Clinical SERS: are we there yet?

Surface Enhanced Raman Spectroscopy or SERS has witnessed many successes over the past 3 decades, owing particularly to its simplicity of use as well as its highly-multiplexing capability. This article provides an overview of SERS and its applicability in the field of bio-medicine. We will preview recent developments in SERS substrate designs, and the various sensing technologies that are based on the SERS phenomenon. An overview of the clinical applications of SERS is also included. Finally, we provide an opinion on the future trends of this unique spectroscopic technique.

[1]  Ajay Agarwal,et al.  Development of highly reproducible nanogap SERS substrates: comparative performance analysis and its application for glucose sensing. , 2011, Biosensors & bioelectronics.

[2]  Younan Xia,et al.  Synthesis of silver nanostructures with controlled shapes and properties. , 2007, Accounts of chemical research.

[3]  C. Giordano,et al.  Physicochemical investigation of surfactant-coated gold nanoparticles synthesized in the confined space of dry reversed micelles , 2006 .

[4]  S. Retterer,et al.  Free-standing optical gold bowtie nanoantenna with variable gap size for enhanced Raman spectroscopy. , 2010, Nano letters.

[5]  Yang Ren,et al.  Plasmonic/magnetic bifunctional nanoparticles. , 2011, Angewandte Chemie.

[6]  Yue Zhou,et al.  A near-infrared fluorescent heptamethine indocyanine dye with preferential tumor accumulation for in vivo imaging. , 2010, Biomaterials.

[7]  Chit Yaw Fu,et al.  The effect of design parameters of metallic substrate on the reproducibility of SERS measurement for biosensing , 2009, NanoScience + Engineering.

[8]  Dor Ben-Amotz,et al.  Adaptive silver films for detection of antibody-antigen binding. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[9]  Hong-Wu Tang,et al.  Chemical Probing of Single Cancer Cells with Gold Nanoaggregates by Surface-Enhanced Raman Scattering , 2008, Applied spectroscopy.

[10]  Wolfgang Kiefer,et al.  Chemical Effect of SERS with Near‐Infrared Excitation , 1996 .

[11]  M. Moskovits.  Surface-enhanced spectroscopy , 1985 .

[12]  Janina Kneipp,et al.  In vivo molecular probing of cellular compartments with gold nanoparticles and nanoaggregates. , 2006, Nano letters.

[13]  Sung Ju Cho,et al.  Combinatorial synthesis of a triphenylmethine library and their application in the development of surface enhanced Raman scattering (SERS) probes. , 2010, Chemical communications.

[14]  Kiang Wei Kho,et al.  Surface enhanced Raman spectroscopic (SERS) study of saliva in the early detection of oral cancer , 2005, SPIE BiOS.

[15]  Jian-hui Jiang,et al.  Immunoassay using surface-enhanced Raman scattering based on aggregation of reporter-labeled immunogold nanoparticles , 2008, Analytical and bioanalytical chemistry.

[16]  Michael S. Feld,et al.  SURFACE-ENHANCED RAMAN SCATTERING : A NEW TOOL FOR BIOMEDICAL SPECTROSCOPY , 1999 .

[17]  Wei Qian,et al.  Cancer cells assemble and align gold nanorods conjugated to antibodies to produce highly enhanced, sharp, and polarized surface Raman spectra: a potential cancer diagnostic marker. , 2007, Nano letters.

[18]  B. Reinhard,et al.  Identification of Tumor Cells through Spectroscopic Profiling of the Cellular Surface Chemistry , 2010 .

[19]  Alexander Marx,et al.  SERS labels for red laser excitation: silica-encapsulated SAMs on tunable gold/silver nanoshells. , 2009, Angewandte Chemie.

[20]  Eun Kyu Lee,et al.  Highly reproducible immunoassay of cancer markers on a gold-patterned microarray chip using surface-enhanced Raman scattering imaging. , 2011, Biosensors & bioelectronics.

[21]  Z. Alfassi.  On the normalization of a mass spectrum for comparison of two spectra , 2004, Journal of the American Society for Mass Spectrometry.

[22]  Rong Chen,et al.  Gastric cancer detection based on blood plasma surface-enhanced Raman spectroscopy excited by polarized laser light. , 2011, Biosensors & bioelectronics.

[23]  M. Porter,et al.  Femtomolar detection of prostate-specific antigen: an immunoassay based on surface-enhanced Raman scattering and immunogold labels. , 2003, Analytical chemistry.

[24]  Wolfgang Petrich,et al.  Quantitative analysis of serum and serum ultrafiltrate by means of Raman spectroscopy. , 2004, The Analyst.

[25]  Luke P. Lee,et al.  Nanophotonic crescent moon structures with sharp edge for ultrasensitive biomolecular detection by local electromagnetic field enhancement effect. , 2005, Nano letters.

