Silver nanoprism etching-based plasmonic ELISA for the high sensitive detection of prostate-specific antigen.

Ultrasensitive and quantitative detection using simple and low-cost assays is critical in clinical diagnostics. In this report, we developed a triangular silver nanoprism (AgNPRs) etching-based plasmonic biosensor for the detection of cancer biomarkers. The triangular AgNPRs-based plasmonic biosensor is an enzyme-linked immunosorbent assay combined with the enzyme-mediated surface plasmon resonance (SPR) of triangular AgNPRs. Triangular AgNPRs uses the immune response of prostate-specific antigen (PSA) to trigger the glucose oxidase (GOx)-catalysed oxidation of glucose (Glu), producing hydrogen peroxide. Hydrogen peroxide acts as an oxidant to etch the triangular AgNPRs into smaller spherical silver nanoparticles, which is accompanied by a substantial blueshift of the SPR peak and a colourimetric blue-to-purple change that can be observed by the naked eye. The SPR peak shift enables the quantitative assessment of PSA due to the remarkable colour change. The triangular AgNPRs-based plasmonic ELISA approach exhibited a quasilinear response to logarithmic PSA concentrations in the range of 10fg/mL to 100pg/mL with a limit of detection (LOD) of 4.1fg/mL. In addition, the LOD of PSA in this approach exceeds that of the conventional HRP-based ELISA (1.25ng/mL) approach by more than 5 orders of magnitude. Patient serum samples from 16 donors were assayed with triangular AgNPRs-based plasmonic ELISA. The results from the triangular AgNPRs-based immunoassay and the time-resolved fluorescence immunoassay showed excellent correlation, and there were no significant differences in the quantified amounts of PSA. The triangular AgNPRs-based plasmonic ELISA approach has advantages (ultrasensitive, cost-effective, ease of operation) that are expected to be of great interest in diagnostics and to be suitable for a point-of-care test.

[1]  Luis M Liz-Marzán,et al.  Enzymatic etching of gold nanorods by horseradish peroxidase and application to blood glucose detection. , 2014, Nanoscale.

[2]  Chunhai Fan,et al.  Graphene-based nanoprobes and a prototype optical biosensing platform. , 2013, Biosensors & bioelectronics.

[3]  Younan Xia,et al.  Shape-controlled synthesis of metal nanostructures: the case of silver. , 2005, Chemistry.

[4]  Bhavya Sharma,et al.  Molecular plasmonics for nanoscale spectroscopy. , 2014, Chemical Society reviews.

[5]  Yucheng Huang,et al.  Facet dependent binding and etching: ultra-sensitive colorimetric visualization of blood uric acid by unmodified silver nanoprisms. , 2014, Biosensors & bioelectronics.

[6]  P. Campíns-Falcó,et al.  Sensitive and selective plasmonic assay for spermine as biomarker in human urine. , 2014, Analytical chemistry.

[7]  Xiaohua Huang,et al.  Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine. , 2008, Accounts of chemical research.

[8]  Xiaogang Liu,et al.  Improving colorimetric assays through protein enzyme-assisted gold nanoparticle amplification. , 2012, Accounts of chemical research.

[9]  Arben Merkoçi,et al.  Enhanced gold nanoparticle based ELISA for a breast cancer biomarker. , 2010, Analytical chemistry.

[10]  Zhiqiang Gao,et al.  A highly sensitive plasmonic DNA assay based on triangular silver nanoprism etching. , 2014, ACS nano.

[11]  Liang Tang,et al.  Magnetic nanoparticle mediated enhancement of localized surface plasmon resonance for ultrasensitive bioanalytical assay in human blood plasma. , 2013, Analytical chemistry.

[12]  Roberto de la Rica,et al.  Plasmonic ELISA for the detection of analytes at ultralow concentrations with the naked eye , 2013, Nature Protocols.

[13]  Dingbin Liu,et al.  Glucose Oxidase-Catalyzed Growth of Gold Nanoparticles Enables Quantitative Detection of Attomolar Cancer Biomarkers , 2014, Analytical chemistry.

[14]  Younan Xia,et al.  Facile synthesis of Ag nanocubes and Au nanocages , 2007, Nature Protocols.

[15]  Ulrich Hohenester,et al.  Highly sensitive plasmonic silver nanorods. , 2011, ACS nano.

[16]  Lingxin Chen,et al.  Highly sensitive and selective colorimetric sensing of Hg2+ based on the morphology transition of silver nanoprisms. , 2013, ACS applied materials & interfaces.

[17]  Chad A Mirkin,et al.  Colloidal gold and silver triangular nanoprisms. , 2009, Small.

[18]  F. Gu,et al.  Branching and size of CTAB-coated gold nanostars control the colorimetric detection of bacteria , 2014 .

[19]  Gang Niu,et al.  Acetylcholinesterase-catalyzed hydrolysis allows ultrasensitive detection of pathogens with the naked eye. , 2013, Angewandte Chemie.

[20]  Molly M Stevens,et al.  Plasmonic ELISA for the ultrasensitive detection of disease biomarkers with the naked eye. , 2012, Nature nanotechnology.

