Abstract
A highly hydrophilic ordered mesoporous carbon–poly(vinyl alcohol) composite with large surface area and good biocompatibility, and exhibiting efficient immobilization and biosensing of protein [e.g., hemoglobin (Hb)] was prepared by intermittent microwave heating techlnique. The as-prepared composite with immobilized Hb is tested for direct electrochemistry and biosensing. The immobilized Hb at the modified electrode had a high adsorption with 32 wt% of the proteins. Moreover, the modified electrode retained its native structure, with improved interfacial electron-communication rate, and showed a good electrochemical performance to detect H2O2, as verified by Raman, UV–Vis absorption, and electrochemical impedance spectroscopies, as well as steady-state current measurements. The proposed biosensor shows a sensitivity of 9.8 µA mM−1 and responds in less than 5 s when the protein concentration ranges from 87.5 to 0.4 µM. This work provides an efficient strategy and a new promising platform for both fundamental investigation of the redox reactions mechanism and the development of third-generation biosensors.
Graphical Abstract
A unique structure and high hydrophilic nature mesoporous carbon has been obtained by a a simple and effective synthesis method. It still retains the ordered mesoporous carbon structure and the mesopore width. The composite enabled a high protein loading and a fast direct electron transfer, resulting in a much higher biocatalytic sensitivity and long-term stability.
Similar content being viewed by others
References
Kresge CT, Leonowicz ME, Roth WJ, Vartull JC, Beck JS (1992) Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359(6397):710–712. doi:10.1038/359710a0
Fan J, Yu C, Gao F, Lei J, Tian B, Wang L, Luo Q, Tu B, Zhou W, Zhao D (2003) Cubic mesoporous silica with large controllable entrance sizes and advanced adsorption properties. Angew Chem Int Ed 42(27):3146–3150. doi:10.1002/anie.200351027
Wang Y, Caruso F (2004) Enzyme encapsulation in nanoporous silica spheres. Chem Commun 13:1528–1529. doi:10.1039/B403871A
Tanev PT, Pinnavaia TJ (1995) A neutral templating route to mesoporous molecular sieves. Science 267(5199):865–867. doi:10.1126/science.267.5199.865
Schüth F (2003) Endo- and exotemplating to create high-surface-area inorganic materials. Angewandte Chemie-International Edition 42(31):3604–3622. doi:10.1002/anie.200300593
Lee D, Lee J, Kim J, Kim J, Na HB, Kim B, Shin CH, Kwak JH, Dohnalkova A, Grate JW, Hyeon T, Kim HS (2005) Simple fabrication of a highly sensitive and fast glucose biosensor using enzymes immobilized in mesocellular carbon foam. Adv Mater 17(23):2828–2833. doi:10.1002/adma.200500793
Liang CD, Li ZJ, Dai S (2008) Mesoporöse Kohlenstoffmaterialien: synthese und modifizierung. Angewandte Chemie-International Edition 120(20):3754–3776. doi:10.1002/ange.200702046
Bahr JL, Tour JM (2002) Covalent chemistry of single-wall carbon nanotubes. J Mater Chem 12:1952–1958. doi:10.1039/B201013P
Katherine PB, Hudson JL, Tour JM (2005) Green chemical functionalization of single-walled carbon nanotubes in ionic liquids. J Am Chem Soc 127(42):14867–14870. doi:10.1021/ja053998c
Minkee C, Ryong R (2003) Ordered nanoporous polymer-carbon composites. Nat Mater 2(7):473–476. doi:10.1038/nmat923
Ryoo R, Joo SH, Jun S (1999) Energetically favored formation of MCM-48 from cationic–neutral surfactant mixtures. J Phys Chem B 103(35):7435–7440. doi:10.1021/jp9911649
Jun S, Joo SH, Ryoo R, Kruk M, Jaroniec M, Liu Z, Ohsuna T, Terasaki O (2000) Synthesis of new, nanoporous carbon with hexagonally ordered mesostructure. J Am Chem Soc 122(43):10712–10713. doi:10.1021/ja002261e
Yu CZ, Fan J, Tian BZ, Zhao DY, Stucky GD (2002) High-yield synthesis of periodic mesoporous silica rods and their replication to mesoporous carbon rods. Adv Mater 14(23):1742–1745. doi:10.1002/1521-4095(20021203)14:23<1742:AID-ADMA1742>3.0.CO;2-3
Kim TW, Park IS, Ryoo R (2003) A synthetic route to ordered mesoporous carbon materials with graphitic pore walls. Angewandte Chemie 42(36):4375–4379. doi:10.1002/anie.200352224
Kim CH, Khil MS, Kim HY, Lee HU, Jahng KY (2006) An improved hydrophilicity via electrospinning for enhanced cell attachment and proliferation. J Biomed Materials Res. Part B: Applied Biomaterials 78b(2):283–290. doi:10.1002/jbm.b.30484
