Abstract
Surface-enhanced Raman scattering (SERS) coupled with micro- or nanofluidics integrated into optofluidic devices offer many advantages over conventional SERS conducted under static conditions. Higher reproducibility, larger intensity, as well as greater enhancement can be achieved by efficient mixing of analytes and SERS enhancers under a continuous flow. Progress and advances in the past 10 years, including the design of channels and efficient mixing conditions, assemblies of SERS substrates for optimal enhancement, and advantages of optofluidic-SERS analysis, are reviewed. Recent results show that optofluidic-SERS effectively overcomes many of the difficulties and limitations plaguing conventional SERS and the novel technique has enormous application potential.
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References
E. Smith and G. Dent: Modern Raman Spectroscopy-A Practical Approach (John Wiley & Sons Ltd., West Sussex, England, 2005).
B. Schrader: Infrared and Raman Spectroscopy (VCH, Weinheim, Germany, 1995).
C.V. Raman and K.S. Krishnan: A new type of secondary radiation. Nature 121, 501 (1928).
M. Schmitt and J. Popp: Raman spectroscopy at the beginning of the twenty-first century. J. Raman Spectrosc. 37, 20 (2006).
M. Fleischmann, P.J. Hendra, and A.J. McQuillan: Raman spectra of pyridine adsorbed at a silver electrode. Chem. Phys. Lett. 26, 163 (1974).
Y.S. Huh, A.J. Chung, and D. Erickson: Surface enhanced Raman spectroscopy and its application to molecular and cellular analysis. Microfluid. Nanofluid. 6, 285 (2009).
D.L. Jeanmaire and R.P. Van Duyne: Surface Raman spectroelectrochemistry. J. Electroanal. Chem. 84, 1 (1977).
S. Chan, S. Kwon, T.W. Koo, L.P. Lee, and A.A. Berlin: Surface-enhanced Raman scattering of small molecules from silver-coated silicon nanopores. Adv. Mater. 15, 1595 (2003).
W.E. Doering and S. Nie: Spectroscopic tags using dye-embedded nanoparticies and surface-enhanced Raman scattering. Anal. Chem. 75, 6171 (2003).
S.P. Mulvaney, M.D. Musick, C.D. Keating, and M.J. Natan: Glass-coated, analyte-tagged nanoparticles: A new tagging system based on detection with surface-enhanced Raman scattering. Langmuir 19, 4784 (2003).
N.R. Jana: Silver coated gold nanoparticles as new surface enhanced Raman substrate at low analyte concentration. Analyst (Lond.) 128, 954 (2003).
K. Kneipp, H. Kneipp, I. Itzkan, R.R. Dasari, and M.S. Feld: Ultrasensitive chemical analysis by Raman spectroscopy. Chem. Rev. 99, 2957 (1999).
Y. Xu, J. Wu, W. Sun, D. Tao, L. Yang, Z. Song, S. Weng, Z. Xu, R.D. Soloway, D. Xu, and G. Xu: A new mechanism of Raman enhancement and its application. Chemistry 8, 5323 (2002).
P. Kambhampati, A. Campion, and O.K. Song: Probing photoinduced charge transfer at atomically smooth metal surfaces using surface-enhanced Raman scattering. Phys. Status Solidi A: Appl. Res. 75, 233 (1999).
T. Qiu, W.J. Zhang, and P.K. Chu: Recent progress in fabrication of anisotropic nanostructures for surface-enhanced Raman spectroscopy. Recent Pat. Nanotechnol. 3, 10 (2009).
M. Moskovits: Surface enhanced spectroscopy. Rev. Mod. Phys. 57, 783 (1985).
M. Moskovits: Surface-enhanced Raman spectroscopy: A brief retrospective. J. Raman Spectrosc. 36, 485 (2005).
L. Chen and J. Choo: Recent advances in surface-enhanced Raman scattering detection technology for microfluidic chips. Electrophoresis 29, 1815 (2008).
J. Ni, R.J. Lipert, G.B. Dawson, and M.D. Porter: Immunoassay readout method using extrinsic Raman labels adsorbed on immunogold colloids. Anal. Chem. 71, 4903 (1999).
