Magnetic Fe3O4@Au composite-enhanced surface plasmon resonance for ultrasensitive detection of magnetic nanoparticle-enriched α-fetoprotein.

Small molecules or analytes present at low concentrations are difficult to detect directly using conventional surface plasmon resonance (SPR) techniques because only small changes in the refractive index of the medium are typically induced by the binding of these analytes. Here, we present an amplification technique using core-shell Fe(3)O(4)@Au magnetic nanoparticles (MNPs) for an SPR bioassay. To evaluate this amplification effect, a novel SPR sensor based on a sandwich immunoassay was developed to detect α-fetoprotein (AFP) by immobilizing a primary AFP antibody (Ab(1)) on the surface of a 3-mercapto-1-propanesulfonate/chitosan-ferrocene/Au NP (MPS/CS-Fc/Au NP) film employing Fe(3)O(4)@Au-AFP secondary antibody conjugates (Fe(3)O(4)@Au-Ab(2)) as the amplification reagent. The stepwise fabrication of the biosensor was characterized using UV-vis spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. A calibration curve of Fe(3)O(4)@Au-Ab(2) conjugates amplification for AFP detection was obtained to yield a correlation in the range of 1.0-200.0 ng mL(-1) with a detection limit of 0.65 ng mL(-1), and a significant increase in sensitivity was therefore afforded through the use of Fe(3)O(4)@Au-Ab(2) conjugates as an amplifier. This magnetic separation and amplification strategy has great potential for the detection of other biomolecules of interest with low interference and high sensitivity by changing the antibody label used in the Fe(3)O(4)@Au-antibody conjugates.

[1]  Michael J. Natan,et al.  SURFACE PLASMON RESONANCE OF AU COLLOID-MODIFIED AU FILMS : PARTICLE SIZE DEPENDENCE , 1999 .

[2]  Jose Melendez,et al.  Detection of Staphylococcus aureus enterotoxin B at femtomolar levels with a miniature integrated two-channel surface plasmon resonance (SPR) sensor. , 2002, Biosensors & bioelectronics.

[3]  Yu Zhang,et al.  A novel reagentless amperometric immunosensor based on gold nanoparticles/TMB/Nafion-modified electrode. , 2009, Biosensors & bioelectronics.

[4]  Willem Haasnoot,et al.  Label-free and multiplex detection of antibiotic residues in milk using imaging surface plasmon resonance-based immunosensor. , 2009, Analytical chemistry.

[5]  Dan Du,et al.  A gold nanoparticle labeling strategy for the sensitive kinetic assay of the carbamate-acetylcholinesterase interaction by surface plasmon resonance. , 2009, Talanta.

[6]  D. Roy,et al.  Surface Plasmon Resonance Studies of Gold and Silver Nanoparticles Linked to Gold and Silver Substrates by 2-Aminoethanethiol and 1,6-Hexanedithiol , 2001 .

[7]  H. Zhou,et al.  Aptamer-based Au nanoparticles-enhanced surface plasmon resonance detection of small molecules. , 2008, Analytical chemistry.

[8]  Norio Miura,et al.  Self-assembled PEG monolayer based SPR immunosensor for label-free detection of insulin. , 2007, Biosensors & bioelectronics.

[9]  X. Xia,et al.  Facile preparation of magnetic core-shell Fe3O4@Au nanoparticle/myoglobin biofilm for direct electrochemistry. , 2010, Biosensors & bioelectronics.

[10]  Ruo Yuan,et al.  Magnetic core-shell Fe3O4@Ag nanoparticles coated carbon paste interface for studies of carcinoembryonic antigen in clinical immunoassay. , 2006, The journal of physical chemistry. B.

[11]  K. Niemax,et al.  Enhancement of the detection power of surface plasmon resonance measurements by optimization of the reflection angle. , 2007, Analytical chemistry.

[12]  N. Browning,et al.  Growth Mechanisms and Oxidation Resistance of Gold-Coated Iron Nanoparticles , 2005, cond-mat/0504314.

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

[14]  L M Lechuga,et al.  Multi-analyte SPR immunoassays for environmental biosensing of pesticides , 2007, Analytical and bioanalytical chemistry.

[15]  Yu-Chie Chen,et al.  Fe3O4/TiO2 core/shell nanoparticles as affinity probes for the analysis of phosphopeptides using TiO2 surface-assisted laser desorption/ionization mass spectrometry. , 2005, Analytical chemistry.

[16]  J. Homola On the sensitivity of surface plasmon resonance sensors with spectral interrogation , 1997 .

[17]  B. Liedberg,et al.  Surface plasmon resonance for gas detection and biosensing , 1983 .

[18]  L. Zaijun,et al.  Synergistic contributions of fullerene, ferrocene, chitosan and ionic liquid towards improved performance for a glucose sensor. , 2010, Biosensors & bioelectronics.

[19]  Bo Liedberg,et al.  A novel biochip technology for detection of explosives – TNT: Synthesis, characterisation and application , 2006 .

[20]  Jing Sun,et al.  Effect of ultrasonic treatment on dispersibility of Fe3O4 nanoparticles and synthesis of multi-core Fe3O4/SiO2 core/shell nanoparticles , 2005 .

[21]  Jian-Ding Qiu,et al.  A label-free amperometric immunosensor based on biocompatible conductive redox chitosan-ferrocene/gold nanoparticles matrix. , 2009, Biosensors & bioelectronics.

