Competitive surface-enhanced Raman scattering assay for the 1,25-dihydroxy metabolite of vitamin D3.

This paper describes the development and preliminary testing of a competitive surface-enhanced Raman scattering (SERS) immunoassay for calcitriol, the 1,25-dihydroxy metabolite (1,25-(OH)(2)-D(3)) of vitamin D(3). Deficiencies in 1,25-(OH)(2)-D have been linked to renal disease, while elevations are linked to hypercalcemia. Thus, there has been a sharp increase in the clinical demand for measurements of this metabolite. The work herein extends the many attributes of SERS-based sandwich immunoassays that have been exploited extensively in the detection of large biolytes (e.g., DNA, proteins, viruses, and microorganisms) into a competitive immunoassay for the low level determination of a small biolyte, 1,25-(OH)(2)-D(3) (M(w) = 416 g mol(-1)). The assay uses surface modified gold nanoparticles as SERS labels, and has a dynamic range of 10-200 pg mL(-1) and a limit of detection of 8.4 ± 1.8 pg mL(-1). These analytical performance metrics match those of tests for 1,25-(OH)(2)-D(3) that rely on radio- or enzyme-labels, while using a much smaller sample volume and eliminating the disposal of radioactive wastes. Moreover, the SERS-based data from pooled-patient sera show strong agreement with that from radioimmunoassays. The merits and potential utility of this new assay are briefly discussed.

[1]  W. Smith,et al.  Assessment of silver and gold substrates for the detection of amphetamine sulfate by surface enhanced Raman scattering (SERS). , 2002, The Analyst.

[2]  Anand Gole,et al.  Surface-enhanced Raman spectroscopy of self-assembled monolayers: sandwich architecture and nanoparticle shape dependence. , 2005, Analytical chemistry.

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

[4]  M. Natan,et al.  Glass-Coated, Analyte-Tagged Nanoparticles: A New Tagging System Based on Detection with Surface-Enhanced Raman Scattering , 2003 .

[5]  Duncan Graham,et al.  SERRS immunoassay for quantitative human CRP analysis. , 2008, The Analyst.

[6]  Ruth Shinar,et al.  Novel biosensor chip for simultaneous detection of DNA-carcinogen adducts with low-temperature fluorescence. , 2004, Biosensors & bioelectronics.

[7]  S. Iqbal,et al.  Vitamin D Metabolism and the Clinical Aspects of Measuring Metabolites , 1994, Annals of clinical biochemistry.

[8]  N. Green,et al.  AVIDIN. 1. THE USE OF (14-C)BIOTIN FOR KINETIC STUDIES AND FOR ASSAY. , 1963, The Biochemical journal.

[9]  M. Natan,et al.  Surface-enhanced Raman scattering: a structure-specific detection method for capillary electrophoresis. , 2000, Analytical chemistry.

[10]  P. D. de Moor,et al.  A radioimmunoassay for 1,25-dihydroxycholecalciferol. , 1978, Clinical chemistry.

[11]  Marc D Porter,et al.  SERS as a bioassay platform: fundamentals, design, and applications. , 2008, Chemical Society reviews.

[12]  D. A. Stuart,et al.  Glucose sensing using near-infrared surface-enhanced Raman spectroscopy: gold surfaces, 10-day stability, and improved accuracy. , 2005, Analytical chemistry.

[13]  M. Porter,et al.  Surface-enhanced Raman scattering immunoassays using a rotated capture substrate. , 2007, Analytical chemistry.

[14]  L. Cabalín,et al.  Flow-injection analysis and liquid chromatography: surface-enhanced Raman spectrometry detection by using a windowless flow cell , 1996 .

[15]  M. Porter,et al.  Low-level detection of viral pathogens by a surface-enhanced Raman scattering based immunoassay. , 2005, Analytical chemistry.

[16]  Yiping Zhao,et al.  The Use of Aligned Silver Nanorod Arrays Prepared by Oblique Angle Deposition as Surface Enhanced Raman Scattering Substrates , 2008 .

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

[18]  Marc D Porter,et al.  Control of antigen mass transport via capture substrate rotation: binding kinetics and implications on immunoassay speed and detection limits. , 2009, Analytical chemistry.

[19]  J. Gershoni,et al.  Biotin binding to avidin. Oligosaccharide side chain not required for ligand association. , 1987, The Biochemical journal.