K. Kneipp, Y. Wang, and H. Kneipp: Single molecule detection using surface-enhanced Raman scattering (SERS). Phys. Rev. Lett. 78, 1667 (1997).
K. Kneipp, H. Kneipp, and V.B. Kartha: Detection and identification of a single DNA base molecule using surface-enhanced Raman scattering (SERS). Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 57, 6281 (1998).
S. Nie and R.S. Emory: Probing single molecules and single nanoparticles by surface-enhanced Raman scattering. Science 275, 1102 (1997).
G.T. Taylor, S.K. Sharma, and K. Mohanan: Optimization of a flow-injection sampling system for quantitative-analysis of dilute aqueous-solutions using combined resonance and surface-enhanced Raman-spectroscopy (SERRS). Appl. Spectrosc. 44, 635 (1990).
J.J. Laserna: Combining fingerprinting capability with trace analytical detection: Surface-enhanced Raman spectrometry. Anal. Chim. Acta 283, 607 (1993).
L. He, M.J. Natan, and C.D. Keating: Surface-enhanced Raman scattering: A structure-specific detection method for capillary electrophoresis. Anal. Chem. 72, 5438 (2000).
P.A. Walker, M.D. Morris, M.A. Burns, and B.N. Johnson: Isotachophoretic separations on a microchip: Normal Raman spectroscopy detection. Anal. Chem. 70, 3766 (1998).
R.M. Connatser, M. Cochran, R.J. Harrison, and M.J. Sepaniak: Analytical optimization of nanocomposite surface-enhanced Raman spectroscopy/scattering detection in microfluidic separation devices. Electrophoresis 29, 1441 (2008).
A. Dölle, M.A. Suhm, and H.J. Weingärtner: Anisotropic molecular reorientation of liquid benzene revisited. A study using 13C magnetic relaxation through chemical shift anisotropy and spin rotation. J. Chem. Phys. 94, 3361 (1991).
K. Kneipp, H. Kneipp, R. Manoharan, E.B. Hanlon, I. Itzkan, R.R. Dasari, and M.S. Feld: Extremely large enhancement factors in surface-enhanced Raman scattering for molecules on colloidal gold clusters. Appl. Spectrosc. 52, 1493 (1998).
A. Chehaidar, R. Carles, A. Zwick, C. Meunier, B. Cros, and J. Durand: Chemical bonding analysis of a-SiC: H films by Raman spectroscopy. J. Non-Cryst. Solids 37, 169 (1994).
A. Ehlert and S. Buettgenbach: Automatic sensor system for groundwater monitoring network. Proc. SPIE 3857, 61 (1999).
D. Psaltis, S.R. Quake, and C. Yang: Developing optofluidic technology through the fusion of microfluidics and optics. Nature 442, 381 (2006).
A. Berthod, J.J. Laserna, and J.D. Winefordner: Surface enhanced Raman spectrometry on silver hydrosols studied by flow-injection analysis. Appl. Spectrosc. 41, 1137 (1987).
A. Manz, D.J. Harrison, E.M. Verpoorte, J.C. Fettinger, A. Paulus, H. Lüdi, and H.M. Widmer: Planar chips technology for miniaturization and integration of separation techniques into monitoring systems-capillary electrophoresis on a chip. J. Chromatog. 593, 253 (1992).
T. Park, S. Lee, G.H. Seong, J. Choo, E.K. Lee, Y.S. Kim, W.H. Ji, S.Y. Hwang, D.G. Gweon, and S. Lee: Highly sensitive signal detection of duplex dye-labelled DNA oligonucleotides in a PDMS microfluidic chip: Confocal surface-enhanced Raman spectroscopic study. Lab Chip 5, 437 (2005).
P.C. Lee and D. Meisel: Adsorption and surface-enhanced Raman of dyes on silver and gold sols. J. Phys. Chem. 86, 3391 (1982).
N. Leopold and B. Lendl: A new method for fast preparation of highly surface-enhanced Raman scattering (SERS) active silver colloids at room temperature by reduction of silver nitrate with hydroxylamine hydrochloride. J. Phys. Chem. B 107, 5723 (2003).
