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Stamped multilayer graphene laminates for disposable in-field electrodes: application to electrochemical sensing of hydrogen peroxide and glucose

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Abstract

A multi-step approach is described for the fabrication of multi-layer graphene-based electrodes without the need for ink binders or post-print annealing. Graphite and nanoplatelet graphene were chemically exfoliated using a modified Hummers’ method and the dried material was thermally expanded. Expanded materials were used in a 3D printed mold and stamp to create laminate electrodes on various substrates. The laminates were examined for potential sensing applications using model systems of peroxide (H2O2) and enzymatic glucose detection. Within the context of these two assay systems, platinum nanoparticle electrodeposition and oxygen plasma treatment were examined as methods for improving sensitivity. Electrodes made from both materials displayed excellent H2O2 sensing capability compared to screen-printed carbon electrodes. Laminates made from expanded graphite and treated with platinum, detected H2O2 at a working potential of 0.3 V (vs. Ag/AgCl [0.1 M KCl]) with a 1.91 μM detection limit and sensitivity of 64 nA·μM−1·cm−2. Electrodes made from platinum treated nanoplatelet graphene had a H2O2 detection limit of 1.98 μM (at 0.3 V), and a sensitivity of 16.5 nA·μM−1·cm−2. Both types of laminate electrodes were also tested as glucose sensors via immobilization of the enzyme glucose oxidase. The expanded nanographene material exhibited a wide analytical range for glucose (3.7 μM to 9.9 mM) and a detection limit of 1.2 μM. The sensing range of laminates made from expanded graphite was slightly reduced (9.8 μM to 9.9 mM) and the detection limit for glucose was higher (18.5 μM). When tested on flexible substrates, the expanded graphite laminates demonstrated excellent adhesion and durability during testing. These properties make the electrodes adaptable to a variety of tests for field-based or wearable sensing applications.

Expanded graphite (eGR) and expanded nanoplatelet graphene (nGN) were chemically exfoliated, thermally expanded, and manually stamped into flexible multi-layer graphene laminate electrodes. Hydrogen peroxide amperometric testing of eGR laminates compared to nGN laminates and a screen printed carbon (SPC) electrode.

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References

  1. Kimmel DW, LeBlanc G, Meschievitz ME, Cliffel DE (2012) Electrochemical sensors and biosensors. Anal Chem 84(2):685–707. https://doi.org/10.1021/ac202878q

    Article  CAS  PubMed  Google Scholar 

  2. Sokolov AN, Roberts ME, Bao Z (2009) Fabrication of low-cost electronic biosensors. Mater Today 12(9):12–20. https://doi.org/10.1016/s1369-7021(09)70247-0

    Article  Google Scholar 

  3. Renedo OD, Alonso-Lomillo MA, Martinez MJA (2007) Recent developments in the field of screen-printed electrodes and their related applications. Talanta 73(2):202–219. https://doi.org/10.1016/j.talanta.2007.03.050

    Article  CAS  PubMed  Google Scholar 

  4. Hayat A, Marty JL (2014) Disposable screen printed electrochemical sensors: tools for environmental monitoring. Sensors 14(6):10432–10453. https://doi.org/10.3390/s140610432

    Article  CAS  PubMed  Google Scholar 

  5. Brownson D, Banks C (2014) The handbook of graphene electrochemistry. Springer. https://doi.org/10.1007/978-1-4471-6428-9

  6. Bollella P, Fusco G, Tortolini C, Sanzo G, Favero G, Gorton L, Antiochia R (2017) Beyond graphene: electrochemical sensors and biosensors for biomarkers detection. Biosens Bioelectron 89:152–166. https://doi.org/10.1016/j.bios.2016.03.068

    Article  CAS  PubMed  Google Scholar 

  7. Geim AK (2009) Graphene: status and prospects. Science 324(5934):1530–1534. https://doi.org/10.1126/science.1158877

    Article  CAS  PubMed  Google Scholar 

  8. Secor EB, Ahn BY, Gao TZ, Lewis JA, Hersam MC (2015) Rapid and versatile photonic annealing of graphene inks for flexible printed electronics. Adv Mater 27(42):6683–668+. https://doi.org/10.1002/adma.201502866

    Article  CAS  PubMed  Google Scholar 

  9. Celik N, Balachandran W, Manivannan N (2015) Graphene-based biosensors: methods, analysis and future perspectives. IET Circuits Dev Sys 9(6):434–445. https://doi.org/10.1049/iet-cds.2015.0235

