A.; Papakonstantinou, P. Electroanalysis 2011, 23, 272.

[32] Huang, K.-J.; Niu, D.-J.; Sun, J.-Y.; Han, C.-H.; Wu, Z.-W.; Li, Y.-L.; Xiong, X.-Q. Colloids Surf. B 2011, 82, 543.

[33] Raj, M. A.; John, S. A. Anal. Chim. Acta 2013, 771, 14.

[34] Liu, J.; Kong, N.; Li, A.; Luo, X.; Cui, L.; Wang, R.; Feng, S. Analyst 2013, 138, 2567.

[35] Giovanni, M.; Bonanni, A.; Pumera, M. Analyst 2012, 137, 580.

[36] Wang, Z.; Zhang, J.; Chen, P.; Zhou, X.; Yang, Y.; Wu, S.; Niu, L.; Han, Y.; Wang, L.; Chen, P.; Boey, F.; Zhang, Q.; Liedberg, B.; Zhang, H. Biosens. Bioelectron. 2011, 26, 3881.

[37] Ma, X.; Chao, M.; Wang, Z. Anal. Methods 2012, 4, 1687.

[38] Alwarappan, S.; Joshi, R. K.; Ram, M. K.; Kumar, A. Appl. Phys. Lett. 2010, 96, 263702.

[39] Wang, Q.; Zheng, M.; Shi, J.; Gao, F.; Gao, F. Electroanalysis 2011, 23, 915.

[40] Nethravathi, C.; Rajamathi, M. Carbon 2008, 46, 1994.

[41] Mallesha, M.; Manjunatha, R.; Nethravathi, C.; Suresh, G. S.; Rajamathi, M.; Melo, J. S.; Venkatesha, T. V. Bioelectrochemistry 2011, 81, 104.

[42] Haque, A. M.; Park, H.; Sung, D.; Jon, S.; Choi, S.-Y.; Kim, K. Anal. Chem. 2012, 84, 1871.

[43] Ling, Y.-Y.; Huang, Q.-A.; Zhu, M.-S.; Feng, D.-X.; Li, X.-Z.; Wei, Y. J. Electroanal. Chem. 2013, 693, 9.

[44] Unnikrishnan, B.; Palanisamy, S.; Chen, S.-M. Biosens. Bioelectron. 2013, 39, 70.

[45] Dong, X.; Wang, X.; Wang, L.; Song, H.; Zhang, H.; Huang, W.; Chen, P. ACS Appl. Mater. Interfaces 2012, 4, 3129.

[46] Kim, Y.-R.; Bong, S.; Kang, Y.-J.; Yang, Y.; Mahajan, R. K.; Kim, J. S.; Kim, H. Biosens. Bioelectron. 2010, 25, 2366.

[47] Wu, P.; Shao, Q.; Hu, Y.; Jin, J.; Yin, Y.; Zhang, H.; Cai, C. Electrochim. Acta 2010, 55, 8606.

[48] Zhou, C.; Kong, J.; Yenilmez, E.; Dai, H. Science 2000, 290, 1552.

[49] Cortes Arriagada, D. J. Mol. Model. 2013, 19, 919.

[50] Guo, B.; Liu, Q.; Chen, E.; Zhu, H.; Fang, L.; Gong, J. R. Nano Lett. 2010, 10, 4975.

[51] Zhang, C.; Fu, L.; Liu, N.; Liu, M.; Wang, Y.; Liu, Z. Adv. Mater. 2011, 23, 1020.

[52] Fan, H.; Li, Y.; Wu, D.; Ma, H.; Mao, K.; Fan, D.; Du, B.; Li, H.; Wei, Q. Anal. Chim. Acta 2011, 711, 24.

[53] Wang, Y.; Shao, Y.; Matson, D. W.; Li, J.; Lin, Y. ACS Nano 2010, 4, 1790.

[54] Sheng, Z.-H.; Zheng, X.-Q.; Xu, J.-Y.; Bao, W.-J.; Wang, F.-B.; Xia, X.-H. Biosens. Bioelectron. 2012, 34, 125.

[55] Tan, S. M.; Poh, H. L.; Sofer, Z.; Pumera, M. Analyst 2013, 138, 4885.