L. Gunnarsson, E.J. Bjerneld, H. Xu, S. Petronis, B. Kasemo, and M. Käll: Interparticle coupling effects in nanofabricated substrates for surface-enhanced Raman scattering. Appl. Phys. Lett. 78, 802 (2001).
L.A. Dick, A.D. McFarland, C.L. Haynes, and R.P. Van Duyne: Metal film over nanosphere (MFON) electrodes for surface-enhanced Raman spectroscopy (SERS): Improvements in surface nanostructure stability and suppression of irreversible loss. J. Phys. Chem. B 106, 853 (2002).
K. Faulds, D. Graham, and W.E. Smith: Evaluation of surface-enhanced resonance Raman scattering for quantitative DNA analysis. Anal. Chem. 76, 412 (2004).
H. Wang, C.S. Levin, and N.J. Halas: Nanosphere arrays with controlled sub-10-nm gaps as surface-enhanced Raman spectroscopy substrates. J. Am. Chem. Soc. 127, 14992 (2005).
I.M. White, H. Oveys, and X. Fan: Liquid core optical ring resonator sensors. Opt. Lett. 31, 1319 (2006).
F.T. Docherty, P.B. Monaghan, R. Keir, D. Graham, W.E. Smith, and J.M. Cooper: The first SERRS multiplexing from labelled oligonucleotides in a microfluidics lab-on-a-chip. Chem. Commun. 1, 118 (2004).
I.M. White, J. Gohring, and X. Fan: SERS-based detection in an optofluidic ring resonator platform. Opt. Express 15, 17434 (2007).
P. Measor, L. Seballos, D. Yin, and J.Z. Zhang: On-chip surface-enhanced Raman scattering detection using integrated liquid-core waveguides. Appl. Phys. Lett. 90, 211107 (2007).
I.M. White, S.I. Shapova, H. Zhu, J.D. Suter, S. Lacey, P. Zhang, H. Oveys, L. Brewington, J. Gohring, and X. Fan: Applications of the liquid core optical ring resonator platform. Proc. SPIE 6757, 675707 (2007).
Y.S. Huh and D. Erickson: Aptamer based surface-enhanced Raman scattering detection of vasopressin using multilayer nanotube arrays. Biosens. Bioelectron. 25, 1240 (2010).
D. Choi, T. Kang, H. Cho, Y. Choi, and L.P. Lee: Additional amplifications of SERS via an optofluidic CD-based platform. Lab Chip 9, 239 (2009).
H. Becker and C. Gartner: Polymer microfabrication methods for microfluidic analytical applications. Electrophoresis 21, 12 (2000).
J.M. Ng, I. Gitlin, A.D. Stroock, and G.M. Whitesides: Components for integrated poly(dimethylsiloxane) microfluidic systems. Electrophoresis 23, 3461 (2002).
H. Becker and L.E. Locascio: Polymer microfluidic devices. Talanta 56, 267 (2002).
A.J. deMello: Control and detection of chemical reactions in microfluidic systems. Nature 442, 394 (2006).
S.K. Sia and G.M. Whitesides: Microfluidic devices fabricated in poly(dimethylsiloxane) for biological studies. Electrophoresis 24, 3563 (2003).
N. Ohnishi, W. Satoh, K. Morimoto, J. Fukuda, and H. Suzuki: Automatic electrochemical sequential processing in a microsystem for urea detection. Sens. Actuators, B: Chem. 144, 146 (2010).
E.R. Choban, L.J. Markoski, A. Wieckowski, and P.J.A. Kenis: Microfluidic fuel cell based on laminar flow. J. Power Sources 128, 54 (2004).
N. Kockmann, J. Kastner, and P. Woias: Reactive particle precipitation in liquid microchannel flow. Chem. Eng. J. 135, 110 (2008).
D. Lee, S. Lee, G.H. Seong, J. Choo, E.K. Lee, D.G. Gweon, and S. Lee: Quantitative analysis of methyl parathion pesticides in a polydimethylsiloxane microfluidic channel using confocal surface-enhanced raman spectroscopy. Appl. Spectrosc. 60, 373 (2006).
