Abstract
A temperature-responsive biosensing film consisting of the temperature-responsive block co-polymer poly (N-isopropylacrylamide)-b-poly(2-acrylamidoethyl benzoate) (referred to as PNIPAM-b-PAAE), graphene oxide (GO), and hemoglobin (Hb) was fabricated and used to modify a glassy carbon electrode (GCE). The film provides a favorable micro-environment for Hb to facilitate the electron transfer to the GCE. Hb at PNIPAM-b-PAAE/GO/Hb (PGH) film exhibits a couple of well-defined redox peaks with a formal potential of −0.371 V (vs. SCE) and displays intrinsic electro-catalytic activity toward H2O2. The sensing film also shows temperature-tunable catalytic activity toward H2O2 that can be stimulated by temperature. Large peak currents can be seen in amperometry at 0.4 V (vs. SCE) in pH 7.0 phosphate buffer only if the temperature is above the lower critical solution temperature (LCST) of 32 °C. The response of the modified GCE is linear in the 0.1 to 3.7 μmol L−1 concentration range if operated at above 32 °C, but in the 0.2 to 3.7 μmol L−1 concentration range at below 30 °C. This behavior is attributed to the temperature-dependent phase transition of PNIPAM-b-PAAE and cooperative effect of GO. The strategy presented here in our perception meets the requirements of switchable sensors for use in bioscience and biotechnology.
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Shan W, He P, Hu N (2005) Electrocatalytic reduction of nitric oxide and other substrates on hydrogel triblock copolymer pluronic films containing hemoglobin or myoglobin based on protein direct electrochemistry. Electrochim Acta 51:432–440
Åsberg P, Inganäs O (2003) Hydrogels of a conducting conjugated polymer as 3-D enzyme electrode. Biosens Bioelectron 19:199–207
Berlin P, Klemm D, Jung A, et al. (2003) Film-forming aminocellulose derivatives as enzyme-compatible support matrices for biosensor developments. Cellulose 10:343–367
Liu H, Rusling JF, Hu N (2004) Electroactive core-shell nanocluster films of heme proteins, polyelectrolytes, and silica nanoparticles. Langmuir 20:10700–10705
Choi J, Rubner MF (2005) Influence of the degree of ionization on weak polyelectrolyte multilayer assembly. Macromolecules 38:116–124
Sugihara S, Kanaoka S, Aoshima S (2005) Double thermosensitive diblock copolymers of vinyl ethers with pendant oxyethylene groups: unique physical gelation. Macromolecules 38:1919–1927
Garcia A, Marquez M, Cai T, Rosario R, et al. (2007) Photo-, thermally, and pH-responsive microgels. Langmuir 23:224–229
Samanta S, Locklin J (2008) Formation of photochromic spiropyran polymer brushes via surface-initiated, ring-opening metathesis polymerization: reversible photocontrol of wetting behavior and solvent dependent morphology changes. Langmuir 24:9558–9565
Walcarius A, Minteer SD, Wang J, Lin Y, Merkoçi A (2013) Nanomaterials for bio-functionalized electrodes: recent trends. J Mater Chem B 1:4878–4908
Dou Y, Han J, Wang T, Wei M, et al. (2012) Temperature-controlled electrochemical switch based on layered double hydroxide/poly(N-isopropylacrylamide) ultrathin films fabricated via layer-by-layer assembly. Langmuir 28:9535–9542
Wan P, Chen Y, Xing Y, Chi L, Zhang X (2010) Combining host-guest systems with nonfouling material for the fabrication of a biosurface: toward nearly complete and reversible resistance of cytochrome c. Langmuir 26:12515–12517
Zhou J, Lu X, Hu J, Li J (2007) Reversible immobilization and direct electron transfer of cytochrome c on a pH-sensitive polymer interface. Chem Eur J 13:2847–2853
Song S, Hu N (2010) "On-off" switchable bioelectrocatalysis synergistically controlled by temperature and sodium sulfate concentration based on poly(N-isopropylacrylamide) films. J Phys Chem B 114:5940–5945
Yehezkeli O, Moshe M, Tel-Vered R, et al. (2010) Switchable photochemical/electrochemical wiring of glucose oxidase with electrodes. Analyst 135:474–476
Fulghum TM, Estillore NC, Vo C-D, et al. (2008) Stimuli-responsive polymer ultrathin films with a binary architecture: combined layer-by-layer polyelectrolyte and surface-initiated polymerization approach. Macromolecules 41:429–435
Hodneland CD, Mrksich M (2000) Biomolecular surfaces that release ligands under electrochemical control. J Am Chem Soc 122:4235–4236
Lion-Dagan M, Katz E, Willner I (1994) A bifunctional monolayer electrode consisting of 4-pyridyl sulfide and photoisomerizable spiropyran: photoswitchable electrical communication between the electrode and cytochrome C. J Chem Soc Chem Commun:2741–2742
Chen D, Feng H, J L (2012) Graphene oxide: preparation, functionalization, and electrochemical applications. Chem Rev 112:6027–6053
Yue R, Lu Q, Zhou Y (2011) A novel nitrite biosensor based on single-layer graphene nanoplatelet–protein composite film. Biosens Bioelectron 26:4436–4441
