Abstract
Surface plasmon resonance (SPR) employs a gold (Au) thin film (ca. 50 nm in thickness) chip to generate a surface plasmonic wave (SPW) for in situ monitoring of the interface/surface, which makes it intrinsically compatible with electrochemistry for combined electrochemical surface plasmon resonance (EC-SPR) investigations. However, conventional SPR Au chips suffers from a high background signal, narrow electrochemical window, and limited electrochemical stability. Presented in this work is a novel SPR chip composed of the Au/long-chain alkane thiol self-assembled monolayer/single-layer graphene (Au/SAM/G) sandwich architecture to address these problems. On this chip, the single-layer graphene serves as a working electrode for electrochemical measurement, and the underlying Au film serves as the SPW support for SPR monitoring; the sandwiched thiol monolayer enables the electrical separation of the graphene and Au film to protect the Au film from electrochemical polarization. Our experiment indicates that the electrochemical window of such a chip extends beyond the hydrogen/oxygen evolution reaction potential on Au with significantly improved electrochemical stability and suppressed background signal. Moreover, its intrinsic SPR sensitivity is completely reserved even compared to that of the conventional SPR Au chip. This Au/SAM/G chip may offer a valuable solution to the EC-SPR investigations in harsh conditions.
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References
Liu C, Hu F, Yang W, Xu J, Chen Y. A critical review of advances in surface plasmon resonance imaging sensitivity. TrAC Trends Anal Chem. 2017;97:354–62.
Su YW, Wang W. Surface plasmon resonance sensing: from purified biomolecules to intact cells. Anal Bioanal Chem. 2018;410(17):3943–51.
Liu C, Wang X, Xu J, Chen Y. Chemical strategy to stepwise amplification of signals in surface plasmon resonance imaging detection of saccharides and glycoconjugates. Anal Chem. 2016;88(20):10011–8.
Hinman SS, McKeating KS, Cheng Q. Surface plasmon resonance: material and interface design for universal accessibility. Anal Chem. 2018;90(1):19–39.
Yao X, Yang ML, Wang Y, Hu Z. Study of the ferrocenylalkanethiol self-assembled monolayers by electrochemical surface plasmon resonance. Sensors Actuators B Chem. 2007;122(2):351–6.
Chen D, Zhao L, Hu W. Protein immobilization and fluorescence quenching on polydopamine thin films. J Colloid Interface Sci. 2016;477:123–30.
Hu W, Chen H, Zhang H, He G, Li X, Zhang X, et al. Sensitive detection of multiple mycotoxins by SPRi with gold nanoparticles as signal amplification tags. J Colloid Interface Sci. 2014;431:71–6.
Hu W, He G, Zhang H, Wu X, Li J, Zhao Z, et al. Polydopamine-functionalization of graphene oxide to enable dual signal amplification for sensitive surface plasmon resonance imaging detection of biomarker. Anal Chem. 2014;86(9):4488–93.
Hu W, He G, Chen T, Guo CX, Lu Z, Selvaraj JN, et al. Graphene oxide-enabled tandem signal amplification for sensitive SPRi immunoassay in serum. Chem Commun. 2014;50:2133–5.
Hu W, Liu Y, Lu Z, Li CM. Poly[oligo(ethylene glycol) methacrylate-co-glycidyl methacrylate] brush substrate for sensitive surface plasmon resonance imaging protein arrays. Adv Funct Mater. 2010;20(20):3497–503.
Jung I, Ih S, Yoo H, Hong S, Park S. Fourier transform surface plasmon resonance of nanodisks embedded in magnetic nanorods. Nano Lett. 2018;18(3):1984–92.
Jiang D, Jiang Y, Li Z, Liu T, Wo X, Fang Y, et al. Optical imaging of phase transition and Li-ion diffusion kinetics of single LiCoO2 nanoparticles during electrochemical cycling. J Am Chem Soc. 2017;139(1):186–92.
Chen D, Mei Y, Hu W, Li CM. Electrochemically enhanced antibody immobilization on polydopamine thin film for sensitive surface plasmon resonance immunoassay. Talanta. 2018;182:470–5.