L.X. Quang, C. Lim, G.H. Seong, J. Choo, K.J. Dob, and S.K. Yoo: A portable surface-enhanced Raman scattering sensor integrated with a lab-on-a-chip for field analysis. Lab Chip 8, 2214 (2008).
D.J. Kim, H.J. Oh, T.H. Park, J.B. Choo, and S.H. Lee: An easily integrative and efficient micromixer and its application to the spectroscopic detection of glucose-catalyst reactions. Analyst (Lond.) 130, 293 (2005).
R.H. Liu, J. Yang, M.Z. Pindera, M. Athavale, and P. Grodzinski: Bubble-induced acoustic micromixing. Lab Chip 2, 151 (2002).
M.H. Oddy, J.G. Santiago, and J.C. Mikkelsen: Electrokinetic instability micromixing. Anal. Chem. 73, 5822 (2001).
Y. Wang, H. Chen, S. Dong, and E. Wang: Surface-enhanced Raman scattering of silver-gold bimetallic nanostructures with hollow interiors. J. Chem. Phys. 125, 044710 (2006).
S.H. Lee, K.C. Bantz, N.C. Lindquist, S.H. Oh, and C.L. Haynes: Self-assembled plasmonic nanohole arrays. Langmuir 25, 13685 (2009).
Z. Luo, W. Yang, A. Peng, Y. Ma, H. Fu, and J. Yao: Net-like assembly of Au nanoparticles as a highly active substrate for surface-enhanced Raman and infrared spectroscopy. J. Phys. Chem. A 113, 2467 (2009).
T. Kang, I. Yoon, J. Kim, H. Ihee, and B. Kim: Au nanowire–Au nanoparticles conjugated system which provides micrometer size molecular sensors. Chemistry 16, 1351 (2010).
T. Qiu, X.L. Wu, J.C. Shen, and P.K. Chu: Silver nanocrystal superlattice coating for molecular sensing by surface-enhanced Raman spectroscopy. Appl. Phys. Lett. 89, 131914 (2006).
T. Qiu, W.J. Zhang, X.Z. Lang, Y.J. Zhou, T.J. Cui, and P.K. Chu: Controlled assembly of highly Raman-enhancing silver nanocap arrays templated by porous anodic alumina membranes. Small 5, 2333 (2009).
M. Fan and A.G. Brolo: Silver nanoparticles self assembly as SERS substrates with near single molecule detection limit. Phys. Chem. Chem. Phys. 11, 7381 (2009).
D.R. Ward, N.K. Grady, C.S. Levin, N.J. Halas, Y.P. Wu, P. Nordlander, and D. Natelson: Electromigrated nanoscale gaps for surface-enhanced Raman spectroscopy. Nano Lett. 7, 1396 (2007).
Q. Min, M.J.L. Santos, E.M. Girotto, A.G. Brolo, and R. Gordon: Localized Raman enhancement from a double-hole nanostructure in a metal film. J. Phys. Chem. C 112, 15098 (2008).
M. Sackmann, S. Bom, T. Balster, and A. Materny: Nanostructured gold surfaces as reproducible substrates for surface-enhanced Raman spectroscopy. J. Raman Spectrosc. 38, 277 (2007).
W.F. Nirode, G.L. Devault, M.J. Sepaniak, and R.O. Cole: On-column surface-enhanced Raman spectroscopy detection in capillary electrophoresis using running buffers containing silver colloidal solutions. Anal. Chem. 72, 1866 (2000).
R.M. Connatser, M. Cochran, R.J. Harrison, and M.J. Sepaniak: Analytical optimization of nanocomposite surface-enhanced Raman spectroscopy/scattering detection in microfluidic separation devices. Electrophoresis 29, 1441 (2008).
W.E. Smith, K. Faulds, and D. Graham: Quantitative surface-enhanced resonance Raman spectroscopy for analysis. Top. Appl. Phys. 103, 381 (2006).
S.E. Bell and N.M. Sirimuthu: Quantitative surface-enhanced Raman spectroscopy. Chem. Soc. Rev. 37, 1012 (2008).
K.R. Ackermann, T. Henkel, and J. Popp: Quantitative online detection of low-concentrated drugs via a SERS microfluidic system. ChemPhysChem 8, 2665 (2007).
