Rapid and sensitive detection of glucose concentrations is very important for human health. Herein, an ultrasensitive photoelectrochemical dual-electron-acceptor biosensor was constructed by modifying the TiO2 nanotubes (NTs) with polydopamine (PDA) and amino-functionalized graphene quantum dots (N-GQDs)/GOx. PDA is grown on the top of the TiO2 NTs by the electropolymerization, and N-GQDs are loaded into the inner of the TiO2 NTs by a microwave-assisted method. The TiO2 NTs/PDA/N-GQD dual-electron-acceptor biosensor exhibited a highly enhanced photoelectric response, excellent electron–hole separation efficiency, low detection limit (0.015 mM), wide linear range (0–11 mM) and ultrahigh sensitivity (13.6 µA mM−1 cm−2). The prepared biosensor reflected high selectivity and excellent stability. This work also provides new insights into other optoelectronic biosensors.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Gratzel M (2001) Photoelectrochemical cells. Nature 414:338–344
Hagfeldt A, Boschloo G, Sun L, Kloo L, Pettersson H (2010) Dye-sensitized solar cells. Chem Rev 110:6595–6663
Osterloh FE (2013) Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting. Chem Soc Rev 42:2294–2320
Drummond TG, Hill MG, Barton JK (2003) Electrochemical DNA sensors. Nat Biotechnol 21:1192–1199
Gill R, Zayats M, Willner I (2008) Semiconductor quantum dots for bioanalysis. Angew Chem Int Ed 47:7602–7625
Yang W, Ratinac KR, Ringer SP, Thordarson P, Gooding JJ, Braet F (2010) Carbon nanomaterials in biosensors: should you use nanotubes or graphene? Angew Chem Int Ed 49:2114–2138
Sljukic B, Banks CE, Compton RG (2006) Iron oxide particles are the active sites for hydrogen peroxide sensing at multiwalled carbon nanotube modified electrodes. Nano Lett 6:1556–1558
Minteer SD, Atanassov P, Luckarift HR, Johnson GR (2012) New materials for biological fuel cells. Mater Today 15:166–173
Lee D, Lee 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 17:2828–2833
Dai H, Zhang S, Gong L, Li Y, Xu G, Lin Y, Hong Z (2015) The photoelectrochemical exploration of multifunctional TiO2 mesocrystals and its enzyme-assisted biosensing application. Biosens Bioelectron 72:18–24
Noell T, Noell G (2011) Strategies for "wiring" redox-active proteins to electrodes and applications in biosensors, biofuel cells, and nanotechnology. Chem Soc Rev 40:3564–3576
Scanlon DO, Dunnill CW, Buckeridge J, Shevlin SA, Logsdail AJ, Woodley SM, Catlow CRA, Powell MJ, Palgrave RG, Parkin IP, Watson GW, Keal TW, Sherwood P, Walsh A, Sokol AA (2013) Band alignment of rutile and anatase TiO2. Nat Mater 12:798–801
Pan D, Xi C, Li Z, Wang L, Chen Z, Luc B, Wu M (2013) Electrophoretic fabrication of highly robust, efficient, and benign heterojunction photoelectrocatalysts based on graphene-quantum-dot sensitized TiO2 nanotube arrays. J Mater Chem A 1:3551–3555
Zhang W, Xu T, Liu Z, Wu N-L, Wei M (2018) Hierarchical TiO2−x imbedded with graphene quantum dots for high-performance lithium storage. Chem Commun 54:1413–1416
Mao W-X, Lin X-J, Zhang W, Chi Z-X, Lyu R-W, Cao A-M, Wan L-J (2016) Core-shell structured TiO2@polydopamine for highly active visible-light photocatalysis. Chem Commun 52:7122–7125
Zhao W-W, Xu J-J, Chen H-Y (2015) Photoelectrochemical bioanalysis: the state of the art. Chem Soc Rev 44:729–741
Sun B, Zhou W, Li H, Ren L, Qiao P, Li W, Fu H (2018) Synthesis of particulate hierarchical tandem heterojunctions toward optimized photocatalytic hydrogen production. Adv Mater. https://doi.org/10.1002/adma.201804282