Chen D, Hu W. In situ investigation of electrochemically mediated surface-initiated atom transfer radical polymerization by electrochemical surface plasmon resonance. Anal Chem. 2017;89(8):4355–8.
Verma R, Gupta BD, Jha R. Sensitivity enhancement of a surface plasmon resonance based biomolecules sensor using graphene and silicon layers. Sensors Actuators B Chem. 2011;160(1):623–31.
Singh M, Holzinger M, Tabrizian M, Winters S, Berner NC, Cosnier S, et al. Noncovalently functionalized monolayer graphene for sensitivity enhancement of surface plasmon resonance immunosensors. J Am Chem Soc. 2015;137(8):2800–3.
Gao C, Lu Z, Liu Y, Zhang Q, Chi M, Cheng Q, et al. Highly stable silver nanoplates for surface plasmon resonance biosensing. Angew Chem Int Ed. 2012;51(23):5629–33.
Wang J, Wang F, Zou X, Xu Z, Dong S. Surface plasmon resonance and electrochemistry for detection of small molecules using catalyzed deposition of metal ions on gold substrate. Electrochem Commun. 2007;9(2):343–7.
Linman MJ, Abbas A, Roberts CC, Cheng Q. Etched glass microarrays with differential resonance for enhanced contrast and sensitivity of surface plasmon resonance imaging analysis. Anal Chem. 2011;83(15):5936–43.
Abbas A, Linman MJ, Cheng Q. Patterned resonance plasmonic microarrays for high-performance SPR imaging. Anal Chem. 2011;83(8):3147–52.
Sexton BA, Feltis BN, Davis TJ. Characterisation of gold surface plasmon resonance sensor substrates. Sens Actuators, A. 2008;141(2):471–5.
Szunerits S, Coffinier Y, Janel S, Boukherroub R. Stability of the gold/silica thin film interface: electrochemical and surface plasmon resonance studies. Langmuir. 2006;22(25):10716–22.
Hoogvliet JC, Bennekom WPV. Gold thin-film electrodes: an EQCM study of the influence of chromium and titanium adhesion layers on the response. Electrochim Acta. 2001;47(4):599–611.
Ghorbanpour M, Falamaki C. A novel method for the production of highly adherent Au layers on glass substrates used in surface plasmon resonance analysis: substitution of Cr or Ti intermediate layers with Ag layer followed by an optimal annealing treatment. J Nanostruct Chem. 2013;3(1):66.
Chang CC, Chiu NF, Lin DS, Yu CS, Liang YH, Lin CW. High-sensitivity detection of carbohydrate antigen 15-3 using a gold/zinc oxide thin film surface plasmon resonance-based biosensor. Anal Chem. 2010;82(4):1207–12.
Phillips KS, Wilkop T, Wu JJ, Alkaysi RO, Cheng Q. Surface plasmon resonance imaging analysis of protein-receptor binding in supported membrane arrays on gold substrates with calcinated silicate films. J Am Chem Soc. 2006;128(30):9590–1.
Phillips KS, Han JH, Martinez M, Wang Z, Carter D, Cheng Q. Nanoscale glassification of gold substrates for surface plasmon resonance analysis of protein toxins with supported lipid membranes. Anal Chem. 2006;78(2):596–603.
Hawley MD, Tatawawadi SV, Piekarski S, Adams RN. Electrochemical studies of the oxidation pathways of catecholamines. J Am Chem Soc. 1967;89(2):447–50.
Li S, Liu J, Lu Y, Zhu L, Li C, Hu L, et al. Mutual promotion of electrochemical-localized surface plasmon resonance on nanochip for sensitive sialic acid detection. Biosens Bioelectron. 2018;117:32–9.
Meneghello A, Sonato A, Ruffato G, Zacco G, Romanato F. A novel high sensitive surface plasmon resonance legionella pneumophila sensing platform. Sensors Actuators B Chem. 2017;250:351–5.
Hu X, Zeng M, Long Y, Liu J, Zhu Y, Zou K, et al. Phase conjugated and transparent wavelength conversions of nyquist 16-QAM signals employing a single-layer graphene coated fiber device. Sci Rep. 2016;6:22379.
