Immunoassay of Tumor Markers Based on Graphene Surface-Enhanced Raman Spectroscopy.

With a unique chemical enhancement capability, graphene oxide is exceptionally suitable to serve as an alternative surface-enhanced Raman scattering (SERS) substrate, which is usually defined as GERS. However, such a GERS matrix with both promising uniformity and molecule enrichment ability has not been applied in the quantitative detection of tumor markers. Herein, an ultrasensitive and specific immunoassay of carcinoembryonic antigens mediated by the GERS matrix was demonstrated. With the assistance of Au NRs as immunoprobes, a reliable limit of detection as low as 3.01 pg/mL was finally achieved because of the collective effect of chemical and electromagnetic enhancements. Meanwhile, a calibration curve with a high R2 value of 0.996 was obtained in the range from 1 μg/mL to 10 pg/mL. These results exhibit that the GERS matrix has a great promise for participating in immunoassay, which may pave a potential avenue for the real utilization of the SERS technique in clinical biomedicine.

[1]  Xiaoling Zhang,et al.  Recyclable label-free SERS-based immunoassay of PSA in human serum mediated by enhanced photocatalysis arising from Ag nanoparticles and external magnetic field , 2020 .

[2]  Weike Wang,et al.  Branched TiO2 Nanorod Arrays Decorated with Au Nanostructure for Plasmon-Enhanced Photoelectrochemical Water Splitting , 2020 .

[3]  M. Correa‐Duarte,et al.  Dual biorecognition by combining molecularly-imprinted polymer and antibody in SERS detection. Application to carcinoembryonic antigen. , 2019, Biosensors & bioelectronics.

[4]  G. He,et al.  Facile fabrication of Ag/graphene oxide/TiO2 nanorod array as a powerful substrate for photocatalytic degradation and surface-enhanced Raman scattering detection , 2019, Applied Catalysis B: Environmental.

[5]  Yu-Chie Chen,et al.  Gold nanocluster-based fluorescence sensing probes for detection of dipicolinic acid. , 2019, The Analyst.

[6]  Xiuli Fu,et al.  A graphene oxide/gold nanoparticle-based amplification method for SERS immunoassay of cardiac troponin I. , 2019, The Analyst.

[7]  L. Petti,et al.  Classification analyses for prostate cancer, benign prostate hyperplasia and healthy subjects by SERS-based immunoassay of multiple tumour markers. , 2018, Talanta.

[8]  D. Cui,et al.  Graphene oxide wrapped with gold nanorods as a tag in a SERS based immunoassay for the hepatitis B surface antigen , 2018, Microchimica Acta.

[9]  C. Zhang,et al.  A novel natural surface-enhanced Raman spectroscopy (SERS) substrate based on graphene oxide-Ag nanoparticles-Mytilus coruscus hybrid system , 2018 .

[10]  A. Wee,et al.  Raman enhancement on ultra-clean graphene quantum dots produced by quasi-equilibrium plasma-enhanced chemical vapor deposition , 2018, Nature Communications.

[11]  Weifeng Huang,et al.  Remarkable SERS Activity Observed from Amorphous ZnO Nanocages. , 2017, Angewandte Chemie.

[12]  Zhonghua Ma,et al.  Rational Design of Wide Spectral-Responsive Heterostructures of Au Nanorod Coupled Ag3PO4 with Enhanced Photocatalytic Performance. , 2017, ACS applied materials & interfaces.

[13]  Huanting Wang,et al.  Bilayer composites consisting of gold nanorods and titanium dioxide as highly sensitive and self-cleaning SERS substrates , 2017, Microchimica Acta.

[14]  Li Li,et al.  Determination of Carcinoembryonic Antigen by Surface-Enhanced Raman Spectroscopy Using Gold Nanobowl Arrays , 2017 .

[15]  Jian-Jun Li,et al.  Detecting glucose by using the Raman scattering of oxidized ascorbic acid: The effect of graphene oxide–gold nanorod hybrid , 2016 .

[16]  Xiaolong Wang,et al.  Bifunctional 4MBA mediated recyclable SERS-based immunoassay induced by photocatalytic activity of TiO2 nanotube arrays. , 2016, Physical chemistry chemical physics : PCCP.

[17]  Luo Wenbo,et al.  Surface-Enhanced Raman Scattering Immunoassay for Carcinoembryonic Antigen Based on Gold Nanostars , 2016 .

[18]  Yi Wang,et al.  Fe3O4@Graphene Oxide@Ag Particles for Surface Magnet Solid-Phase Extraction Surface-Enhanced Raman Scattering (SMSPE-SERS): From Sample Pretreatment to Detection All-in-One. , 2016, ACS applied materials & interfaces.

[19]  Chao Zhang,et al.  Facile synthesis of large-area and highly crystalline WS2 film on dielectric surfaces for SERS , 2016 .

[20]  Yanbin Wang,et al.  Self-assembly of mildly reduced graphene oxide monolayer for enhanced Raman scattering , 2016 .