[26]  A. Kudelski.  Analytical applications of Raman spectroscopy. , 2008, Talanta.

[27]  F J García de Abajo,et al.  Optical properties of gold nanorings. , 2003, Physical review letters.

[28]  R. V. Van Duyne,et al.  A glucose biosensor based on surface-enhanced Raman scattering: improved partition layer, temporal stability, reversibility, and resistance to serum protein interference. , 2004, Analytical chemistry.

[29]  K. Kneipp,et al.  One- and two-photon excited optical ph probing for cells using surface-enhanced Raman and hyper-Raman nanosensors. , 2007, Nano letters.

[30]  M. Altaş,et al.  Differentiation of Healthy Brain Tissue and Tumors Using Surface-Enhanced Raman Scattering , 2009, Applied spectroscopy.

[31]  L. Liz‐Marzán,et al.  Homogeneous silica coating of vitreophobic colloids , 1996 .

[32]  D. A. Stuart,et al.  Surface Enhanced Raman Spectroscopy: New Materials, Concepts, Characterization Tools, and Applications , 2005 .

[33]  John Maier,et al.  Raman molecular imaging: a novel spectroscopic technique for diagnosis of bladder cancer in urine specimens. , 2011, European urology.

[34]  Clive G. Wilson,et al.  Surface-Enhanced Raman Scattering Spectroscopy as a Sensitive and Selective Technique for the Detection of Folic Acid in Water and Human Serum , 2008, Applied spectroscopy.

[35]  Kort Travis,et al.  Plasmon resonance coupling of metal nanoparticles for molecular imaging of carcinogenesis in vivo. , 2007, Journal of biomedical optics.

[36]  J. Cooper,et al.  SERS mapping of nanoparticle labels in single cells using a microfluidic chip. , 2010, Chemical communications.

[37]  C. Sow,et al.  An effective surface-enhanced Raman scattering template based on a Ag nanocluster–ZnO nanowire array , 2009, Nanotechnology.

[38]  Joseph Irudayaraj,et al.  Surface-enhanced Raman scattering based nonfluorescent probe for multiplex DNA detection. , 2007, Analytical chemistry.

[39]  A. Haes,et al.  Silica-void-gold nanoparticles: temporally stable surface-enhanced Raman scattering substrates. , 2008, Journal of the American Chemical Society.

[40]  Chun-yang Zhang,et al.  Sensitive detection of nucleic acids with rolling circle amplification and surface-enhanced Raman scattering spectroscopy. , 2010, Analytical chemistry.

[41]  Chit Yaw Fu,et al.  Development of biocompatible SERS nanotag with increased stability by chemisorption of reporter molecule for in vivo cancer detection. , 2010, Biosensors & bioelectronics.

[42]  Younan Xia,et al.  Polyol Synthesis of Silver Nanoparticles: Use of Chloride and Oxygen to Promote the Formation of Single-Crystal, Truncated Cubes and Tetrahedrons , 2004 .

[43]  B. Wilson,et al.  Concentration measurements of multiple analytes in human sera by near-infrared laser Raman spectroscopy. , 1999, Applied optics.

[44]  Yiping Zhao,et al.  Detection of Mycoplasma pneumoniae in Simulated and True Clinical Throat Swab Specimens by Nanorod Array-Surface-Enhanced Raman Spectroscopy , 2010, PLoS ONE.

[45]  Jürgen Popp,et al.  Tumour cell identification by means of Raman spectroscopy in combination with optical traps and microfluidic environments. , 2011, Lab on a chip.

[46]  Melik C Demirel,et al.  Quantitative analysis of creatinine in urine by metalized nanostructured parylene. , 2010, Journal of biomedical optics.

[47]  Andrew G. Glen,et al.  APPL , 2001 .

[48]  Zufang Huang,et al.  Nasopharyngeal cancer detection based on blood plasma surface-enhanced Raman spectroscopy and multivariate analysis. , 2010, Biosensors & bioelectronics.

[49]  Alexander Marx,et al.  Immuno‐Raman microspectroscopy: In situ detection of antigens in tissue specimens by surface‐enhanced Raman scattering , 2006 .

[50]  Yiping Zhao,et al.  Quantitative Surface-Enhanced Raman Spectroscopy Based Analysis of MicroRNA Mixtures , 2009, Applied spectroscopy.

[51]  M. Albrecht,et al.  Anomalously intense Raman spectra of pyridine at a silver electrode , 1977 .

[52]  Jonathan M Cooper,et al.  Plasmonic split-ring resonators as dichroic nanophotonic DNA biosensors. , 2009, Journal of the American Chemical Society.

[53]  Richard P Van Duyne,et al.  Transcutaneous glucose sensing by surface-enhanced spatially offset Raman spectroscopy in a rat model. , 2010, Analytical chemistry.