[56] Li, X.-R.; Kong, F.-Y.; Liu, J.; Liang, T.-M.; Xu, J.-J.; Chen, H.-Y. Adv. Funct. Mater. 2012, 22, 1981.

[57] Li, X.-R.; Liu, J.; Kong, F.-Y.; Liu, X.-C.; Xu, J.-J.; Chen, H.-Y. Electrochem. Commun. 2012, 20, 109.

[58] Liu, Y.; Wang, M.; Zhao, F.; Xu, Z.; Dong, S. Biosens. Bioelectron. 2005, 21, 984.

[59] Sorlier, P.; Denuziere, A.; Viton, C.; Domard, A. Biomacromolecules 2001, 2, 765.

[60] Kang, X.; Wang, J.; Wu, H.; Aksay, I. A.; Liu, J.; Lin, Y. Biosens. Bioelectron. 2009, 25, 901.

[61] Wang, Y.; Li, Y.; Tang, L.; Lu, J.; Li, J. Electrochem. Commun. 2009, 11, 889.

[62] Han, D.; Han, T.; Shan, C.; Ivaska, A.; Niu, L. Electroanalysis 2010, 22, 2001.

[63] Qiu, J.-D.; Huang, J.; Liang, R.-P. Sens. Actuators, B 2011, 160, 287.

[64] Zhou, Y.; Liu, S.; Jiang, H.-J.; Yang, H.; Chen, H.-Y. Electroanalysis 2010, 22, 1323.

[65] Xu, H.; Dai, H.; Chen, G. Talanta 2010, 81, 334.

[66] Freeman, R.; Finder, T.; Bahshi, L.; Willner, I. Nano Lett. 2009, 9, 2073.

[67] Tan, L.; Zhou, K.-G.; Zhang, Y.-H.; Wang, H.-X.; Wang, X.-D.; Guo, Y.-F.; Zhang, H.-L. Electrochem. Commun. 2010, 12, 557.

[68] Guo, Y.; Guo, S.; Ren, J.; Zhai, Y.; Dong, S.; Wang, E. ACS Nano 2010, 4, 4001.

[69] Lv, W.; Guo, M.; Liang, M.-H.; Jin, F.-M.; Cui, L.; Zhi, L.; Yang, Q.-H. J. Mater. Chem. 2010, 20, 6668.

[70] Zhang, Q.; Qiao, Y.; Hao, F.; Zhang, L.; Wu, S.; Li, Y.; Li, J.; Song, X.-M. Chem. Eur. J. 2010, 16, 8133.

[71] Lv, W.; Jin, F.-M.; Guo, Q.; Yang, Q.-H.; Kang, F. Electrochim. Acta 2012, 73, 129.

[72] Patil, A. J.; Vickery, J. L.; Scott, T. B.; Mann, S. Adv. Mater. 2009, 21, 3159.

[73] Li, C.; Shi, G. Electrochim. Acta 2011, 56, 10737.

[74] Bai, H.; Li, C.; Shi, G. Adv. Mater. 2011, 23, 1089.

[75] Alwarappan, S.; Liu, C.; Kumar, A.; Li, C.-Z. J. Phys. Chem. C 2010, 114, 12920.

[76] Scott, C. L.; Zhao, G.; Pumera, M. Electrochem. Commun. 2010, 12, 1788.

[77] Zhuang, Z.; Li, J.; Xu, R.; Xiao, D. Int. J. Electrochem. Sci. 2011, 6, 2149.

[78] Bo, Y.; Yang, H.; Hu, Y.; Yao, T.; Huang, S. Electrochim. Acta 2011, 56, 2676.

[79] Bai, H.; Xu, Y.; Zhao, L.; Li, C.; Shi, G. Chem. Commun. 2009, 1667.

[80] Liu, Q.; Zhu, X.; Huo, Z.; He, X.; Liang, Y.; Xu, M. Talanta 2012, 97, 557.

[81] Shen, Y.; Zhang, Y.; Qiu, X.; Guo, H.; Niu, L.; Ivaska, A. Green Chem. 2007, 9, 746.