Lee SY, Lim SY, Seo D, Lee J-Y, Chung TD (2016) Light-driven highly selective conversion of CO2 to formate by electrosynthesized enzyme/cofactor thin film electrode. Adv Energy Mater. https://doi.org/10.1002/aenm.201502207
Aguilar LE, Tumurbaatar B, Ghavaminejad A, Park CH, Kim CS (2017) Functionalized non-vascular nitinol stent via electropolymerized polydopamine thin film coating loaded with bortezomib adjunct to hyperthermia therapy. Sci Rep. https://doi.org/10.1038/s41598-017-08833-x
Lee H, Dellatore SM, Miller WM, Messersmith PB (2007) Mussel-inspired surface chemistry for multifunctional coatings. Science (New York, NY) 318:426–430
Yan Y, Chen J, Li N, Tian J, Li K, Jiang J, Liu J, Tian Q, Chen P (2018) Systematic bandgap engineering of graphene quantum dots and applications for photocatalytic water splitting and CO2 reduction. ACS Nano 12:3523–3532
Qian Y, Yuan Y, Wang H, Liu H, Zhang J, Shi S, Guo Z, Wang N (2018) Highly efficient uranium adsorption by salicylaldoxime/polydopamine graphene oxide nanocomposites. J Mater Chem A 6:24676–24685
Reuillard B, Le Goff A, Holzinger M, Cosnier S (2014) Non-covalent functionalization of carbon nanotubes with boronic acids for the wiring of glycosylated redox enzymes in oxygen-reducing biocathodes. J Mater Chem B 2:2228–2232
Deng X, Zhang H, Guo R, Cui Y, Ma Q, Zhang X, Cheng X, Li B, Xie M, Cheng Q (2018) Effect of fabricating parameters on photoelectrocatalytic performance of CeO2/TiO2 nanotube arrays photoelectrode. Sep Purif Technol 193:264–273
Kim S, Moon G-h, Kim G, Kang U, Park H, Choi W (2017) TiO2 complexed with dopamine-derived polymers and the visible light photocatalytic activities for water pollutants. J Catal 346:92–100
Gnanasekaran L, Hemamalini R, Ravichandran K (2015) Synthesis and characterization of TiO2 quantum dots for photocatalytic application. J Saudi Chem Soc 19:589–594
Atchudan R, Edison TNJI, Perumal S, Vinodh R, Lee YR (2018) In-situ green synthesis of nitrogen-doped carbon dots for bioimaging and TiO2 nanoparticles@nitrogen-doped carbon composite for photocatalytic degradation of organic pollutants. J Alloys Compd 766:12–24
Han Z, Tang Z, Shen S, Zhao B, Zheng G, Yang J (2014) Strengthening of graphene aerogels with tunable density and high adsorption capacity towards Pb2+. Sci Rep. https://doi.org/10.1038/srep05025
Liu H, Xi P, Xie G, Shi Y, Hou F, Huang L, Chen F, Zeng Z, Shao C, Wang J (2012) Simultaneous reduction and surface functionalization of graphene oxide for hydroxyapatite mineralization. J Phys Chem C 116:3334–3341
Zhang R, Chen W (2014) Nitrogen-doped carbon quantum dots: Facile synthesis and application as a "turn-off' fluorescent probe for detection of Hg2+ ions. Biosens Bioelectron 55:83–90
Olivares O, Likhanova N, Gomez B, Navarrete J, Llanos-Serrano M, Arce E, Hallen JJASS (2006) Electrochemical and XPS studies of decylamides of α-amino acids adsorption on carbon steel in acidic environment. Appl Surf Sci 252:2894–2909
Yang H, Zhang X (2009) Synthesis, characterization and computational simulation of visible-light irradiated fluorine-doped titanium oxide thin films. J Mater Chem 19:6907–6914
Ding H, Wei J-S, Xiong H-M (2014) Nitrogen and sulfur co-doped carbon dots with strong blue luminescence. Nanoscale 6:13817–13823
Campos BB, Abellan C, Zougagh M, Jimenez-Jimenez J, Rodriguez-Castellon E, Esteves da Silva JCG, Rios A, Algarra M (2015) Fluorescent chemosensor for pyridine based on N-doped carbon dots. J Colloid Interface Sci 458:209–216