[21]  Liyong Chen,et al.  Engineering aggregation-induced SERS-active porous Au@ZnS multi-yolk–shell structures for visualization of guest species loading , 2016 .

[22]  Guanhong Xu,et al.  Detection of CEA in human serum using surface-enhanced Raman spectroscopy coupled with antibody-modified Au and γ-Fe₂O₃@Au nanoparticles. , 2016, Journal of pharmaceutical and biomedical analysis.

[23]  Lianhui Wang,et al.  Combination assay of lung cancer associated serum markers using surface-enhanced Raman spectroscopy. , 2016, Journal of materials chemistry. B.

[24]  Shana O Kelley,et al.  Aptamer and Antisense-Mediated Two-Dimensional Isolation of Specific Cancer Cell Subpopulations. , 2016, Journal of the American Chemical Society.

[25]  Zhenyu Hou,et al.  Exploration of the value of MRCP combined with tumor marker CA19-9 in the diagnosis of pancreatic cancer , 2016, Artificial cells, nanomedicine, and biotechnology.

[26]  Shikuan Yang,et al.  Ultrasensitive surface-enhanced Raman scattering detection in common fluids , 2015, Proceedings of the National Academy of Sciences.

[27]  Jian Dong,et al.  Multiplexing determination of lung cancer biomarkers using electrochemical and surface-enhanced Raman spectroscopic techniques , 2015 .

[28]  R. Zare,et al.  Polypyrrole nanoparticles for tunable, pH-sensitive and sustained drug release. , 2015, Nanoscale.

[29]  Hongjun Wang,et al.  Rational design of Au nanorods assemblies for highly sensitive and selective SERS detection of prostate specific antigen , 2015 .

[30]  Jian Dong,et al.  SERS tags-based novel monodispersed hollow gold nanospheres for highly sensitive immunoassay of CEA , 2015, Journal of Materials Science.

[31]  Tao Jiang,et al.  Silver nanocube-mediated sensitive immunoassay based on surface-enhanced Raman scattering assisted by etched silicon nanowire arrays. , 2014, The Analyst.

[32]  Y. Chai,et al.  Enhanced SERS Stability of R6G Molecules with Monolayer Graphene , 2014 .

[33]  Kenneth T. V. Grattan,et al.  Gold nanorod-based localized surface plasmon resonance biosensors: A review , 2014 .

[34]  Nannan Mao,et al.  Graphene: a platform for surface-enhanced Raman spectroscopy. , 2013, Small.

[35]  Liu Yong,et al.  One-pot, green, rapid synthesis of flowerlike gold nanoparticles/reduced graphene oxide composite with regenerated silk fibroin as efficient oxygen reduction electrocatalysts. , 2013, ACS applied materials & interfaces.

[36]  Wen Ren,et al.  A binary functional substrate for enrichment and ultrasensitive SERS spectroscopic detection of folic acid using graphene oxide/Ag nanoparticle hybrids. , 2011, ACS nano.

[37]  Yi Lv,et al.  Highly sensitive immunoassay based on immunogold-silver amplification and inductively coupled plasma mass spectrometric detection. , 2011, Analytical chemistry.

[38]  Jing Kong,et al.  Can graphene be used as a substrate for Raman enhancement? , 2010, Nano letters.

[39]  Yiping Cui,et al.  Highly sensitive immunoassay based on Raman reporter-labeled immuno-Au aggregates and SERS-active immune substrate. , 2009, Biosensors & bioelectronics.

[40]  Y. Ozaki,et al.  Protein-mediated sandwich strategy for surface-enhanced Raman scattering: application to versatile protein detection. , 2009, Analytical chemistry.

[41]  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.

[42]  A. W. Contryman,et al.  Atomic and electronic structure of graphene-oxide. , 2009, Nano letters.

[43]  Yongsheng Chen,et al.  High-Efficiency Loading and Controlled Release of Doxorubicin Hydrochloride on Graphene Oxide , 2008 .

[44]  N. Pieczonka,et al.  Single molecule analysis by surfaced-enhanced Raman scattering. , 2008, Chemical Society reviews.

[45]  S. Ghosh,et al.  Biomolecule induced nanoparticle aggregation: effect of particle size on interparticle coupling. , 2007, Journal of colloid and interface science.

[46]  R. Broll,et al.  Diagnosis and Monitoring of Colorectal Cancer by L6 Blood Serum Polymerase Chain Reaction Is Superior to Carcinoembryonic Antigen–Enzyme-Linked Immunosorbent Assay , 2003, Diseases of the colon and rectum.

[47]  Mostafa A. El-Sayed,et al.  Preparation and Growth Mechanism of Gold Nanorods (NRs) Using Seed-Mediated Growth Method , 2003 .

[48]  Alexander McPherson,et al.  The three-dimensional structure of an intact monoclonal antibody for canine lymphoma , 1992, Nature.

[49]  J. Coligan,et al.  Electron microscopy and physical characterization of the carcinoembryonic antigen. , 1975, Biochemistry.

[50]  Alankar Shrivastava,et al.  Methods for the determination of limit of detection and limit of quantitation of the analytical methods , 2011 .