[54]  Zufang Huang,et al.  Gold Nanoparticle Based Surface-Enhanced Raman Scattering Spectroscopy of Cancerous and Normal Nasopharyngeal Tissues under Near-Infrared Laser Excitation , 2009, Applied spectroscopy.

[55]  Duncan Graham,et al.  Prospects of deep Raman spectroscopy for noninvasive detection of conjugated surface enhanced resonance Raman scattering nanoparticles buried within 25 mm of mammalian tissue. , 2010, Analytical chemistry.

[56]  A. Moore,et al.  Noninvasive MRI-SERS imaging in living mice using an innately bimodal nanomaterial. , 2011, ACS nano.

[57]  Mitchell F. Balish,et al.  New insights into the pathogenesis and detection of Mycoplasma pneumoniae infections. , 2008, Future microbiology.

[58]  Hongxing Xu,et al.  Interparticle coupling effects in nanofabricated substrates for surface-enhanced Raman scattering , 2001 .

[59]  Ines Delfino,et al.  Single-molecule detection of yeast cytochrome c by Surface-Enhanced Raman Spectroscopy. , 2005, Biophysical chemistry.

[60]  C. Mirkin,et al.  Nanoparticles with Raman spectroscopic fingerprints for DNA and RNA detection. , 2002, Science.

[61]  Duncan Graham,et al.  Simple multiplex genotyping by surface-enhanced resonance Raman scattering. , 2002, Analytical chemistry.

[62]  Daniel I. C. Wang,et al.  Seedless, Surfactantless, High-Yield Synthesis of Branched Gold Nanocrystals in HEPES Buffer Solution , 2007 .

[63]  Duncan Graham,et al.  Combining functionalised nanoparticles and SERS for the detection of DNA relating to disease. , 2011, Faraday discussions.

[64]  Huabing Yin,et al.  Characterization of cellular chemical dynamics using combined microfluidic and Raman techniques , 2007, Analytical and bioanalytical chemistry.

[65]  Joseph Irudayaraj,et al.  PCR-free quantification of multiple splice variants in a cancer gene by surface-enhanced Raman spectroscopy. , 2009, The journal of physical chemistry. B.

[66]  Chad A. Mirkin,et al.  DPN-Generated Nanostructures Made of Gold, Silver, and Palladium , 2004 .

[67]  C. Haynes,et al.  Nanosphere Lithography: A Versatile Nanofabrication Tool for Studies of Size-Dependent Nanoparticle Optics , 2001 .

[68]  M. Fleischmann,et al.  Raman spectra of pyridine adsorbed at a silver electrode , 1974 .

[69]  L. J. Guo,et al.  Nanoimprint Lithography: Methods and Material Requirements , 2007 .

[70]  Matthew D. Keller,et al.  Effect of normal variations on disease classification of Raman spectra from cervical tissue. , 2011, The Analyst.

[71]  F. Adrian.  Charge transfer effects in surface‐enhanced Raman scatteringa) , 1982 .

[72]  Eun Kyu Lee,et al.  SERS imaging of HER2-overexpressed MCF7 cells using antibody-conjugated gold nanorods. , 2009, Physical chemistry chemical physics : PCCP.

[73]  Jürgen Popp,et al.  Quantitative online detection of low-concentrated drugs via a SERS microfluidic system. , 2007, ChemPhysChem.

[74]  Hongjie Dai,et al.  Protein microarrays with carbon nanotubes as multicolor Raman labels , 2008, Nature Biotechnology.

[75]  Luke P. Lee,et al.  Aptamer-based SERRS sensor for thrombin detection. , 2008, Nano letters.

[76]  Chi-Hung Lin,et al.  A High Speed Detection Platform Based on Surface-Enhanced Raman Scattering for Monitoring Antibiotic-Induced Chemical Changes in Bacteria Cell Wall , 2009, PloS one.

[77]  A. Shen,et al.  Classification of normal and malignant human gastric mucosa tissue with confocal Raman microspectroscopy and wavelet analysis. , 2008, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[78]  Bernhard Lamprecht,et al.  Optical properties of two interacting gold nanoparticles , 2003 .

[79]  Olga Lyandres,et al.  Rapid detection of an anthrax biomarker by surface-enhanced Raman spectroscopy. , 2005, Journal of the American Chemical Society.

[80]  Egon Matijević,et al.  Preparation of monodispersed metal particles , 1998 .

[81]  Vasilis Ntziachristos,et al.  Performance of the red-shifted fluorescent proteins in deep-tissue molecular imaging applications. , 2008, Journal of biomedical optics.

[82]  S. Zou,et al.  Sensitive carbohydrate detection using surface enhanced Raman tagging. , 2010, Analytical chemistry.

[83]  D. L. Jeanmaire,et al.  Surface raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode , 1977 .