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

[21]  Yong-Kweon Kim,et al.  Surface-enhanced Raman spectroscopic-encoded beads for multiplex immunoassay. , 2007, Journal of combinatorial chemistry.

[22]  Marc D Porter,et al.  Giant magenetoresistive sensors. 2. Detection of biorecognition events at self-referencing and magnetically tagged arrays. , 2008, Analytical chemistry.

[23]  R. Kumar Vitamin D: Basic And Clinical Aspects , 2011 .

[24]  R. Álvarez-Puebla,et al.  SERS detection of environmental pollutants in humic acid-gold nanoparticle composite materials. , 2007, The Analyst.

[25]  Robert M. Corn,et al.  Covalent Attachment and Derivatization of Poly(l-lysine) Monolayers on Gold Surfaces As Characterized by Polarization−Modulation FT-IR Spectroscopy , 1996 .

[26]  H. Abruña,et al.  Dithiobissuccinimidyl propionate as an anchor for assembling peroxidases at electrodes surfaces and its application in a H2O2 biosensor. , 1999, Analytical chemistry.

[27]  J. Adams Vitamin D metabolite-mediated hypercalcemia. , 1989, Endocrinology and metabolism clinics of North America.

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

[29]  W. Reichert,et al.  Influence of biotin lipid surface density and accessibility on avidin binding to the tip of an optical fiber sensor , 1992 .

[30]  M. Natan,et al.  Surface-enhanced Raman scattering tags for rapid and homogeneous detection of circulating tumor cells in the presence of human whole blood. , 2008, Journal of the American Chemical Society.

[31]  J. Wayment,et al.  Biotin-avidin binding kinetics measured by single-molecule imaging. , 2009, Analytical chemistry.

[32]  D. Fernig,et al.  Determination of size and concentration of gold nanoparticles from UV-vis spectra. , 2007, Analytical chemistry.

[33]  M. Haussler,et al.  Filter assay for 1alpha, 25-dihydroxyvitamin D3. Utilization of the hormone's target tissue chromatin receptor. , 1974, Biochemistry.

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

[35]  M. Porter,et al.  Cetyltrimethylammonium bromide-modified spherical and cube-like gold nanoparticles as extrinsic Raman labels in surface-enhanced Raman spectroscopy based heterogeneous immunoassays. , 2008, Analytical chemistry.

[36]  M. Haussler,et al.  Radioreceptor Assay for 1α,25-Dihydroxyvitamin D3 , 1974, Science.

[37]  R. G. Freeman,et al.  SERS as a Foundation for Nanoscale, Optically Detected Biological Labels , 2007 .

[38]  Marc D Porter,et al.  Control of antigen mass transfer via capture substrate rotation: an absolute method for the determination of viral pathogen concentration and reduction of heterogeneous immunoassay incubation times. , 2006, Journal of virological methods.

[39]  R. Horst,et al.  A microassay for 1,25-dihydroxyvitamin D not requiring high performance liquid chromatography: application to clinical studies. , 1984, The Journal of clinical endocrinology and metabolism.

[40]  Robert J. Lipert,et al.  Impact of Protein Shedding on Detection of Mycobacterium avium subsp. paratuberculosis by a Whole-Cell Immunoassay Incorporating Surface-Enhanced Raman Scattering , 2007, Clinical and Vaccine Immunology.

[41]  Jing Zhao,et al.  Ultrastable substrates for surface-enhanced Raman spectroscopy: Al2O3 overlayers fabricated by atomic layer deposition yield improved anthrax biomarker detection. , 2006, Journal of the American Chemical Society.

[42]  Robert J. Lipert,et al.  Detection of Mycobacterium avium subsp. paratuberculosis by a Sonicate Immunoassay Based on Surface-Enhanced Raman Scattering , 2007, Clinical and Vaccine Immunology.

[43]  Duncan Graham,et al.  Quantitative SERRS immunoassay for the detection of human PSA. , 2009, The Analyst.

[44]  Siegfried Schneider,et al.  Combination of high-performance liquid chromatography and SERS detection applied to the analysis of drugs in human blood and urine , 2004 .

[45]  M. Holick,et al.  Vitamin D deficiency: a worldwide problem with health consequences. , 2008, The American journal of clinical nutrition.