Li H, Kong W, Liu J, Liu N, Huang H, Liu Y, Kang Z (2015) Fluorescent N-doped carbon dots for both cellular imaging and highly-sensitive catechol detection. Carbon 91:66–75
Nurunnabi M, Khatun Z, Nafiujjaman M, Lee D-g, Lee Y-k (2013) Surface coating of graphene quantum dots using mussel-inspired polydopamine for biomedical optical imaging. ACS Appl Mater Interfaces 5:8246–8253
Zhang R, Bao J, Pan Y, Sun C-F (2019) Highly reversible potassium-ion intercalation in tungsten disulfide. Chem Sci 10:2604–2612
Cai J, Huang J, Ge M, Iocozzia J, Lin Z, Zhang K-Q, Lai Y (2017) Immobilization of Pt nanoparticles via rapid and reusable electropolymerization of dopamine on TiO2 nanotube arrays for reversible SERS substrates and nonenzymatic glucose sensors. Small. https://doi.org/10.1002/smll.201604240
Nassef HM, Civit L, Fragoso A, O'Sullivan CK (2009) Amperometric immunosensor for detection of celiac disease toxic gliadin based on fab fragments. Anal Chem 81:5299–5307
Zhang J-J, Kang T-F, Hao Y-C, Lu L-P, Cheng S-Y (2015) Electrochemiluminescent immunosensor based on CdS quantum dots for ultrasensitive detection of microcystin-LR. Sensor Actuat B Chem 214:117–123
Muthuchamy N, Atchudan R, Edison TNJI, Perumal S, Lee YR (2018) High-performance glucose biosensor based on green synthesized zinc oxide nanoparticle embedded nitrogen-doped carbon sheet. J Electroanal Chem 816:195–204
Komathi S, Gopalan AI, Muthuchamy N, Lee KP (2017) Polyaniline nanoflowers grafted onto nanodiamonds via a soft template- guided secondary nucleation process for high-performance glucose sensing. RSC Adv 7:15342–15351
Zhang L, Ruan Y-F, Liang Y-Y, Zhao W-W, Yu X-D, Xu J-J, Cheng H-Y (2018) Bismuth oxyiodide couples with glucose oxidase: a special synergized dual-catalysis mechanism for photoelectrochemical enzymatic bioanalysis. ACS Appl Mater Interfaces 10:3372–3379
Shang M, Qi H, Du C, Huang H, Wu S, Zhang J, Song W (2018) One-step electrodeposition of high-quality amorphous molybdenum sulfide/RGO photoanode for visible-light sensitive photoelectrochemical biosensing. Sensor Actuat B Chem 266:71–79
Wang Y, Bai L, Wang Y, Qin D, Shan D, Lu X (2018) Ternary nanocomposites of Au/CuS/TiO2 for an ultrasensitive photoelectrochemical non-enzymatic glucose sensor. Analyst 143:1699–1704
Liu X, Huo X, Liu P, Tang Y, Xu J, Liu X, Zhou Y (2017) Assembly of MoS2 nanosheet-TiO2 nanorod heterostructure as sensor scaffold for photoelectrochemical biosensing. Electrochim Acta 242:327–336
Ryu GM, Lee M, Choi DS, Park CB (2015) A hematite-based photoelectrochemical platform for visible light-induced biosensing. J Mater Chem B 3:4483–4486
Wu S, Huang H, Shang M, Du C, Wu Y, Song W (2017) High visible light sensitive MoS2 ultrathin nanosheets for photoelectrochemical biosensing. Biosens Bioelectron 92:646–653
This research was financially supported by Key Research and Development Project of Hainan Province (No. ZDYF2018106), National Natural Science Foundation of China (Nos. 51762012, and 51862006) and Key Laboratory Open Project Fund of Hainan University (2018008).
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
About this article
Cite this article
Yang, W., Xu, W., Zhang, N. et al. TiO2 nanotubes modified with polydopamine and graphene quantum dots as a photochemical biosensor for the ultrasensitive detection of glucose. J Mater Sci (2020). https://doi.org/10.1007/s10853-020-04422-y