[82] Yang, F.; Jiao, L.; Shen, Y.; Xu, X.; Zhang, Y.; Niu, L. J. Electroanal. Chem. 2007, 608, 78.

[83] Yang, H.; Shan, C.; Li, F.; Han, D.; Zhang, Q.; Niu, L. Chem. Commun. 2009, 3880.

[84] Liao, H.-g.; Wu, H.; Wang, J.; Liu, J.; Jiang, Y.-X.; Sun, S.-G.; Lin, Y. Electroanalysis 2010, 22, 2297.

[85] Liu, K.; Zhang, J.; Yang, G.; Wang, C.; Zhu, J.-J. Electrochem. Commun. 2010, 12, 402.

[86] Qiu, Y.; Qu, X.; Dong, J.; Ai, S.; Han, R. J. Hazard. Mater. 2011, 190, 480.

[87] Wu, J.-W.; Wang, C.-H.; Wang, Y.-C.; Chang, J.-K. Biosens. Bioelectron. 2013, 46, 30.

[88] Shan, C.; Yang, H.; Song, J.; Han, D.; Ivaska, A.; Niu, L. Anal. Chem. 2009, 81, 2378.

[89] Shan, C.; Yang, H.; Han, D.; Zhang, Q.; Ivaska, A.; Niu, L. Biosens. Bioelectron. 2010, 25, 1504.

[90] Niu, X.; Yang, W.; Guo, H.; Ren, J.; Gao, J. Biosens. Bioelectron. 2013, 41, 225.

[91] Welch, C. M.; Compton, R. G. Anal. Bioanal. Chem.2006, 384, 601.

[92] Shan, C.; Yang, H.; Han, D.; Zhang, Q.; Ivaska, A.; Niu, L. Biosens. Bioelectron. 2010, 25, 1070.

[93] Hong, W.; Bai, H.; Xu, Y.; Yao, Z.; Gu, Z.; Shi, G. J. Phys. Chem. C 2010, 114, 1822.

[94] Xiao, F.; Song, J.; Gao, H.; Zan, X.; Xu, R.; Duan, H. ACS Nano 2012, 6, 100.

[95] Wang, Z.; Zhang, J.; Yin, Z.; Wu, S.; Mandler, D.; Zhang, H. Nanoscale 2012, 4, 2728.

[96] Liu, S.; Yan, J.; He, G.; Zhong, D.; Chen, J.; Shi, L. Y.; Zhou, X.; Jiang, H. J. Electroanal. Chem. 2012, 672, 40.

[97] Chen, Y.; Li, Y.; Sun, D.; Tian, D.; Zhang, J.; Zhu, J.-J. J. Mater. Chem. 2011, 21, 7604.

[98] Du, M.; Yang, T.; Jiao, K. J. Mater. Chem. 2010, 20, 9253.

[99] Zheng, J.; He, Y.; Sheng, Q.; Zhang, H. J. Mater. Chem. 2011, 21, 12873.

[100] Xia, Q.; Luo, D.; Li, Z. Acta Chim. Sinica 2012, 70, 2079. (夏前芳, 罗丹, 李在均, 化学学报, 2012, 70, 2079.)

[101] Zhang, Q.; Wu, S.; He, M.; Zhang, L.; Liu, Y.; Li, J.; Song, X.-M. Acta Chim. Sinica 2012, 70, 2213. (张谦, 吴抒遥, 何茂伟, 张玲, 刘洋, 李景虹, 宋溪明, 化学学报, 2012, 70, 2213.)

[102] Xia, Q.; Huang, Y.; Yang, X.; Li, Z. Acta Chim. Sinica 2012, 70, 1315. (夏前芳, 黄颖娟, 杨雪, 李在均, 化学学报, 2012, 70, 1315.)

[103] Lu, W.; Luo, Y.; Chang, G.; Sun, X. Biosens. Bioelectron. 2011, 26, 4791.

[104] Guo, S.; Wen, D.; Zhai, Y.; Dong, S.; Wang, E. ACS Nano 2010, 4, 3959.

[105] Wu, H.; Wang, J.; Kang, X.; Wang, C.; Wang, D.; Liu, J.; Aksay, I. A.; Lin, Y. Talanta 2009, 80, 403.