Liu Y, Yu D, Zeng C, et al. (2011) Biocompatible graphene oxide-based glucose biosensors. Langmuir 26:6158–6160
Fujishige S, Kubota K, Ando I (1989) Phase transition of aqueous solutions of poly(N-iso propylacrylamide) and poly(N-isopropylmethacrylamide). J Phys Chem 93:3311–3313
Katsumoto Y, Tanaka T, Sato H, Ozaki Y (2002) Conformational change of poly(N-isopropyl acrylamide) during the coil − globule transition investigated by attenuated total reflection/infrared spectroscopy and density functional theory calculation. J Phys Chem A 106:3429–3435
Riedinger A, Leal MP, Deka SR, et al. (2011) “Nanohybrids” based on pH-responsive hydrogels and inorganic nanoparticles for drug delivery and sensor applications. Nano Lett 11:3136–3141
Katz E, Willner I (2005) A quinone-functionalized electrode in conjunction with hydrophobic magnetic nanoparticles acts as a "write-read-erase" information storage system. Chem Commun 45:5641–5643
Zhao X, Liu Y, Lu J, et al. (2012) Temperature-responsive polymer/carbon nanotube hybrids: smart conductive nanocomposite films for modulating the bioelectrocatalysis of NADH. Chem Eur J 18:3687–3694
WS HJ, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1339
Zhou Y, Chen C, Zhao J, Fei J, Ding Y, Cai Y (2016) Reversible switched detection of dihydroxybenzenes using a temperature-sensitive electrochemical sensing film. Electrochim Acta 192:158–166
Lu L, Zhang H, Yang N, Cai Y (2006) Toward rapid and well-controlled ambient temperature RAFT polymerization under UV − vis radiation: effect of radiation wave range. Macromolecules 39:3770–3776
TK T, Pita M, Trotsenko O, et al. (2010) Reversible "closing" of an electrode interface functionalized with a polymer brush by an electrochemical signal. Langmuir 26:4506–4513
Muirhead H, Perutz MF (1963) Structure of hemoglobin. A three-dimensional Fourier synthesis of reduced human hemoglobin at 5.5 Å resolution. Nature 199:633–638
Laviron E (1979) General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J Electroanal Chem 101:19–28
Bai J, Wu L, Wang X, Zhang HM (2015) Hemoglobin-graphene modified carbon fiber microelectrode for direct electrochemistry and electrochemical H2O2 sensing. Electrochim Acta 185:142–147
Liu R, Han Y, Nie F, et al. (2014) Direct electrochemistry of hemoglobin and its biosensing for hydrogen peroxide on TiO2–polystyrene nanofilms. J Iran Chem Soc 11:1569–1577
Baccarin M, Janegitz BC, Berté, et al. (2015) Direct electrochemistry of hemoglobin and biosensing for hydrogen peroxide using a film containing silver nanoparticles and poly(amidoamine) dendrimer. Mater Sci Eng C 58:97–102
Baghayeri M, Zare EN, Lakouraj MM (2015) Monitoring of hydrogen peroxide using a glassy carbon electrode modified with hemoglobin and a polypyrrole-based nanocomposite. Microchim Acta 182:771–779
He S, Qiu W, Wang L, et al. (2016) Hollow MnS nanospheres as electron transfer promoters of hemoglobin and their electrochemical sensing applications. J Mater Sci:1–14. doi:10.1007/s10853-016-9996-2
Baghayeri M, Veisi H (2015) Fabrication of a facile electrochemical biosensor for hydrogen peroxide using efficient catalysis of hemoglobin on the porous Pd@Fe3O4-MWCNT nanocomposite. Biosens Bioelectron 74:190–198
Yu CM, Guo JW, Gu HY (2009) Direct electrochemical behavior of hemoglobin at surface of Au@Fe3O4 magnetic nanoparticles. Microchim Acta 166:215–220
Li F, Nie M, He X (2014) Direct electrochemistry and electrocatalysis of hemoglobin on a glassy carbon electrode modified with poly(ethylene glycol diglycidyl ether) and gold nanoparticles on a quaternized cellulose support. A sensor for hydrogen peroxide and nitric oxide. Microchim Acta 181:1541–1549
Xuan J, Jia XD, Jing LP, et al. (2012) Gold nanoparticle-assembled capsules and their application as hydrogen peroxide biosensor based on hemoglobin. Bioelectrochemistry 84:32–37
Chen S, Yuan R, Chai Y, Hu F (2013) Electrochemical sensing of hydrogen peroxide using metal nanoparticles: a review. Microchim Acta 180:15–32
Acknowledgments
This research was financially supported by the NSF of China (Grants No. 21475114 and 21275123), Program for Changjiang Scholars and Innovative Research Team in University (1337304), Project of Hunan provincial natural science Foundation of China (14JJ1019), Research fund for the doctoral program of higher education of china, Ministry of education of China (20134301110005).
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Zhou, Y., Cao, J., Zhao, J. et al. Temperature-responsive amperometric H2O2 biosensor using a composite film consisting of poly(N-isopropylacrylamide)-b-poly (2-acrylamidoethyl benzoate), graphene oxide and hemoglobin. Microchim Acta 183, 2501–2508 (2016). https://doi.org/10.1007/s00604-016-1893-5
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DOI: https://doi.org/10.1007/s00604-016-1893-5