[21]  Paresh Chandra Ray,et al.  Ultrasensitive and highly selective detection of Alzheimer's disease biomarker using two-photon Rayleigh scattering properties of gold nanoparticle. , 2009, ACS nano.

[22]  Joseph Wang,et al.  Ultrasensitive electrical biosensing of proteins and DNA: carbon-nanotube derived amplification of the recognition and transduction events. , 2004, Journal of the American Chemical Society.

[23]  Dingbin Liu,et al.  Gold nanoparticle-based activatable probe for sensing ultralow levels of prostate-specific antigen. , 2013, ACS nano.

[24]  J. Liu,et al.  Enzyme-antibody dual labeled gold nanoparticles probe for ultrasensitive detection of κ-casein in bovine milk samples. , 2014, Biosensors & bioelectronics.

[25]  Indira Hewlett,et al.  Nanoparticle-based immunoassays for sensitive and early detection of HIV-1 capsid (p24) antigen. , 2010, The Journal of infectious diseases.

[26]  A. Coovadia,et al.  Evaluation of the Ultrasensitive Human Immunodeficiency Virus Type 1 (HIV-1) p24 Antigen Assay Performed on Dried Blood Spots for Diagnosis of HIV-1 Infection in Infants , 2007, Clinical and Vaccine Immunology.

[27]  Michael H. Huang,et al.  Shape‐Controlled Synthesis of Polyhedral Nanocrystals and Their Facet‐Dependent Properties , 2012 .

[28]  Young Keun Kim,et al.  A highly sensitive and selective diagnostic assay based on virus nanoparticles. , 2009, Nature nanotechnology.

[29]  C. Che,et al.  Oxidative dissolution of silver nanoparticles by biologically relevant oxidants: a kinetic and mechanistic study. , 2010, Chemistry, an Asian journal.

[30]  I. Willner,et al.  Cysteine-mediated aggregation of Au nanoparticles: the development of a H2O2 sensor and oxidase-based biosensors. , 2013, ACS nano.

[31]  Miaofang Chi,et al.  Highly stable silver nanoplates for surface plasmon resonance biosensing. , 2012, Angewandte Chemie.

[32]  Younan Xia,et al.  Dissolving Ag from Au-Ag Alloy Nanoboxes with H(2)O(2): A Method for Both Tailoring the Optical Properties and Measuring the H(2)O(2) Concentration. , 2010, The journal of physical chemistry. C, Nanomaterials and interfaces.

[33]  H. Klocker,et al.  Nanoparticle-based bio-barcode assay redefines “undetectable” PSA and biochemical recurrence after radical prostatectomy , 2009, Proceedings of the National Academy of Sciences.

[34]  Haili He,et al.  Enzymatic Plasmonic Engineering of Ag/Au Bimetallic Nanoshells and Their Use for Sensitive Optical Glucose Sensing , 2012, Advanced materials.

[35]  Luis M Liz-Marzán,et al.  Plasmonic nanosensors with inverse sensitivity by means of enzyme-guided crystal growth. , 2018, Nature materials.

[36]  C. Sönnichsen,et al.  Multiplexed plasmon sensor for rapid label-free analyte detection. , 2013, Nano letters.

[37]  Na Li,et al.  A systematic study of the synthesis of silver nanoplates: is citrate a "magic" reagent? , 2011, Journal of the American Chemical Society.

[38]  David M. Rissin,et al.  Single-Molecule enzyme-linked immunosorbent assay detects serum proteins at subfemtomolar concentrations , 2010, Nature Biotechnology.

[39]  R F Oulton,et al.  Active nanoplasmonic metamaterials. , 2012, Nature materials.

[40]  Molly M Stevens,et al.  Plasmonic nanomaterials for biodiagnostics. , 2014, Chemical Society reviews.

[41]  Shouzhuo Yao,et al.  A plasmonic blood glucose monitor based on enzymatic etching of gold nanorods. , 2013, Chemical communications.

[42]  Rong Huang,et al.  Plasmonic ELISA for the ultrasensitive detection of Treponema pallidum. , 2014, Biosensors & bioelectronics.

[43]  Chad A. Mirkin,et al.  Drivers of biodiagnostic development , 2009, Nature.

[44]  X. Wang,et al.  Modified enzyme-linked immunosorbent assay strategy using graphene oxide sheets and gold nanoparticles functionalized with different antibody types. , 2013, Analytical chemistry.

[45]  J. Storhoff,et al.  Selective colorimetric detection of polynucleotides based on the distance-dependent optical properties of gold nanoparticles. , 1997, Science.

[46]  Jochen Feldmann,et al.  Label-free biosensing based on single gold nanostars as plasmonic transducers. , 2010, ACS nano.

[47]  Jingjing Ye,et al.  Colorimetric visualization of glucose at the submicromole level in serum by a homogenous silver nanoprism-glucose oxidase system. , 2013, Analytical chemistry.

[48]  M. Kappes,et al.  Gold mesostructures with tailored surface topography and their self-assembly arrays for surface-enhanced Raman spectroscopy. , 2010, Nano letters.