[106] Sun, C.-L.; Lee, H.-H.; Yang, J.-M.; Wu, C.-C. Biosens. Bioelectron. 2011, 26, 3450.

[107] Lu, L.-M.; Li, H.-B.; Qu, F.; Zhang, X.-B.; Shen, G.-L.; Yu, R.-Q. Biosens. Bioelectron. 2011, 26, 3500.

[108] Wang, Q.; Cui, X.; Chen, J.; Zheng, X.; Liu, C.; Xue, T.; Wang, H.; Jin, Z.; Qiao, L.; Zheng, W. RSC Adv. 2012, 2, 6245.

[109] You, J.-M.; Kim, D.; Kim, S. K.; Kim, M.-S.; Han, H. S.; Jeon, S. Sens. Actuators, B 2013, 178, 450.

[110] Wang, X.; Wu, M.; Tang, W.; Zhu, Y.; Wang, L.; Wang, Q.; He, P.; Fang, Y. J. Electroanal. Chem. 2013, 695, 10.

[111] Pingarron, J. M.; Yanez-Sedeno, P.; Gonzalez-Cortes, A. Electrochim. Acta 2008, 53, 5848.

[112] Lu, J.; Do, I.; Drzal, L. T.; Worden, R. M.; Lee, I. ACS Nano 2008, 2, 1825.

[113] Lim, S. H.; Wei, J.; Lin, J.; Li, Q.; You, J. K. Biosens. Bioelectron. 2005, 20, 2341.

[114] Fan, Y.; Lu, H.-T.; Liu, J.-H.; Yang, C.-P.; Jing, Q.-S.; Zhang, Y.-X.; Yang, X.-K.; Huang, K.-J. Colloids Surf. B 2011, 83, 78.

[115] Fan, Y.; Liu, J.-H.; Lu, H.-T.; Zhang, Q. Colloids Surf. B 2011, 85, 289.

[116] Jang, H. D.; Kim, S. K.; Chang, H.; Roh, K. M.; Choi, J. W.; Huang, J. Biosens. Bioelectron. 2012, 38, 184.

[117] Yang, A.; Xue, Y.; Zhang, Y.; Zhang, X.; Zhao, H.; Li, X.; He, Y.; Yuan, Z. J. Mater. Chem. B 2013, 1, 1804.

[118] Sun, W.; Wang, X.; Wang, Y.; Ju, X.; Xu, L.; Li, G.; Sun, Z. Electrochim. Acta 2013, 87, 317.

[119] Palanisamy, S.; Vilian, A. T. E.; Chen, S.-M. Int. J. Electrochem. Sci. 2012, 7, 2153.

[120] Xie, L.; Xu, Y.; Cao, X. Colloids Surf. B 2013, 107, 245.

[121] Ensafi, A. A.; Jafari-Asl, M.; Rezaei, B. Talanta 2013, 103, 322.

[122] Liu, M.; Liu, R.; Chen, W. Biosens. Bioelectron. 2013, 45, 206.

[123] Xiao, F.; Li, Y.; Gao, H.; Ge, S.; Duan, H. Biosens. Bioelectron. 2013, 41, 417.

[124] Huang, T.-Y.; Huang, J.-H.; Wei, H.-Y.; Ho, K.-C.; Chu, C.-W. Biosens. Bioelectron. 2013, 43, 173.

[125] Mani, V.; Devadas, B.; Chen, S.-M. Biosens. Bioelectron. 2013, 41, 309.

[126] Sun, C.-L.; Chang, C.-T.; Lee, H.-H.; Zhou, J.; Wang, J.; Sham, T.-K.; Pong, W.-F. ACS Nano 2011, 5, 7788.

[127] Chen, J.; Zhao, L.; Bai, H.; Shi, G. J. Electroanal. Chem. 2011, 657, 34.

[128] Wu, L.; Feng, L.; Ren, J.; Qu, X. Biosens. Bioelectron. 2012, 34, 57.

[129] Zeng, G.; Xing, Y.; Gao, J.; Wang, Z.; Zhang, X. Langmuir 2010, 26, 15022.

[130] Melde, B. J.; Johnson, B. J. Anal. Bioanal. Chem. 2010, 398, 1565.