Synthesis and Characterization of (3-Aminopropyl)Triethoxysilane-Modified Epitaxial Graphene

Abstract:

Electrochemical immunosensor devices comprise of an antibody immobilised onto a semiconducting or conducting substrate. The use of epitaxial graphene in immunosensors allows for the detection of an antigen specifically bound to the immobilised antibody by monitoring the current modulation of lithographically fabricated graphene channel devices. Multilayer epitaxial graphene (MEG) was produced on semi-insulating 4H-SiC(0001) substrates by annealing at 1700°C at 1x 10^-5 mbar using a graphite cap. Thickness and morphology of the graphene was studied using Raman spectroscopy, XPS, AFM, and SEM. Selective areas of graphene were targeted for modification by adding a protective window of PMMA. In order to immobilise the antibody to the graphene substrate, an amine-terminated surface is required. (3-aminopropyl) triethoxysilane (APTES), is used to achieve amine termination, which is itself bound to a hydroxyliated graphene surface. Hydroxylation was achieved using Fenton chemistry and changes in surface hydrophobicity are confirmed using contact angle measurements. Attachment of APTES to the hydroxyl terminated graphene channel was confirmed using cyclic voltammetry (CV), XPS, and Raman spectroscopy. This functionalization method can be used to attach any antibody to the graphene substrate that can bind to an amine group. This platform is therefore easily adaptable for the fabrication of a range of immunosensor devices for the detection of different biomarkers.

• Periodical: Materials Science Forum (Volume 806)
• Pages: 95-102
• DOI: https://doi.org/10.4028/www.scientific.net/MSF.806.95
• Online since: October 2014
• Authors: Gregory Burwell*, Sofia Teixeira, Ambroise Castaing, Owen James Guy
• Keywords: 4H-SiC, APTES, Chemical Modification, Epitaxial Graphene, Functionalization

References

[1] Berger, C., Ruan, M., Palmer, J., Hankinson, J., Hu, Y., Guo, Z., Dong, R., Conrad, E. H., & De Heer, W. A. (2011), ECS Transactions 41, 43-55.

DOI: 10.1149/1.3633284

[2] Lara-Avila, S., Kalaboukhov, A., Paolillo, S., Syväjärvi, M., Yakimova, R., Fal'ko, V., Tzalenchuk, A., & Kubatkin, S. (2009), arXiv preprint arXiv: 0909. 1193.

DOI: 10.1038/nnano.2009.474

[3] Ang, P. K., Chen, W., Wee, A. T. S., & Loh, K. P. (2008), Journal of the American Chemical Society 130, 14392-14393.

[4] Guy, O. J., Burwell, G., Tehrani, Z., Castaing, A., Walker, K. A., & Doak, S. (2012), 711, 246-252.

DOI: 10.4028/www.scientific.net/msf.711.246

[5] Georgakilas, V., Otyepka, M., Bourlinos, A. B., Chandra, V., Kim, N., Kemp, K. C., Hobza, P., Zboril, R., & Kim, K. S. (2012), Chemical Reviews 112, 6156-6214.

DOI: 10.1021/cr3000412

[6] Coletti, C., Riedl, C., Lee, D., Krauss, B., Patthey, L., von Klitzing, K., Smet, J., & Starke, U. (2010), Physical Review B 81, 235401.

DOI: 10.1103/physrevb.81.235401

[7] Boukhvalov, D. (2011), Nanotechnology 22, 055708.

[8] De Heer, W. A., Berger, C., Wu, X., First, P. N., Conrad, E. H., Li, X., Li, T., Sprinkle, M., Hass, J., Sadowski, M. L., & others (2007), Solid State Communications 143, 92-100.

DOI: 10.1016/j.ssc.2007.04.023

[9] Varchon, F., Feng, R., Hass, J., Li, X., Nguyen, B. N., Naud, C., Mallet, P., Veuillen, J. Y., Berger, C., Conrad, E., & others (2007), Physical review letters 99, 126805.

DOI: 10.1103/physrevlett.99.126805

[10] Camara, N., Huntzinger, J. R., Rius, G., Tiberj, A., Mestres, N., Pérez-Murano, F., Godignon, P., & Camassel, J. (2009), Physical Review B 80, 125410.

DOI: 10.4028/www.scientific.net/msf.615-617.203

[11] Luppa, P. B., Sokoll, L. J., & Chan, D. W. (2001), Clinica chimica acta; international journal of clinical chemistry 314, 1.

[12] Skládal, P. (1997), Electroanalysis 9, 737-745.

[13] Rhodes, D. R., Sanda, M. G., Otte, A. P., Chinnaiyan, A. M., & Rubin, M. A. (2003), Journal of the National Cancer Institute 95, 661-668.

[14] Orlandi, F., Rossi, C., Allegra, A., Krantz, D., Hallahan, T., Orlandi, E., & Macri, J. (2002), Prenatal diagnosis 22, 718-721.

DOI: 10.1002/pd.390

[15] Chiou, C. C., Chang, P. Y., Chan, E. C., Wu, T. L., Tsao, K. C., & Wu, J. T. (2003), Clinica chimica acta 334, 87-94.

[16] Niyogi, S., Bekyarova, E., Itkis, M. E., Zhang, H., Shepperd, K., Hicks, J., Sprinkle, M., Berger, C., Lau, C. N., Deheer, W. A., & others (2010), Nano letters.

DOI: 10.1021/nl1021128

[17] Bindoli, A., Fukuto, J. M., & Forman, H. J. (2008), Antioxidants \& redox signaling 10, 1549-1564.

DOI: 10.1089/ars.2008.2063

[18] Kathi, J. & Rhee, K. (2008), Journal of Materials Science 43, 33-37.

[19] Halliwell, C. M. & Cass, A. E. (2001), Analytical chemistry 73, 2476-2483.

[20] Camara, N., Tiberj, A., Jouault, B., Caboni, A., Jabakhanji, B., Mestres, N., Godignon, P., & Camassel, J. (2010), Journal of Physics D: Applied Physics 43, 374011.

DOI: 10.1088/0022-3727/43/37/374011

[21] Bradley, R. H., Cassity, K., Andrews, R., Meier, M., Osbeck, S., Andreu, A., Johnston, C., & Crossley, A. (2012), Applied Surface Science.

DOI: 10.1016/j.apsusc.2012.01.008

[22] Seah, M. & Dench, W. (1979), Surface and interface analysis 1, 2-11.

[23] Jung, N., Kim, N., Jockusch, S., Turro, N. J., Kim, P., & Brus, L. (2009), Nano letters 9, 4133-4137.

DOI: 10.1021/nl902362q

[24] Riegel, B., Blittersdorf, S., Kiefer, W., Hofacker, S., Müller, M., & Schottner, G. (1998), I. Journal of non-crystalline solids 226, 76-84.

DOI: 10.1016/s0022-3093(97)00487-0

[25] Fang, M., Wang, K., Lu, H., Yang, Y., & Nutt, S. (2009), Journal of Materials Chemistry 19, 7098-7105.

[26] Huang, P., Zhu, H., Jing, L., Zhao, Y., & Gao, X. (2011), ACS nano 5, 7945-7949.

[27] Kudin, K. N., Ozbas, B., Schniepp, H. C., Prud'Homme, R. K., Aksay, I. A., & Car, R. (2008), Nano Letters 8, 36-41.

[28] Collyer, S. D., Davis, F., Lucke, A., Stirling, C. J., & Higson, S. P. (2003), Journal of Electroanalytical Chemistry 549, 119-127.