    Article  Google Scholar 

  10. Maduraiveeran G, Sasidharan M, Ganesan V (2018) Electrochemical sensor and biosensor platforms based on advanced nanomaterials for biological and biomedical applications. Biosens Bioelectron 103:113–129. https://doi.org/10.1016/j.bios.2017.12.031

    Article  CAS  PubMed  Google Scholar 

  11. Antiochia R, Tortolini C, Tasca F, Gorton L, Bollella P (2018) Chapter 1 - graphene and 2D-like nanomaterials: different biofunctionalization pathways for electrochemical biosensor development. In: Tiwari A (ed) Graphene bioelectronics. Elsevier, pp 1–35. https://doi.org/10.1016/B978-0-12-813349-1.00001-9

    Chapter  Google Scholar 

  12. Ahmad R, Wolfbeis OS, Hahn Y-B, Alshareef HN, Torsi L, Salama KN (2018) Deposition of nanomaterials: a crucial step in biosensor fabrication. Materials Today Communications 17:289–321. https://doi.org/10.1016/j.mtcomm.2018.09.024

    Article  CAS  Google Scholar 

  13. Pumera M, Sánchez S, Ichinose I, Tang J (2007) Electrochemical nanobiosensors. Sensors Actuators B Chem 123(2):1195–1205. https://doi.org/10.1016/j.snb.2006.11.016

    Article  CAS  Google Scholar 

  14. Kitte SA, Gao W, Zholudov YT, Qi L, Nsabimana A, Liu Z, Xu G (2017) Stainless steel electrode for sensitive Luminol Electrochemiluminescent detection of H2O2, glucose, and glucose oxidase activity. Anal Chem 89(18):9864–9869. https://doi.org/10.1021/acs.analchem.7b01939

    Article  CAS  PubMed  Google Scholar 

  15. Miao X, Feng Z, Tian J, Peng X (2014) Glucose detection at attomole levels using dynamic light scattering and gold nanoparticles. SCIENCE CHINA Chem 57(7):1026–1031. https://doi.org/10.1007/s11426-014-5079-x

    Article  CAS  Google Scholar 

  16. Guo X, Liang B, Jian J, Zhang Y, Ye X (2014) Glucose biosensor based on a platinum electrode modified with rhodium nanoparticles and with glucose oxidase immobilized on gold nanoparticles. Microchim Acta 181(5):519–525. https://doi.org/10.1007/s00604-013-1143-z

    Article  CAS  Google Scholar 

  17. Martín-Yerga D, Carrasco-Rodríguez J, Fierro JLG, García Alonso FJ, Costa-García A (2017) Copper-modified titanium phosphate nanoparticles as electrocatalyst for glucose detection. Electrochim Acta 229:102–111. https://doi.org/10.1016/j.electacta.2017.01.143

    Article  CAS  Google Scholar 

  18. Xu Q, Gu S-X, Jin L, Y-e Z, Yang Z, Wang W, Hu X (2014) Graphene/polyaniline/gold nanoparticles nanocomposite for the direct electron transfer of glucose oxidase and glucose biosensing. Sensors Actuators B Chem 190:562–569. https://doi.org/10.1016/j.snb.2013.09.049

    Article  CAS  Google Scholar 

  19. Berger C, Song ZM, Li XB, Wu XS, Brown N, Naud C, Mayou D, Li TB, Hass J, Marchenkov AN, Conrad EH, First PN, de Heer WA (2006) Electronic confinement and coherence in patterned epitaxial graphene. Science 312(5777):1191–1196. https://doi.org/10.1126/science.1125925

    Article  CAS  PubMed  Google Scholar 

  20. Bilek MM, McKenzie DR (2010) Plasma modified surfaces for covalent immobilization of functional biomolecules in the absence of chemical linkers: towards better biosensors and a new generation of medical implants. Biophys Rev 2(2):55–65. https://doi.org/10.1007/s12551-010-0028-1

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. Ren J, Shi W, Li K, Ma Z (2012) Ultrasensitive platinum nanocubes enhanced amperometric glucose biosensor based on chitosan and nafion film. Sensors Actuators B Chem 163(1):115–120. https://doi.org/10.1016/j.snb.2012.01.017

    Article  CAS  Google Scholar 

  22. Mani V, Dinesh B, Chen S-M, Saraswathi R (2014) Direct electrochemistry of myoglobin at reduced graphene oxide-multiwalled carbon nanotubes-platinum nanoparticles nanocomposite and biosensing towards hydrogen peroxide and nitrite. Biosens Bioelectron 53:420–427. https://doi.org/10.1016/j.bios.2013.09.075

