Highly sensitive immunoassay of anti-cyclic citrullinated peptide marker using surface-enhanced Raman scattering detection

We report a highly sensitive anti-cyclic citrullinated peptide (anti-CCP) detection method for early diagnosis of rheumatoid arthritis (RA) using surface-enhanced Raman scattering (SERS)-based immunoassay. Herein, cyclic citrullinated peptide (CCP)-conjugated magnetic beads and anti-human IgG-conjugated hollow gold nanospheres (HGNs) were used as substrates and SERS nano-tags, respectively. First, its detection sensitivity was evaluated using anti-CCP standard solutions. Then quantitative anti-CCP levels, determined by the SERS-based assay, were compared with those obtained from three commercially available anti-CCP assay kits (Immunoscan CCPlus, ImmunnLisa™ CCP and BioPlex™ 2200) to assess its potential utility as a clinical tool. Finally, clinical samples from 20 RA patients were investigated using them. In the SERS-based assay, the anti-CCP level in human serum was successfully determined by monitoring the characteristic Raman peak intensity of SERS nano-tags. The diagnostic performance of our SERS-based immunoassay for clinical samples shows a good agreement with those measured by three commercial anti-CCP kits. In addition, our SERS-based assay results are more consistent in the low concentration range (0–25 U/mL) than those achieved by the commercial kits. Accordingly, it is estimated that the SERS-based assay is a potentially useful diagnostic tool for early diagnosis of RA.

[1]  T. S. Alstrøm,et al.  Surface-enhanced Raman spectroscopy based quantitative bioassay on aptamer-functionalized nanopillars using large-area Raman mapping. , 2013, ACS nano.

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

[3]  J. Choo,et al.  Preparation of silica-encapsulated hollow gold nanosphere tags using layer-by-layer method for multiplex surface-enhanced raman scattering detection. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[4]  Frederick Wolfe,et al.  Rheumatoid arthritis , 2010, The Lancet.

[5]  Jian-hui Jiang,et al.  Ag/SiO2 core-shell nanoparticle-based surface-enhanced Raman probes for immunoassay of cancer marker using silica-coated magnetic nanoparticles as separation tools. , 2007, Biosensors & bioelectronics.

[6]  Glenn P. Goodrich,et al.  Controlled texturing modifies the surface topography and plasmonic properties of Au nanoshells. , 2005, The journal of physical chemistry. B.

[7]  Leif O. Brown,et al.  Self-assembly approach to multiplexed surface-enhanced Raman spectral-encoder beads. , 2009, Analytical chemistry.

[8]  N. Wu,et al.  Three-dimensional hierarchical plasmonic nano-architecture enhanced surface-enhanced Raman scattering immunosensor for cancer biomarker detection in blood plasma. , 2013, ACS nano.

[9]  W. Bablok,et al.  A New Biometrical Procedure for Testing the Equality of Measurements from Two Different Analytical Methods. Application of linear regression procedures for method comparison studies in Clinical Chemistry, Part I , 1983, Journal of clinical chemistry and clinical biochemistry. Zeitschrift fur klinische Chemie und klinische Biochemie.

[10]  G. Pruijn,et al.  Anti-CCP antibodies: the past, the present and the future , 2011, Nature Reviews Rheumatology.

[11]  Jaebum Choo,et al.  Simultaneous immunoassay for the detection of two lung cancer markers using functionalized SERS nanoprobes. , 2011, Chemical communications.

[12]  J. Choo,et al.  Highly sensitive immunoassay of lung cancer marker carcinoembryonic antigen using surface-enhanced Raman scattering of hollow gold nanospheres. , 2009, Analytical chemistry.

[13]  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.

[14]  Yukihiro Ozaki,et al.  Fluorescein isothiocyanate linked immunoabsorbent assay based on surface-enhanced resonance Raman scattering. , 2008, Analytical chemistry.

[15]  L. Trouw,et al.  Closing the serological gap: promising novel biomarkers for the early diagnosis of rheumatoid arthritis. , 2012, Autoimmunity reviews.

[16]  M. Liang,et al.  The American Rheumatism Association 1987 revised criteria for the classification of rheumatoid arthritis. , 1988, Arthritis and rheumatism.

[17]  Thomas Huser,et al.  Improving nanoprobes using surface-enhanced Raman scattering from 30-nm hollow gold particles. , 2006, Analytical chemistry.

[18]  Eun Kyu Lee,et al.  SERS-based competitive immunoassay of troponin I and CK-MB markers for early diagnosis of acute myocardial infarction. , 2014, Chemical communications.

[19]  W. Vanvenrooij,et al.  Autoantibodies to citrullinated proteins in rheumatoid arthritis: clinical performance and biochemical aspects of an RA-specific marker. , 2004, Clinica chimica acta; international journal of clinical chemistry.

[20]  Zhen Liu,et al.  A boronate affinity sandwich assay: an appealing alternative to immunoassays for the determination of glycoproteins. , 2014, Angewandte Chemie.

[21]  Bing Yan,et al.  SERS tags: novel optical nanoprobes for bioanalysis. , 2013, Chemical reviews.

[22]  G. Pruijn,et al.  The use of citrullinated peptides and proteins for the diagnosis of rheumatoid arthritis , 2010, Arthritis research & therapy.

[23]  Jaebum Choo,et al.  SERS-based immunoassay of anti-cyclic citrullinated peptide for early diagnosis of rheumatoid arthritis , 2014 .

[24]  M. Trau,et al.  Duplex Microfluidic SERS Detection of Pathogen Antigens with Nanoyeast Single-Chain Variable Fragments , 2014, Analytical chemistry.