[22]  Xiangmin Zhang,et al.  Fe3O4@Al2O3 magnetic core-shell microspheres for rapid and highly specific capture of phosphopeptides with mass spectrometry analysis. , 2007, Journal of chromatography. A.

[23]  Na Li,et al.  New Antibody Immobilization Strategy Based on Gold Nanoparticles and Azure I/Multi-Walled Carbon Nanotube Composite Membranes for an Amperometric Enzyme Immunosensor , 2007 .

[24]  Dan Du,et al.  Electrochemical Immunoassay of Human Chorionic Gonadotrophin Based on Its Immobilization in Gold Nanoparticles‐Chitosan Membrane , 2006 .

[25]  Jiří Homola,et al.  Surface plasmon resonance sensor based on an array of diffraction gratings for highly parallelized observation of biomolecular interactions , 2008 .

[26]  C. Lowe,et al.  The resonant mirror: a novel optical sensor for direct sensing of biomolecular interactions part II: applications , 1993 .

[27]  Yusong Wang,et al.  Functionalized carbon nanotubes with polystyrene-block-poly (N-isopropylacrylamide) by in situ RAFT polymerization , 2007 .

[28]  Ying Liu,et al.  Highly sensitive detection of protein toxins by surface plasmon resonance with biotinylation-based inline atom transfer radical polymerization amplification. , 2010, Analytical chemistry.

[29]  Zhichuan J. Xu,et al.  Magnetic core/shell Fe3O4/Au and Fe3O4/Au/Ag nanoparticles with tunable plasmonic properties. , 2007, Journal of the American Chemical Society.

[30]  Y. Chai,et al.  Nanostructured conductive material containing ferrocenyl for reagentless amperometric immunosensors. , 2008, Biomaterials.

[31]  D. Zhao,et al.  Superparamagnetic high-magnetization microspheres with an Fe3O4@SiO2 core and perpendicularly aligned mesoporous SiO2 shell for removal of microcystins. , 2008, Journal of the American Chemical Society.

[32]  M. Natan,et al.  Colloidal Au-enhanced surface plasmon resonance immunosensing. , 1998, Analytical chemistry.

[33]  Shu-I Tu,et al.  SPR biosensor for the detection of L. monocytogenes using phage-displayed antibody. , 2007, Biosensors & bioelectronics.

[34]  Huaping Peng,et al.  Ferrocene-modified Fe3O4@SiO2 magnetic nanoparticles as building blocks for construction of reagentless enzyme-based biosensors , 2007 .

[35]  Y. Chai,et al.  A Reagentless Amperometric Immunosensor for Alpha‐Fetoprotein Based on Gold Nanoparticles/TiO2 Colloids/Prussian Blue Modified Platinum Electrode , 2007 .

[36]  Jin Luo,et al.  Fabrication of magnetic core@shell Fe oxide@Au nanoparticles for interfacial bioactivity and bio-separation. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[37]  Y. Chai,et al.  On‐Off PVC Membrane Based Potentiometric Immunosensor for Label‐Free Detection of Alpha‐Fetoprotein , 2007 .

[38]  Zanzan Zhu,et al.  Magnetic nanoparticle enhanced surface plasmon resonance sensing and its application for the ultrasensitive detection of magnetic nanoparticle-enriched small molecules. , 2010, Analytical chemistry.

[39]  Ying Zhang,et al.  A new potentiometric immunosensor for determination of α-fetoprotein based on improved gelatin-silver complex film , 2006 .

[40]  Tae Jung Park,et al.  Directed self-assembly of gold binding polypeptide-protein A fusion proteins for development of gold nanoparticle-based SPR immunosensors. , 2009, Biosensors & bioelectronics.

[41]  Cristina Tortolini,et al.  Multifunctional au nanoparticle dendrimer-based surface plasmon resonance biosensor and its application for improved insulin detection. , 2010, Analytical chemistry.

[42]  Jin Luo,et al.  Monodispersed core-shell Fe3O4@Au nanoparticles. , 2005, The journal of physical chemistry. B.

[43]  Changqing Sun,et al.  Synthesis of Ferrocene‐Branched Chitosan Derivatives: Redox Polysaccharides and their Application to Reagentless Enzyme‐Based Biosensors , 2007 .

[44]  Ying Zhang,et al.  A reagentless amperometric immunosensor based on gold nanoparticles/thionine/Nafion-membrane-modified gold electrode for determination of α-1-fetoprotein , 2005 .

[45]  G. van Koten,et al.  SPR Studies of Carbohydrate–Protein Interactions: Signal Enhancement of Low‐Molecular‐Mass Analytes by Organoplatinum(II)‐Labeling , 2005, Chembiochem : a European journal of chemical biology.

[46]  Pei Wang,et al.  Surface plasmon resonance hydrogen sensor based on metallic grating with high sensitivity. , 2008, Optics express.

[47]  Yinqiu Wu,et al.  Surface plasmon resonance assay for chloramphenicol. , 2008, Analytical chemistry.

[48]  Yali Shi,et al.  Preparation of alkanethiolate-functionalized core/shell Fe3O4@Au nanoparticles and its interaction with several typical target molecules. , 2008, Analytical chemistry.

[49]  Jian Wang,et al.  Sensitivity enhancement of SPR biosensor with silver mirror reaction on the Ag/Au film. , 2009, Talanta.