    Article  CAS  PubMed  Google Scholar 

  23. Qian J, Yang X, Yang Z, Zhu G, Mao H, Wang K (2015) Multiwalled carbon nanotube@reduced graphene oxide nanoribbon heterostructure: synthesis, intrinsic peroxidase-like catalytic activity, and its application in colorimetric biosensing. J Mater Chem B 3(8):1624–1632. https://doi.org/10.1039/C4TB01702A

    Article  CAS  PubMed  Google Scholar 

  24. Tran TS, Dutta NK, Choudhury NR (2018) Graphene inks for printed flexible electronics: graphene dispersions, ink formulations, printing techniques and applications. Adv Colloid Interf Sci. https://doi.org/10.1016/j.cis.2018.09.003

  25. Hondred J, Stromberg L, Mosher C, Claussen J (2017) High resolution graphene films for electrochemical sensing via inkjet Maskless lithography. ACS Nano. https://doi.org/10.1021/acsnano.7b03554

  26. Secor EB, Gao TZ, Islam AE, Rao R, Wallace SG, Zhu J, Putz KW, Matuyama B, Hersam MC (2017) Enhanced conductivity, adhesion, and environmental stability of printed graphene inks with nitrocellulose. Chem Mater 29(5):2332–2340. https://doi.org/10.1021/acs.chemmater.7b00029

    Article  CAS  Google Scholar 

  27. Das S, Srinivasan S, Stromberg L, He Q, Garland N, Straszheim W, Ajayan P, Balasubramanian G, Claussen J (2017) Superhydrophobic inkjet printed flexible graphene circuits via direct-pulsed laser writing. Nanoscale Advance Article 9:19058–19065. https://doi.org/10.1039/C7NR06213C

  28. Malekpour H, Chang KH, Chen JC, Lu CY, Nika DL, Novoselov KS, Balandin AA (2014) Thermal conductivity of graphene laminate. Nano Lett 14(9):5155–5161. https://doi.org/10.1021/nl501996v

    Article  CAS  PubMed  Google Scholar 

  29. Gao W, Singh N, Song L, Liu Z, Reddy AL, Ci L, Vajtai R, Zhang Q, Wei B, Ajayan PM (2011) Direct laser writing of micro-supercapacitors on hydrated graphite oxide films. Nat Nanotechnol 6(8):496–500. https://doi.org/10.1038/nnano.2011.110

    Article  CAS  PubMed  Google Scholar 

  30. Huang XJ, Leng T, Zhang X, Chen JC, Chang KH, Geim AK, Novoselov KS, Hu ZR (2015) Binder-free highly conductive graphene laminate for low cost printed radio frequency applications. Appl Phys Lett 106(20). https://doi.org/10.1063/1.4919935

  31. Rinaldi A, Proietti A, Tamburrano A, Ciminello M, Sarto MS (2015) Graphene-based strain sensor Array on carbon Fiber composite laminate. IEEE Sensors J 15(12):7295–7303. https://doi.org/10.1109/jsen.2015.2472595

    Article  CAS  Google Scholar 

  32. Huang XJ, Leng T, Georgiou T, Abraham J, Nair RR, Novoselov KS, Hu ZR (2018) Graphene oxide dielectric permittivity at GHz and its applications for wireless humidity sensing. Sci Rep 8. https://doi.org/10.1038/s41598-017-16886-1

  33. Cai W, Lai T, Du H, Ye J (2014) Electrochemical determination of ascorbic acid, dopamine and uric acid based on an exfoliated graphite paper electrode: a high performance flexible sensor. Sens Actuators B Chem 193:492–500. https://doi.org/10.1016/j.snb.2013.12.004

    Article  CAS  Google Scholar 

  34. Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun ZZ, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved synthesis of graphene oxide. ACS Nano 4(8):4806–4814. https://doi.org/10.1021/nn1006368

    Article  CAS  PubMed  Google Scholar 

  35. Reynolds RA, Greinke RA (2001) Influence of expansion volume of intercalated graphite on tensile properties of flexible graphite. Carbon 39(3):479–481. https://doi.org/10.1016/s0008-6223(00)00291-8

    Article  Google Scholar 

  36. Martinkova P, Pohanka M (2015) Biosensors for blood glucose and diabetes diagnosis: evolution, construction, and current status. Anal Lett 48(16):2509–2532. https://doi.org/10.1080/00032719.2015.1043661

