Cu@Au alloy nanoparticle as oligonucleotides labels for electrochemical stripping detection of DNA hybridization.

Synthesis of the novel Cu@Au alloy nanoparticle and its application in an electrochemical DNA hybridization detection assay is described in this article. We report a low-temperature method for generating core-shell particles consisting of a core of Cu and a thin layer of Au shell that can be readily functionalized with oligonucleotides. Core-shell Cu@Au particles were successfully labeled to a 5'-alkanethiol capped oligonucleotides probe that is related to the colitoxin gene. The DNA genetic sensing assay relies on the electrostatic adsorption of target oligonucleotides onto conducting polypyrrole (PPy) surface at the glassy carbon electrode (GCE), and its hybridization to the alloy particle-oligonucleotides DNA probe. Hybridization events between probe and target were monitored by the release of the copper metal atoms anchored on the hybrids by oxidative metal dissolution and the indirectly determination of the solubilized Cu2+ ions by sensitive anodic stripping voltammetry (ASV). The detection limit is 5.0 pmol l(-1) of target oligonucleotides. The Cu@Au core-shell nanoparticles combining the surface modification properties of Au with the good electrochemical activity of Cu core shows their perspective application in the electrochemical DNA hybridization analysis assay.

[1]  D. Caruana,et al.  Enzyme-Amplified Amperometric Detection of Hybridization and of a Single Base Pair Mutation in an 18 Base Oligonucleotide on a 7 µm Diameter Microelectrode , 1999 .

[2]  J. Storhoff,et al.  A DNA-based method for rationally assembling nanoparticles into macroscopic materials , 1996, Nature.

[3]  Mostafa A. El-Sayed,et al.  Alloy Formation of Gold−Silver Nanoparticles and the Dependence of the Plasmon Absorption on Their Composition , 1999 .

[4]  Ningning Zhu,et al.  An electrochemical DNA hybridization detection assay based on a silver nanoparticle label. , 2002, The Analyst.

[5]  P He,et al.  Electrochemical detection of sequence-specific DNA using a DNA probe labeled with aminoferrocene and chitosan modified electrode immobilized with ssDNA. , 2001, The Analyst.

[6]  G. Dodin,et al.  DNA adsorption onto conducting polypyrrole , 1997 .

[7]  C. Mirkin,et al.  Scanometric DNA array detection with nanoparticle probes. , 2000, Science.

[8]  T. Mukherjee,et al.  Influence of I− anions on the formation and stabilization of copper nanoparticles , 2002 .

[9]  Everett E. Carpenter,et al.  Gold-coated iron (Fe@Au) nanoparticles: Synthesis, characterization, and magnetic field-induced self-assembly , 2001 .

[10]  J. Dougherty,et al.  Rapid hybridization kinetics of DNA attached to submicron latex particles. , 1987, Nucleic acids research.

[11]  Thomas E. Mallouk,et al.  Orthogonal Self‐Assembly on Colloidal Gold‐Platinum Nanorods , 1999 .

[12]  S. Cosnier Biomolecule immobilization on electrode surfaces by entrapment or attachment to electrochemically polymerized films. A review. , 1999, Biosensors & bioelectronics.

[13]  C. Mirkin,et al.  DNA-modified core-shell Ag/Au nanoparticles. , 2001, Journal of the American Chemical Society.

[14]  Joseph Wang,et al.  New label-free DNA recognition based on doping nucleic-acid probes within conducting polymer films , 1999 .

[15]  T. Livache,et al.  Polypyrrole DNA chip on a silicon device: example of hepatitis C virus genotyping. , 1998, Analytical biochemistry.

[16]  L. Authier,et al.  Gold nanoparticle-based quantitative electrochemical detection of amplified human cytomegalovirus DNA using disposable microband electrodes. , 2001, Analytical chemistry.

[17]  Susan R. Mikkelsen,et al.  Electrochecmical biosensors for DNA sequence detection , 1996 .

[18]  K. Hashimoto,et al.  Sequence-specific gene detection with a gold electrode modified with DNA probes and an electrochemically active dye. , 1994, Analytical chemistry.

[19]  S. Nie,et al.  Quantum dot bioconjugates for ultrasensitive nonisotopic detection. , 1998, Science.

[20]  Y. Ci,et al.  Chemiluminescence investigation of the interaction of metalloporphyrins with nucleic acids , 1993 .

[21]  S. Nie,et al.  Quantum-dot-tagged microbeads for multiplexed optical coding of biomolecules , 2001, Nature Biotechnology.

[22]  Joseph Wang,et al.  Metal nanoparticle-based electrochemical stripping potentiometric detection of DNA hybridization. , 2001, Analytical chemistry.

[23]  Joseph Wang,et al.  Silver-Enhanced Colloidal Gold Electrochemical Stripping Detection of DNA Hybridization , 2001 .

[24]  S. Pathak,et al.  Hydroxylated quantum dots as luminescent probes for in situ hybridization. , 2001, Journal of the American Chemical Society.

[25]  B. Limoges,et al.  Hybridization assay at a disposable electrochemical biosensor for the attomole detection of amplified human cytomegalovirus DNA. , 2000, Analytical biochemistry.

[26]  G. Mathis,et al.  Europium(III) cryptate: a fluorescent label for the detection of DNA hybrids on solid support. , 1991, Analytical biochemistry.

[27]  K. M. Millan,et al.  Voltammetric DNA biosensor for cystic fibrosis based on a modified carbon paste electrode. , 1994, Analytical chemistry.

[28]  Chad A. Mirkin,et al.  Programmed Assembly of DNA Functionalized Quantum Dots , 1999 .

[29]  Joseph Wang,et al.  Towards Genoelectronics: Electrochemical Biosensing of DNA Hybridization , 1999 .

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

[31]  J Wang,et al.  DNA electrochemical biosensor for the detection of short DNA sequences related to the human immunodeficiency virus. , 1996, Analytical chemistry.

[32]  Santiago Sánchez-Cortés,et al.  Mixed Silver/Gold Colloids: A Study of Their Formation, Morphology, and Surface-Enhanced Raman Activity , 2000 .