Hrapovic S, Liu YL, Luong JHT (2007) Reusable platinum nanoparticle modified boron doped diamond microelectrodes for oxidative determination of arsenite. Anal Chem 79(2):500–507. doi:10.1021/ac061528a
Davis ME (2002) Ordered porous materials for emerging applications. Nature 417:813–821. doi:10.1038/nature00785
Kim J, Jia HF, Wang P (2006) Challenges in biocatalysis for enzyme-based biofuel cells. Biotechnol Adv 24(3):296–308. doi:10.1016/j.biotechadv.2005.11.006
Feng JJ, Xu JJ, Chen HY (2007) Direct electron transfer and electrocatalysis of hemoglobin adsorbed on mesoporous carbon through layer-by-layer assembly. Biosens Bioelectron 22(8):1618–1624. doi:10.1017/S0376892907003839
Bajpai AK, Rajpoot M (1999) Adsorption techniques: a review. J Sci Ind Res 58(11):844–860
Dai ZH, Ju HX (2004) Direct electron transfer of protein immobilized on mesoporous molecular sieves matrix. Acta Phys Chim Sin 20(10):1262–1266. doi:10.3866/PKU.WHXB20041020
Cao DF, Hu NF (2006) Direct electron transfer between hemoglobin and pyrolytic graphite electrodes enhanced by Fe3O4 nanoparticles in their layer-by-layer self-assembly films. Biophys Chem 121(3):209–217. doi:10.1016/j.bpc.2005.11.003
Wang CH, Yang C, Song YY, Gao W, Xia XH (2005) Adsorption and direct electron transfer from hemoglobin into a three-dimensionally ordered macroporous gold film & dagger. Adv Funct Mater 15(8):1267–1275. doi:10.1002/adfm.200500048
Zhang L, Jiang XU, Wang EK, Dong SJ (2005) Attachment of gold nanoparticles to glassy carbon electrode and its application for the direct electrochemistry and electrocatalytic behavior of hemoglobin. Biosens Bioelectron 21(2):337–345. doi:10.1016/j.bios.2004.10.021
Sun W, Wang DD, Gao RF, Jiao K (2007) Direct electrochemistry and electrocatalysis of hemoglobin in sodium alginate film on a BMIMPF6 modified carbon paste electrode. Electrochem Commun 9(5):1159–1164. doi:10.1016/j.elecom.2007.01.003
Bond AM (1980) Modern polarographic methods in analytical chemistry. Marcel Dekker, New York
Shan D, Han E, Xue HG, Cosnier S (2007) Self-assembled films of hemoglobin/laponite/chitosan: application for the direct electrochemistry and catalysis to hydrogen peroxide. Biomacromolecules 8(10):3041–3046. doi:10.1021/bm070329d
Fan J, Lei J, Wang LM, Yu CZ, Tu B, Zhao DY (2003) Rapid and high-capacity immobilization of enzymes based on mesoporous silicas with controlled morphologies. Chem Commun 17(17):2140–2141. doi:10.1039/B304391F
Sakamoto A, Sakurao S, Fukunaga K, Matsubara T, Ueda-Hashimoto M, Tsukamoto S, Takahashi M, Morikawa H (2004) Three distinct Arabidopsis hemoglobins exhibit peroxidase-like activity and differentially mediate nitrite-dependent protein nitration. FEBS Lett 572(1–3):27–32. doi:10.1016/j.febslet.2004.07.005
Zhang XJ, Ju HX, Wang J (2008) Electrochemical sensors, biosensors and their biomedical applications. Elsevier, New York
Njagi J, Andreescu S (2007) Stable enzyme biosensors based on chemically synthesized Au-polypyrrole nanocomposites. Biosens Bioelectron 23(2):168–175. doi:10.1016/j.tet.2006.01.047
Bao SJ, Li CM, Zang JF, Cui XQ, Qiao Y, Guo J (2008) New nanostructured TiO2 for direct electrochemistry and glucose sensor applications. Adv Funct Mater 18(4):591–599. doi:10.1002/adfm.200700728
Xu Y, Liang J, Hu C, Wang F, Hu S, He Z (2007) A hydrogen peroxide biosensor based on the direct electrochemistry of hemoglobin modified with quantum dots. J Biol Inorg Chem 12(3):421–427. doi:10.1007/s00775-006-0198-2
Wang Y, Qian WP, Tan Y, Ding SH, Zhang HQ (2007) Direct electrochemistry and electroanalysis of hemoglobin adsorbed in self-assembled films of gold nanoshells. Talanta 72(3):1134–1140. doi:10.1016/j.talanta.2007.01.026
Acknowledgments
The authors acknowledge the support from the National Natural Science Foundation of China (21443004), the 47th (1792) Scientific Research Foundation for the Returned Overseas Chinese Scholars, the Chunhui planning project (Z2014083), the Ministry of Education, and the Technology Research Project of Chongqing Education Board (KJ1401217).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Zhang, G., Cao, T., Huang, H. et al. Highly hydrophilic ordered mesoporous carbon–organic polymer composite and its applications in direct electrochemistry and the possibility of biosensing1. J Appl Electrochem 46, 593–601 (2016). https://doi.org/10.1007/s10800-016-0944-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10800-016-0944-2