Wang Y, Shan X, Wang H, Wang S, Tao N. Plasmonic imaging of surface electrochemical reactions of single gold nanowires. J Am Chem Soc. 2017;139(4):1376–9.
Wei W, Nong J, Zhu Y, Zhang G, Wang N, Luo S, et al. Graphene/Au-enhanced plastic clad silica fiber optic surface plasmon resonance sensor. Plasmonics. 2018;13(2):483–91.
Zagorodko O, Spadavecchia J, Serrano AY, Larroulet I, Pesquera A, Zurutuza A, et al. Highly sensitive detection of DNA hybridization on commercialized graphene-coated surface plasmon resonance interfaces. Anal Chem. 2014;86(22):11211–6.
Novoselov KS, Fal'Ko VI, Colombo L, Gellert PR, Schwab MG, Kim K. A roadmap for graphene. Nat. 2012;490:192–200.
Pothipor C, Lertvachirapaiboon C, Shinbo K, Kato K, Kaneko F, Ounnunkad K, et al. Development of graphene oxide/poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) thin film-based electrochemical surface plasmon resonance immunosensor for detection of human immunoglobulin G. Jpn J Appl Phys. 2018;57.
Wei W, Nong J, Mei Y, Zhong C, Lan G, Hu W. Single-layer graphene-coated gold chip for enhanced SPR imaging immunoassay. Sensors Actuators B Chem. 2018;273:1548–55.
Hu W, Lu Z, Liu Y, Li CM. In situ surface plasmon resonance investigation of the assembly process of multiwalled carbon nanotubes on an alkanethiol self-assembled monolayer for efficient protein immobilization and detection. Langmuir. 2010;26(11):8386–91.
Yuan L, Tao N, Wang W. Plasmonic imaging of electrochemical impedance. Ann Rev Anal Chem. 2017;10:183–200.
Zhai P, Guo J, Xiang J, Zhou F. Electrochemical surface plasmon resonance spectroscopy at bilayered silver/gold films. J Phys Chem C. 2007;111(2):981–6.
Liang CP, Gong HR. Fundamental influence of hydrogen on various properties of α-titanium. Int J Hydrog Energy. 2010;35(8):3812–6.
Teter DF, Robertson IM, Birnbaum HK. The effects of hydrogen on the deformation and fracture of β-titanium. Acta Mater. 2001;49(20):4313–23.
Zhang C, Ou Y, Lei WX, Wan LS, Ji J, Xu ZK. CuSO4/H2O2-induced rapid deposition of polydopamine coatings with high uniformity and enhanced stability. Angew Chem. 2016;55(9):3054–7.
Briant CL, Wang ZF, Chollocoop N. Hydrogen embrittlement of commercial purity titanium. Corros Sci. 2002;44(8):1875–88.
Kelly RG, Frost AJ, Shahrabi T, Newman RC. Brittle fracture of an Au/Ag alloy induced by a surface film. Metall Trans A. 1991;22(2):531–41.
Szunerits S, Castel X, Boukherroub R. Surface plasmon resonance investigation of silver and gold films coated with thin indium tin oxide layers: influence on stability and sensitivity. J Phys Chem C. 2008;112(40):15813–7.
Funding
This study was financially supported by the National Natural Science Foundation of China (21273173, 61675037, 61405021), the Natural Science Foundation Project of CQ CSTC (cstc2016jcyjA0493, cstc2017jcyjBX0048), and the Fundamental Research Funds for the Central Universities (XDJK2018B001, 2018CDQYGD0022, cqu2018CDHB1B03).
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Published in the topical collection Young Investigators in (Bio-)Analytical Chemistry with guest editors Erin Baker, Kerstin Leopold, Francesco Ricci, and Wei Wang.
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Mei, Y., Zhong, C., Li, L. et al. Single-layer graphene-coated gold chip for electrochemical surface plasmon resonance study. Anal Bioanal Chem 411, 4577–4585 (2019). https://doi.org/10.1007/s00216-018-1456-1
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DOI: https://doi.org/10.1007/s00216-018-1456-1