    Article  CAS  Google Scholar 

  37. Sato K, Kang WH, Saga K, Sato KT (1989) Biology of sweat glands and their disorders. 1. Normal sweat-gland-function. J Am Acad Dermatol 20(4):537–563. https://doi.org/10.1016/s0190-9622(89)70063-3

    Article  CAS  PubMed  Google Scholar 

  38. Agustini D, Bergamini MF, Marcolino-Junior LH (2017) Tear glucose detection combining microfluidic thread based device, Amperometric biosensor and microflow injection analysis. Biosens Bioelectron 98:161–167. https://doi.org/10.1016/j.bios.2017.06.035

    Article  CAS  PubMed  Google Scholar 

  39. Jurysta C, Bulur N, Oguzhan B, Satman I, Yilmaz TM, Malaisse WJ, Sener A (2009) Salivary glucose concentration and excretion in Normal and diabetic subjects. J Biomed Biotechnol. https://doi.org/10.1155/2009/430426

  40. Chung DDL (2016) A review of exfoliated graphite. J Mater Sci 51(1):554–568. https://doi.org/10.1007/s10853-015-9284-6

    Article  CAS  Google Scholar 

  41. Gu JL, Leng Y, Gao Y, Liu H, Kang FY, Shen WN (2002) Fracture mechanism of flexible graphite sheets. Carbon 40(12):2169–2176. https://doi.org/10.1016/s0008-6223(02)00075-1

    Article  CAS  Google Scholar 

  42. Lu J, Drzal LT, Worden RM, Lee I (2007) Simple fabrication of a highly sensitive glucose biosensor using enzymes immobilized in exfoliated graphite Nanoplatelets Nafion membrane. Chem Mater 19(25):6240–6246. https://doi.org/10.1021/cm702133u

    Article  CAS  Google Scholar 

  43. Dikin DA, Stankovich S, Zimney EJ, Piner RD, Dommett GHB, Evmenenko G, Nguyen ST, Ruoff RS (2007) Preparation and characterization of graphene oxide paper. Nature 448(7152):457–460. https://doi.org/10.1038/nature06016

    Article  CAS  PubMed  Google Scholar 

  44. Ferrari AC (2007) Raman spectroscopy of graphene and graphite: disorder, Electron-phonon coupling, doping and nonadiabatic effects. Solid State Commun 143(1–2):47–57. https://doi.org/10.1016/j.ssc.2007.03.052

    Article  CAS  Google Scholar 

  45. Lotya M, Hernandez Y, King PJ, Smith RJ, Nicolosi V, Karlsson LS, Blighe FM, De S, Wang ZM, McGovern IT, Duesberg GS, Coleman JN (2009) Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions. J Amer Chem Soc 131(10):3611–3620. https://doi.org/10.1021/ja807449u

    Article  CAS  Google Scholar 

  46. Ambrosi A, Chua CK, Latiff NM, Loo AH, Wong CHA, Eng AYS, Bonanni A, Pumera M (2016) Graphene and its electrochemistry - an update. Chem Soc Rev 45(9):2458–2493. https://doi.org/10.1039/c6cs00136j

    Article  PubMed  Google Scholar 

  47. Malekzad H, Sahandi Zangabad P, Mirshekari H, Karimi M, Hamblin Michael R (2017) Noble metal nanoparticles in biosensors: recent studies and applications. Nanotechnol Rev 6:301–329. https://doi.org/10.1515/ntrev-2016-0014

    Article  CAS  PubMed  Google Scholar 

  48. Hrapovic S, Liu Y, Male KB, Luong JHT (2004) Electrochemical biosensing platforms using platinum nanoparticles and carbon nanotubes. Anal Chem 76(4):1083–1088. https://doi.org/10.1021/ac035143t

    Article  CAS  PubMed  Google Scholar 

  49. Saei AA, Dolatabadi JEN, Najafi-Marandi P, Abhari A, de la Guardia M (2013) Electrochemical biosensors for glucose based on metal nanoparticles. TrAC Trends Anal Chem 42:216–227. https://doi.org/10.1016/j.trac.2012.09.011

    Article  CAS  Google Scholar 

  50. Hayashino Y, Fukuhara S, Suzukamo Y, Okamura T, Tanaka T, Ueshima H (2007) Normal fasting plasma glucose levels and type 2 diabetes: the high-risk and population strategy for occupational health promotion (HIPOP-CHP) study. Acta Diabetol 44(3):164–166. https://doi.org/10.1007/s00592-007-0258-2

