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TiO2 nanotubes modified with polydopamine and graphene quantum dots as a photochemical biosensor for the ultrasensitive detection of glucose

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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.

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  1. 1

    Gratzel M (2001) Photoelectrochemical cells. Nature 414:338–344

  2. 2

    Hagfeldt A, Boschloo G, Sun L, Kloo L, Pettersson H (2010) Dye-sensitized solar cells. Chem Rev 110:6595–6663

  3. 3

    Osterloh FE (2013) Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting. Chem Soc Rev 42:2294–2320

  4. 4

    Drummond TG, Hill MG, Barton JK (2003) Electrochemical DNA sensors. Nat Biotechnol 21:1192–1199

  5. 5

    Gill R, Zayats M, Willner I (2008) Semiconductor quantum dots for bioanalysis. Angew Chem Int Ed 47:7602–7625

  6. 6

    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

  7. 7

    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

  8. 8

    Minteer SD, Atanassov P, Luckarift HR, Johnson GR (2012) New materials for biological fuel cells. Mater Today 15:166–173

  9. 9

    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

  10. 10

    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

  11. 11

    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

  12. 12

    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

  13. 13

    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

  14. 14

    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

  15. 15

    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

  16. 16

    Zhao W-W, Xu J-J, Chen H-Y (2015) Photoelectrochemical bioanalysis: the state of the art. Chem Soc Rev 44:729–741

  17. 17

    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.

  18. 18

    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.

  19. 19

    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.

  20. 20

    Lee H, Dellatore SM, Miller WM, Messersmith PB (2007) Mussel-inspired surface chemistry for multifunctional coatings. Science (New York, NY) 318:426–430

  21. 21

    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

  22. 22

    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

  23. 23

    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

  24. 24

    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

  25. 25

    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

  26. 26

    Gnanasekaran L, Hemamalini R, Ravichandran K (2015) Synthesis and characterization of TiO2 quantum dots for photocatalytic application. J Saudi Chem Soc 19:589–594

  27. 27

    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

  28. 28

    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.

  29. 29

    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

  30. 30

    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

  31. 31

    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

  32. 32

    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

  33. 33

    Ding H, Wei J-S, Xiong H-M (2014) Nitrogen and sulfur co-doped carbon dots with strong blue luminescence. Nanoscale 6:13817–13823

  34. 34

    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

  35. 35

    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

  36. 36

    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

  37. 37

    Zhang R, Bao J, Pan Y, Sun C-F (2019) Highly reversible potassium-ion intercalation in tungsten disulfide. Chem Sci 10:2604–2612

  38. 38

    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.

  39. 39

    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

  40. 40

    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

  41. 41

    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

  42. 42

    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

  43. 43

    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

  44. 44

    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

  45. 45

    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

  46. 46

    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

  47. 47

    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

  48. 48

    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

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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).

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Correspondence to Jinchun Tu.

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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).

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