Label-free Detection of Proteins from Dried-suspended Droplets Using Surface Enhanced

A simple sample preparation method to obtain rich and reproducible surface-enhanced Raman scattering (SERS) spectra from proteins regardless of their surface properties and dimensions for label-free detection and identification is reported. The method uses colloidal silver nanoparticles (AgNPs) as substrates and is based on suspending the droplet of a mixture containing AgNPs and proteins from a hydrophobic surface. Drying the droplet at this suspended configuration allows the accumulation and packing of AgNPs and protein molecules in the middle of the droplet area rather than getting jammed at the edges of drying droplets as the solvent evaporates. A detection limit of down to 0.05 μg mL(-1) for some of the model proteins used in this study is obtained with this simple approach. The advantage of this method is its simplicity and improved sensitivity over other approaches reported in the literature.

[1]  Peter M. Fredericks,et al.  Surface-enhanced Raman spectroscopy of peptides and proteins adsorbed on an electrochemically prepared silver surface , 1999 .

[2]  Mustafa Çulha,et al.  Characterization of Thermophilic Bacteria Using Surface-Enhanced Raman Scattering , 2008, Applied spectroscopy.

[3]  Mustafa Culha,et al.  Differential separation of protein mixtures using convective assembly and label-free detection with surface enhanced Raman scattering. , 2011, Chemical communications.

[4]  Louis E. Brus,et al.  Single Molecule Raman Spectroscopy at the Junctions of Large Ag Nanocrystals , 2003 .

[5]  Mustafa Culha,et al.  Label-free detection of proteins from self-assembled protein-silver nanoparticle structures using surface-enhanced Raman scattering. , 2010, Analytical chemistry.

[6]  Mustafa Culha,et al.  Rapid identification of bacteria and yeast using surface‐enhanced Raman scattering , 2010 .

[7]  Yi Cheng,et al.  Mixing intensification by chaotic advection inside droplets for controlled nanoparticle preparation , 2010 .

[8]  J. M. Worlock,et al.  Surface picosecond raman gain spectroscopy of a cyanide monolayer on silver , 1979 .

[9]  Chih-Ming Ho,et al.  Minimal size of coffee ring structure. , 2010, The journal of physical chemistry. B.

[10]  R. Larson,et al.  Marangoni effect reverses coffee-ring depositions. , 2006, The journal of physical chemistry. B.

[11]  Wei Song,et al.  Detection of proteins on silica-silver core-shell substrates by surface-enhanced Raman spectroscopy. , 2011, Journal of colloid and interface science.

[12]  Mustafa Çulha,et al.  Convective assembly of bacteria for surface-enhanced Raman scattering. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[13]  D. Meisel,et al.  Adsorption and surface-enhanced Raman of dyes on silver and gold sols , 1982 .

[14]  Ou Dong,et al.  Silver nanoparticles as surface-enhanced Raman substrate for quantitative identification of label-free proteins , 2011 .

[15]  A. Agostino,et al.  Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy , 2014 .

[16]  Tuan Vo-Dinh,et al.  Surface-enhanced Raman scattering substrate based on a self-assembled monolayer for use in gene diagnostics. , 2003, Analytical chemistry.

[17]  M. Dillon Lasers in surgery and medicine : a review of selected topics , 1991 .

[18]  Yukihiro Ozaki,et al.  Analytical technique for label-free multi-protein detection based on Western blot and surface-enhanced Raman scattering. , 2008, Analytical chemistry.

[19]  M. Dresselhaus,et al.  Surface-enhanced and normal stokes and anti-stokes Raman spectroscopy of single-walled carbon nanotubes. , 2000, Physical review letters.

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

[21]  Manuel Cardona,et al.  Light Scattering in Solids VII , 1982 .

[22]  Burghardt Wittig,et al.  Novel optical nanosensors for probing and imaging live cells. , 2010, Nanomedicine : nanotechnology, biology, and medicine.

[23]  D. Bostwick,et al.  Current evaluation of the tissue localization and diagnostic utility of prostate specific membrane antigen , 1998, Cancer.

[24]  D. Chan,et al.  Proteomics and bioinformatics approaches for identification of serum biomarkers to detect breast cancer. , 2002, Clinical chemistry.

