A label-free electrochemiluminescence immunosensor based on KNbO3-Au nanoparticles@Bi2S3 for the detection of prostate specific antigen.

A high sensitive label-free electrochemiluminescence (ECL) immunosensor was fabricated for the detection of prostate specific antigen (PSA) based on potassium niobate-Au nanoparticles@bismuth sulfide (KNbO3-Au NPs@Bi2S3) modified glassy carbon electrode (GCE). The prepared Bi2S3 nanosheets exhibited strong and stable cathodic ECL activity. The synthesized KNbO3-Au NPs was firstly used to fabricate ECL modified electrodes and Bi2S3 nanosheets worked as luminophores for the first time in ECL sensors. Au NPs were used to combine with Bi2S3 and anti-PSA via the Au-S covalent bond and Au-NH2 covalent bond without the usage of crosslinking agents respectively, further enhancing the sensitivity and stability of immunosensor. Under the optimum experimental conditions, the ECL signal of KNbO3-Au NPs@Bi2S3 linearly decreased with the increase of PSA concentration in the range of 0.005-5 ng/mL with a detection limit of 3 pg/mL. The preparated label-free ECL immunosensor exhibited high sensitivity and selectivity, good repeatability and long-term stability. The applicability of the proposed ECL immunosensor was also evaluated by detecting PSA in real samples.

[1]  Minghui Yang,et al.  Colorimetric platform for visual detection of cancer biomarker based on intrinsic peroxidase activity of graphene oxide. , 2011, Biosensors & bioelectronics.

[2]  Bing Sun,et al.  Effective signal-on photoelectrochemical immunoassay of subgroup J avian leukosis virus based on Bi2S3 nanorods as photosensitizer and in situ generated ascorbic acid for electron donating. , 2014, Biosensors & bioelectronics.

[3]  Yanbin Li,et al.  AFM and impedance spectroscopy characterization of the immobilization of antibodies on indium-tin oxide electrode through self-assembled monolayer of epoxysilane and their capture of Escherichia coli O157:H7. , 2005, Biosensors & bioelectronics.

[4]  Z. Ye,et al.  Synthesis and second harmonic generation response of KNbO3 nanoneedles , 2012 .

[5]  Hailing Hu,et al.  Optoelectronic properties of chemically deposited Bi2S3 thin films and the photovoltaic performance of Bi2S3/P3OT solar cells , 2012 .

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

[7]  Z. Chang,et al.  Highly sensitive electrogenerated chemiluminescence (ECL) method for famotidine with pre-anodizing technique to improve ECL reaction microenvironment at graphite electrode surface , 2006 .

[8]  A. Bard,et al.  Electrogenerated Chemiluminescence of CdSe Nanocrystals , 2002 .

[9]  Feng Yu,et al.  Electrochemical biosensor based on graphene oxide-Au nanoclusters composites for L-cysteine analysis. , 2012, Biosensors & bioelectronics.

[10]  Linqin Jiang,et al.  Potassium niobate nanostructures: controllable morphology, growth mechanism, and photocatalytic activity , 2013 .

[11]  Minghui Yang,et al.  Ultrasensitive immunosensor for the detection of cancer biomarker based on graphene sheet. , 2010, Biosensors & bioelectronics.

[12]  Yang-Wei Lin,et al.  DNA functionalized gold nanoparticles for bioanalysis. , 2009, Analytical methods : advancing methods and applications.

[13]  Lindsay E. Pell,et al.  Electrochemistry and Electrogenerated Chemiluminescence from Silicon Nanocrystal Quantum Dots , 2002, Science.

[14]  Bibhutosh Adhikary,et al.  Single source precursor approach to the synthesis of Bi2S3 nanoparticles: A new amperometric hydrogen peroxide biosensor , 2014 .

[15]  Ute Kaiser,et al.  Deactivation of a Au/CeO2 catalyst during the low-temperature water-gas shift reaction and its reactivation : A combined TEM, XRD, XPS, DRIFTS, and activity study , 2007 .

[16]  H. Cui,et al.  A label-free electrochemiluminescence aptasensor for thrombin based on novel assembly strategy of oligonucleotide and luminol functionalized gold nanoparticles. , 2013, Biosensors & bioelectronics.

[17]  A. Bard,et al.  Effect of Surface Passivation on the Electrogenerated Chemiluminescence of CdSe/ZnSe Nanocrystals , 2003 .

[18]  P. Ran,et al.  Impedance sensing of allergen-antibody interaction on glassy carbon electrode modified by gold electrodeposition. , 2007, Bioelectrochemistry.

[19]  Xiurong Yang,et al.  Chitosan mediated assembly of gold nanoparticles multilayer , 2003 .

[20]  Arunas Ramanavicius,et al.  Electrochemical Impedance Spectroscopy Based Evaluation of 1,10-Phenanthroline-5,6-dione and Glucose Oxidase Modified Graphite Electrode , 2014 .

[21]  F. Tanfani,et al.  Chelating, film‐forming, and coagulating ability of the chitosan–glucan complex from Aspergillus niger industrial wastes , 1980, Biotechnology and bioengineering.

[22]  H. Ju,et al.  Anodic electrochemiluminescence of CdTe quantum dots and its energy transfer for detection of catechol derivatives. , 2007, Analytical chemistry.

[23]  Yu Zhou,et al.  A perovskite-type KNbO3 nanoneedles based biosensor for direct electrochemistry of hydrogen peroxide , 2014 .

[24]  S. Kingsmore.  Multiplexed protein measurement: technologies and applications of protein and antibody arrays , 2006, Nature Reviews Drug Discovery.

[25]  J. Kiel,et al.  Use of magnetic beads in selection and detection of biotoxin aptamers by electrochemiluminescence and enzymatic methods. , 2002, BioTechniques.