[84]  Weiyang Li,et al.  Dimers of silver nanospheres: facile synthesis and their use as hot spots for surface-enhanced Raman scattering. , 2009, Nano letters.

[85]  Y. Ozaki,et al.  Surface-enhanced Raman scattering for protein detection , 2009, Analytical and bioanalytical chemistry.

[86]  M. Porter,et al.  Immunoassay readout method using extrinsic Raman labels adsorbed on immunogold colloids. , 1999, Analytical chemistry.

[87]  Mads S. Bergholt,et al.  Combining near-infrared-excited autofluorescence and Raman spectroscopy improves in vivo diagnosis of gastric cancer. , 2011, Biosensors & bioelectronics.

[88]  Duncan Graham,et al.  Chemical and bioanalytical applications of surface enhanced Raman scattering spectroscopy. , 2008, Chemical Society reviews.

[89]  S. Retterer,et al.  An integrated portable Raman sensor with nanofabricated gold bowtie array substrates for energetics detection. , 2011, The Analyst.

[90]  Emilia Giorgetti,et al.  Surface-Enhanced Raman Scattering from Copper Nanoparticles Obtained by Laser Ablation , 2011 .

[91]  Matthew D. Keller,et al.  Development of a spatially offset Raman spectroscopy probe for breast tumor surgical margin evaluation. , 2011, Journal of biomedical optics.

[92]  W. Stöber,et al.  Controlled growth of monodisperse silica spheres in the micron size range , 1968 .

[93]  Faraday Discuss , 1985 .

[94]  Sanjiv S. Gambhir,et al.  Multiplexed imaging of surface enhanced Raman scattering nanotags in living mice using noninvasive Raman spectroscopy , 2009, Proceedings of the National Academy of Sciences.

[95]  L. Fonseca,et al.  Biosensors as rapid diagnostic tests for tropical diseases , 2010 .

[96]  C. Mirkin,et al.  Multipole plasmon resonances in gold nanorods. , 2006, The journal of physical chemistry. B.

[97]  Kiang Wei Kho,et al.  Polymer-based microfluidics with surface-enhanced Raman-spectroscopy-active periodic metal nanostructures for biofluid analysis. , 2008, Journal of biomedical optics.

[98]  A. Hohenau,et al.  Multipolar surface plasmon peaks on gold nanotriangles. , 2008, The Journal of chemical physics.

[99]  Yong-mei Wang,et al.  Synthesis of a Au/silica/polymer trilayer composite and the corresponding hollow polymer microsphere with a movable Au core. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[100]  R. Dasari,et al.  Single Molecule Detection Using Surface-Enhanced Raman Scattering (SERS) , 1997 .

[101]  Im Joo Rhyu,et al.  Surface-enhanced Raman scattering imaging of HER2 cancer markers overexpressed in single MCF7 cells using antibody conjugated hollow gold nanospheres. , 2009, Biosensors & bioelectronics.

[102]  Ericka Stricklin-Parker,et al.  Ann , 2005 .

[103]  David R Walt,et al.  Multiplexed spectroscopic detections. , 2008, Annual review of analytical chemistry.

[104]  Marc D Porter,et al.  Competitive surface-enhanced Raman scattering assay for the 1,25-dihydroxy metabolite of vitamin D3. , 2010, The Analyst.

[105]  Andrew A Berlin,et al.  Composite organic-inorganic nanoparticles as Raman labels for tissue analysis. , 2007, Nano letters.

[106]  Signal enhancement of surface enhanced Raman scattering and surface enhanced resonance Raman scattering using in situ colloidal synthesis in microfluidics. , 2010, Analytical chemistry.

[107]  K. S. Krishnan,et al.  A New Type of Secondary Radiation , 1928, Nature.

[108]  Michael H. Huang,et al.  Direct synthesis of branched gold nanocrystals and their transformation into spherical nanoparticles. , 2006, The journal of physical chemistry. B.

[109]  Joseph Irudayaraj,et al.  DNA-gold nanoparticle reversible networks grown on cell surface marker sites: application in diagnostics. , 2011, ACS nano.

[110]  Tuan Vo-Dinh,et al.  Multiplex detection of breast cancer biomarkers using plasmonic molecular sentinel nanoprobes , 2009, Nanotechnology.

[111]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[112]  Sang Woo Han,et al.  High-yield synthesis of multi-branched gold nanoparticles and their surface-enhanced Raman scattering properties. , 2009, Journal of colloid and interface science.

[113]  M. Olivo,et al.  Multiplex cancer cell detection by SERS nanotags with cyanine and triphenylmethine Raman reporters. , 2011, Chemical communications.

[114]  Dmitri Petrov,et al.  Diffusion and cellular uptake of drugs in live cells studied with surface-enhanced Raman scattering probes. , 2010, Journal of biomedical optics.