R. Tantra, R.J. Brown, and M.J. Milton: Strategy to improve the reproducibility of colloidal SERS. J. Raman Spectrosc. 38, 1469 (2007).
C. McLaughlin, D. MacMillan, C. McCardle, and W.E. Smith: Quantitative analysis of mitoxantrone by surface-enhanced resonance Raman scattering. Anal. Chem. 74, 3160 (2002).
D. Cialla, U. Hubner, H. Schneidewind, R. Moller, and J. Popp: Probing innovative microfabricated substrates for their reproducible SERS activity. ChemPhysChem 9, 758 (2008).
M.J.A. Canada, A.R. Medina, J. Frank, and B. Lendl: Bead injection for surface enhanced Raman spectroscopy: Automated on-line monitoring of substrate generation and application in quantitative analysis. Analyst (Lond.) 127, 1365 (2002).
A. Marz, K.R. Ackermann, D. Malsch, T. Bocklitz, and T.H. Popp: Towards a quantitative SERS approach-online monitoring of analytes in a microfluidic system with isotope-edited internal standards. J. Biophoton. 2, 232 (2009).
J.H. Jung, J. Choo, D.J. Kim, and S. Lee: Quantitative determination of nicotine in a PDMS microfluidic channel using surface enhanced Raman spectroscopy. Bull. Korean Chem. Soc. 27, 277 (2006).
S. Lee, J. Choi, L. Chen, B. Park, J.B. Kyong, G.H. Seong, J. Choo, Y. Lee, K.H. Shin, E.K. Lee, S.W. Joo, and K.H. Lee: Fast and sensitive trace analysis of malachite green using a surface-enhanced Raman microfluidic sensor. Anal. Chim. Acta 590, 139 (2007).
B. Bose, L. Motiwale, and K.V.K. Rao: DNA damage and G2/M arrest in Syrian hamster embryo cells during Malachite green exposure are associated with elevated phosphorylation of ERK1 and JNK1. Cancer Lett. 230, 260 (2005).
A. Stammati, C. Nebbia, I. De Angelis, A.G. Albo, M. Carletti, C. Rebecchi, F. Zampaglioni, and M. Dacasto: Effects of malachite green (MG) and its major metabolite, leucomalachite green (LMG), in two human cell lines. Toxicol. In Vitro 19, 853 (2005).
A. Huebner, M. Srisa-Art, D. Holt, C. Abell, F. Hollfelder, A.J. deMello, and J.B. Edel: Quantitative detection of protein expression in single cells using droplet microfluidics.: Chem. Commun. (Camb.) 12, 1218 (2007).
M. Srisa-Art, A.J. deMello, and J.B. Edel: High-throughput DNA droplet assays using picoliter reactor volumes. Anal. Chem. 79, 6682 (2007).
A. Huebner, S. Sharma, M. Srisa-Art, F. Hollfelder, J.B. Edel, and A.J. deMello: Microdroplets: A sea of applications? Lab Chip 8, 1244 (2008).
M. Srisa-Art, I.C. Bonzani, A. Williams, M.M. Stevens, A.J. deMello, and J.B. Edel: Identification of rare progenitor cells from human periosteal tissue using droplet microfluidics. Analyst (Lond.) 134, 2239 (2009).
M. Srisa-Art, A.J. deMello, and J.B. Edel: High-throughput confinement and detection of single DNA molecules in aqueous microdroplets. Chem. Commun. (Camb.) 43, 6548 (2009).
M. Srisa-Art, D.K. Kang, J. Hong, H. Park, R.J. Leatherbarrow, J.B. Edel, S.I. Chang, and A.J. deMello: Analysis of protein–protein interactions by using droplet-based microfluidics. ChemBioChem 10, 1605 (2009).
K.R. Strehle, D. Cialla, P. Rosch, T. Henkel, M. Kohler, and J. Popp: A reproducible surface-enhanced Raman spectroscopy approach: Online SERS measurements in a segmented microfluidic system. Anal. Chem. 79, 1542 (2007).