[26]  Yi Wang,et al.  Prostate specific antigen biosensor based on long range surface plasmon-enhanced fluorescence spectroscopy and dextran hydrogel binding matrix. , 2009, Analytical chemistry.

[27]  Jinyi Wang,et al.  Electrogenerated chemiluminescence biosensing for the detection of prostate PC-3 cancer cells incorporating antibody as capture probe and ruthenium complex-labelled wheat germ agglutinin as signal probe. , 2015, Analytica chimica acta.

[28]  R. Yu,et al.  A novel electrochemical immunosensor based on colabeled silica nanoparticles for determination of total prostate specific antigen in human serum. , 2008, Talanta.

[29]  T. Morita,et al.  (K,Na)NbO3 lead-free piezoelectric ceramics synthesized from hydrothermal powders , 2010 .

[30]  Yuan Yu,et al.  M\TiO₂ (M=Au, Ag) transparent aqueous sols and its application on polymeric surface antibacterial post-treatment. , 2015, Journal of colloid and interface science.

[31]  He-lin Niu,et al.  Fabrication of GO/PANi/CdSe nanocomposites for sensitive electrochemiluminescence biosensor. , 2013, Biosensors & bioelectronics.

[32]  Taihong Wang,et al.  Positive potential operation of a cathodic electrogenerated chemiluminescence immunosensor based on luminol and graphene for cancer biomarker detection. , 2011, Analytical chemistry.

[33]  Jiaguo Yu,et al.  Enhancing photocatalytic activity of one-dimensional KNbO3 nanowires by Au nanoparticles under ultraviolet and visible-light , 2011 .

[34]  S. Haile,et al.  Hydrothermal synthesis of KNbO_3 and NaNbO_3 powders , 2003 .

[35]  Ken‐Tsung Wong,et al.  Synthesis, properties, and electrogenerated chemiluminescence (ECL) of a novel carbazole-based chromophore , 2005 .

[36]  Agustín Costa-García,et al.  Simultaneous detection of free and total prostate specific antigen on a screen-printed electrochemical dual sensor. , 2009, Biosensors & bioelectronics.

[37]  Christine Galez,et al.  Harmonic nanocrystals for biolabeling: a survey of optical properties and biocompatibility. , 2012, ACS nano.

[38]  Comparative study of anchoring groups for molecular electronics: structure and conductance of Au-S-Au and Au-NH(2)-Au junctions. , 2008, Journal of physics. Condensed matter : an Institute of Physics journal.

[39]  D. Riley,et al.  Band-Edge Tuning in Self-Assembled Layers of Bi2S3 Nanoparticles Used To Photosensitize Nanocrystalline TiO2 , 2003 .

[40]  S. Dong,et al.  Electrochemiluminescent detection of chlorpromazine by selective preconcentration at a lauric acid-modified carbon paste electrode using tris(2,2'-bipyridine)ruthenium(II). , 2000, Analytical chemistry.

[41]  Paolo Bertoncello,et al.  Nanostructured materials for electrochemiluminescence (ECL)-based detection methods: recent advances and future perspectives. , 2009, Biosensors & bioelectronics.

[42]  X. Xia,et al.  Electrochemically deposited nanocomposite film of CS-Fc/Au NPs/GOx for glucose biosensor application. , 2009, Biosensors & bioelectronics.

[43]  Jeong-Woo Choi,et al.  3D label-free prostate specific antigen (PSA) immunosensor based on graphene-gold composites. , 2015, Biosensors & bioelectronics.

[44]  I. Rubinstein,et al.  Electrogenerated chemiluminescence. 37. Aqueous ecl systems based on tris(2,2'-bipyridine)ruthenium(2+) and oxalate or organic acids , 1981 .

[45]  X. Lu,et al.  Facile fabrication of porous thin films of Bi2O3/Bi2S3 nanocomposite semiconductors at gas/liquid interface and their photoelectrochemical performances , 2014 .

[46]  Qinghui Tang,et al.  Quantum Dots Based Electrochemiluminescent Immunosensor for Ultrasensitive and Specific Determination of Mercury (II) Ions Using Gold Nanoparticles and a Monoclonal Antibody , 2015 .

[47]  J. Rusling,et al.  Carbon nanotube microwell array for sensitive electrochemiluminescent detection of cancer biomarker proteins. , 2011, Analytical chemistry.

[48]  Ü. Demir,et al.  Formation of Bi2S3 thin films on Au(111) by electrochemical atomic layer epitaxy: kinetics of structural changes in the initial monolayers , 2002 .

[49]  Hongyuan Chen,et al.  Electrochemiluminescence immunosensor based on CdSe nanocomposites. , 2008, Analytical chemistry.

[50]  Y. Perera,et al.  Development and validation of a quantitative ELISA for the measurement of PSA concentration. , 2002, Clinica chimica acta; international journal of clinical chemistry.

[51]  Henghui Zhou,et al.  Topotactic Transformation of Single‐Crystalline Precursor Discs into Disc‐Like Bi2S3 Nanorod Networks , 2008 .

[52]  Peter J. Pauzauskie,et al.  Tunable nanowire nonlinear optical probe , 2007, Nature.

[53]  A. Bard,et al.  Electrochemistry and electrogenerated chemiluminescence of CdTe nanoparticles , 2004 .

[54]  Ruo Yuan,et al.  Bi-enzyme synergetic catalysis to in situ generate coreactant of peroxydisulfate solution for ultrasensitive electrochemiluminescence immunoassay. , 2012, Biosensors & bioelectronics.

[55]  Arunas Ramanavicius,et al.  Comparative study of surface plasmon resonance, electrochemical and electroassisted chemiluminescence methods based immunosensor for the determination of antibodies against human growth hormone. , 2012, Biosensors & bioelectronics.