    Article  CAS  PubMed  Google Scholar 

  51. Rosenbloom AL (2010) Hyperglycemic hyperosmolar state: an emerging pediatric problem. J Pediatr 156(2):180–184. https://doi.org/10.1016/j.jpeds.2009.11.057

    Article  PubMed  Google Scholar 

  52. Lee Y-H, Wong DT (2009) Saliva: an emerging biofluid for early detection of diseases. Am J Dent 22(4):241–248

    PubMed  PubMed Central  Google Scholar 

  53. Gao W, Emaminejad S, Nyein HYY, Challa S, Chen KV, Peck A, Fahad HM, Ota H, Shiraki H, Kiriya D, Lien DH, Brooks GA, Davis RW, Javey A (2016) Fully integrated wearable sensor arrays for multiplexed in situ perspiration analysis. Nature 529(7587):509–50+. https://doi.org/10.1038/nature16521

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  54. Ganguly A, Sharma S, Papakonstantinou P, Hamilton J (2011) Probing the thermal deoxygenation of graphene oxide using high-resolution in situ X-ray-based spectroscopies. J Phys Chem C 115(34):17009–17019. https://doi.org/10.1021/jp203741y

    Article  CAS  Google Scholar 

  55. Duggleby RG (1995) [3] analysis of enzyme progress curves by nonlinear regression. In: Methods in enzymology, vol 249. Academic Press, pp 61–90. https://doi.org/10.1016/0076-6879(95)49031-0

  56. Leatherbarrow RJ (1990) Using linear and non-linear regression to fit biochemical data. Trends Biochem Sci 15(12):455–458. https://doi.org/10.1016/0968-0004(90)90295-M

    Article  PubMed  Google Scholar 

  57. Stroberg W, Schnell S (2016) On the estimation errors of KM and V from time-course experiments using the Michaelis–Menten equation. Biophys Chem 219:17–27. https://doi.org/10.1016/j.bpc.2016.09.004

    Article  CAS  PubMed  Google Scholar 

  58. Yagati AK, Pyun J-C, Min J, Cho S (2016) Label-free and direct detection of C-reactive protein using reduced graphene oxide-nanoparticle hybrid impedimetric sensor. Bioelectrochemistry 107:37–44. https://doi.org/10.1016/j.bioelechem.2015.10.002

    Article  CAS  PubMed  Google Scholar 

  59. Motulsky H, Christopoulos A (2004) Fitting models to biological data using linear and nonlinear regression: a practical guide to curve fitting. Oxford University Press

  60. Mani V, Govindasamy M, Chen S-M, Chen T-W, Kumar AS, Huang S-T (2017) Core-shell heterostructured multiwalled carbon nanotubes@reduced graphene oxide nanoribbons/chitosan, a robust nanobiocomposite for enzymatic biosensing of hydrogen peroxide and nitrite. Sci Rep 7(1):11910. https://doi.org/10.1038/s41598-017-12050-x

    Article  CAS  PubMed  PubMed Central  Google Scholar 

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Acknowledgements

We gratefully acknowledge funding support from the National Science Foundation under award number CBET-1706994 and ECCS-1841649, the National Institute of Food and Agriculture, U.S. Department of Agriculture, award numbers 2018-67011-27989 and 2016-67021-25038, and the Iowa State University Mechanical Engineering Departmental Fund. We would also like to thank Abraham Polonia-Suarez for his help with initial experiments.

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  1. Department of Mechanical Engineering, Iowa State University, Ames, Iowa, 50011, USA

    Loreen R. Stromberg, John A. Hondred, Delaney Sanborn, Carmen Gomes & Jonathan C. Claussen

  2. Department of Chemistry, Iowa State University, Ames, Iowa, 50011, USA

    Deyny Mendivelso-Perez & Emily Smith

  3. Department of Industrial and Systems Engineering, Rochester Institute of Technology, Rochester, New York, 14623, USA

    Srikanthan Ramesh & Iris V. Rivero

  4. Science and Technology Department, Naval Surface Warfare Center, Panama City, Florida, 32407, USA

    Josh Kogot

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Stromberg, L.R., Hondred, J.A., Sanborn, D. et al. Stamped multilayer graphene laminates for disposable in-field electrodes: application to electrochemical sensing of hydrogen peroxide and glucose. Microchim Acta 186, 533 (2019). https://doi.org/10.1007/s00604-019-3639-7

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