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

[26]  Xu,et al.  Electromagnetic contributions to single-molecule sensitivity in surface-enhanced raman scattering , 2000, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[27]  Siu Kai Kong,et al.  Surface-enhanced Raman scattering biosensor for DNA detection on nanoparticle island substrates. , 2009, Applied optics.

[28]  Jeffrey S. Morris,et al.  Reproducibility of SELDI-TOF protein patterns in serum: comparing datasets from different experiments , 2004, Bioinform..

[29]  Thomas E. Furtak,et al.  Surface-Enhanced Raman Scattering , 1982 .

[30]  Mustafa Culha,et al.  Characterization of Yeast Species Using Surface-Enhanced Raman Scattering , 2009, Applied spectroscopy.

[31]  S. Qu,et al.  Quantitative surface enhanced Raman scattering detection based on the "sandwich" structure substrate. , 2011, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[32]  Dor Ben-Amotz,et al.  Raman detection of proteomic analytes. , 2003, Analytical chemistry.

[33]  Yukihiro Ozaki,et al.  Experimental parameters for the SERS of nitrate ion for label‐free semi‐quantitative detection of proteins and mechanism for proteins to form SERS hot sites: a SERS study , 2011 .

[34]  K. Takano,et al.  Growth of large protein crystals by a large‐scale hanging‐drop method , 2010 .

[35]  D. Weitz,et al.  Fractal structures formed by kinetic aggregation of aqueous gold colloids , 1984 .

[36]  Troy A Alexander Development of methodology based on commercialized SERS-active substrates for rapid discrimination of Poxviridae virions. , 2008, Analytical chemistry.

[37]  M. Çulha,et al.  Assembly of nanoparticles at the contact line of a drying droplet under the influence of a dipped tip. , 2011, Journal of colloid and interface science.

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

[39]  H. Tashiro,et al.  Efficient Characterization for Protein Crystals Using Confocal Raman Spectroscopy , 2007, Applied spectroscopy.

[40]  M. Çulha,et al.  Silver nanoparticle thin films with nanocavities for surface-enhanced Raman scattering. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[41]  Yukihiro Ozaki,et al.  Label-free highly sensitive detection of proteins in aqueous solutions using surface-enhanced Raman scattering. , 2009, Analytical chemistry.

[42]  Yiping Zhao,et al.  Rapid and sensitive detection of respiratory virus molecular signatures using a silver nanorod array SERS substrate. , 2006, Nano letters.

[43]  S. Bell,et al.  Surface-enhanced Raman spectroscopy (SERS) for sub-micromolar detection of DNA/RNA mononucleotides. , 2006, Journal of the American Chemical Society.

[44]  Michael S. Feld,et al.  Surface-Enhanced Raman Spectroscopy in Single Living Cells Using Gold Nanoparticles , 2002 .

[45]  N. Ichikawa,et al.  Investigation of Marangoni and natural convection during protein crystal growth , 2003 .

[46]  Faraday Discuss , 1985 .

[47]  B. Krauskopf,et al.  Proc of SPIE , 2003 .

[48]  T. Dupont,et al.  Capillary flow as the cause of ring stains from dried liquid drops , 1997, Nature.

[49]  Francesco De Angelis,et al.  Nano-patterned SERS substrate: application for protein analysis vs. temperature. , 2009, Biosensors & bioelectronics.

[50]  F. Angelis,et al.  Principal component analysis based methodology to distinguish protein SERS spectra , 2011 .

[51]  A. Lindahl,et al.  Sustained embryoid body formation and culture in a non-laborious three dimensional culture system for human embryonic stem cells , 2011, Cytotechnology.

[52]  C. Y. Chen,et al.  Giant Raman scattering by pyridine and CN− adsorbed on silver , 1979 .

[53]  Vladimir P. Safonov,et al.  Spectral Dependence of Selective Photomodification in Fractal Aggregates of Colloidal Particles , 1998 .

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

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

[56]  Chad A Mirkin,et al.  Raman dye-labeled nanoparticle probes for proteins. , 2003, Journal of the American Chemical Society.