G. Wang, C. Lim, L. Chen, H. Chon, J. Choo, J. Hong, and A.J. deMello: Surface-enhanced Raman scattering in nanoliter droplets: Towards high-sensitivity detection of mercury (II) ions. Anal. Bioanal. Chem. 394, 1827 (2009).
C.G. Blatchford, J.R. Campbell, and J.A. Creighton: Plasma resonance-enhanced Raman-scattering by adsorbates on gold colloids: The effects of aggregation. Surf. Sci. 120, 435 (1982).
O. Siiman, L.A. Bumm, R. Callaghan, C.G. Blatchford, and M. Kerker: Surface-enhanced Raman scattering by citrate on colloidal silver. J. Phys. Chem. 87, 1014 (1983).
S.R. Emory, R.A. Jensen, T. Wenda, M. Han, and S.M. Nie: Re-examining the origins of spectral blinking in single-molecule and single-nanoparticle SERS. Faraday Discuss. 132, 249 (2006).
A.D. McFarland, M.A. Young, J.A. Dieringer, and R.P. Van Duyne: Wavelength-scanned surface-enhanced Raman excitation spectroscopy. J. Phys. Chem. B 109, 11279 (2005).
M. Cyrankiewicz, T. Wybranowski, and S. Kruszewski: Study of SERS efficiency of metallic colloidal systems. J. Phys.: Conf. Ser. 79, 012013 (2007).
Y. Yang, S. Matsubara, M. Nogamia, and J. Shi: Controlling the aggregation behavior of gold nanoparticles. Mater. Sci. Eng., B 140, 172 (2007).
A.M. Schwartzberg, C.D. Grant, A. Wolcott, C.E. Talley, T.R. Huser, R. Bogomolni, and J.Z. Zhang: Unique gold nanoparticle aggregates as a highly active surface-enhanced Raman scattering substrate. J. Phys. Chem. B 108, 19191 (2004).
J.D. Guingab, B. Lauly, B.W. Smith, N. Omenetto, and J.D. Winefordner: Stability of silver colloids as substrate for surface enhanced Raman spectroscopy detection of dipicolinic acid. Talanta 74, 271 (2007).
C.C. Busby and J.A. Creighton: Efficient gold and silver electrodes for surface enchanced Raman spectral studies of electrochemical systems: The behavior of pyridine and naphthalene adsorbed on roughened gold electrodes. J. Electroanal. Chem. 140, 379 (1982).
M. Wang, M. Benford, N. Jing, G. Cote, and J. Kameoka: Optofluidic device for ultra-sensitive detection of proteins using surface-enhanced Raman spectroscopy. Microfluid. Nanofluid. 6, 411 (2009).
Y.S. Huh, A.J. Chung, B. Cordovez, and D. Erickson: Enhanced on-chip SERS based biomolecular detection using electrokinetically active microwells. Lab Chip 9, 433 (2008).
L. Tong, M. Righini, M.U. Gonzalez, R. Quidantb, and M. Käll: Optical aggregation of metal nanoparticles in a microfluidic channel for surface-enhanced Raman scattering analysis. Lab Chip 9, 193 (2009).
C. Lim, J. Hong, B.G. Chung, A.J. deMello, and J. Choo: Optofluidic platforms based on surface-enhanced Raman scattering. Analyst (Lond.) 135, 837 (2010).
ACKNOWLEDGMENTS
This work was jointly supported by the National Natural Science Foundation of China under Grant No. 50801013, Natural Science Foundation of Jiangsu Province, China under Grant No. BK2009291, Specialized Research Fund for the Doctoral Program of Higher Education under Grant No. 200802861065, Excellent Young Teachers Program of Southeast University, Hong Kong Research Grants Council (RGC) General Research Fund (GRF) No. CityU 112307, and City University of Hong Kong Strategic Research Grant (SRG) No. 7008009.
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Yin, Y., Qiu, T., Zhang, W. et al. Recent developments in optofluidic-surface-enhanced Raman scattering systems: Design, assembly, and advantages. Journal of Materials Research 26, 170–185 (2011). https://doi.org/10.1557/jmr.2010.18
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DOI: https://doi.org/10.1557/jmr.2010.18