Enzyme/semiconductor nanoclusters combined systems for novel amperometric biosensors.

In this work quantum-sized CdS nanocrystals were synthesized using a quaternary water-in-oil microemulsion and immobilized onto gold working electrode by self-assembled monolayers techniques. Formaldehyde dehydrogenase was covalently immobilized onto a protecting membrane, which was stratified on part of the semiconductor nanoparticles modified electrode. The covalent enzyme immobilization has been required to improve the stability of the catalytic oxidation of formaldehyde, which occurs after light stimulation of the semiconductor through the electron/hole recombination. A study about the best electrochemical oxidation potentials under different flow conditions was performed. Preliminary sensor stability and interferences tests were also carried out, for a sensitive and selective detection of formaldehyde. A detection limit of 41ppb of formaldehyde was calculated and an operational stability of 6h was achieved under flow conditions by means of this novel amperometric biosensor based on FDH-semiconductor hybrid systems, not requiring NAD(+)/NADH as charge transfer in the enzymatic reaction.

[1]  M. L. Curri,et al.  Photocatalytic activity of organic-capped anatase TiO2 nanocrystals in homogeneous organic solutions , 2003 .

[2]  M. L. Curri,et al.  High quality CdS nanocrystals: surface effects , 2003 .

[3]  Andrew J. Williamson,et al.  InAs quantum dots: Predicted electronic structure of free-standing versus GaAs-embedded structures , 1999 .

[4]  W. Knoll,et al.  Chemical deposition of PbS on self-assembled monolayers of 16-mercaptohexadecanoic acid , 1997 .

[5]  Norris,et al.  Observation of the "Dark exciton" in CdSe quantum dots. , 1995, Physical review letters.

[6]  I. E. Bechmann,et al.  Determination of formaldehyde in frozen fish with formaldehyde dehydrogenase using a flow injection system with an incorporated gel-filtration chromatography column , 1996 .

[7]  C. Lowe,et al.  Nanobiotechnology: the fabrication and applications of chemical and biological nanostructures. , 2000, Current opinion in structural biology.

[8]  M. Pileni,et al.  Nanosized Particles Made in Colloidal Assemblies , 1997 .

[9]  Liberato Manna,et al.  Shape Control of Colloidal Semiconductor Nanocrystals , 2002 .

[10]  Eric Bourillot,et al.  Performance of interdigitated nanoelectrodes for electrochemical DNA biosensor. , 2003, Ultramicroscopy.

[11]  M. L. Curri,et al.  Photochemical sensitisation process at photosynthetic pigments/Q-sized colloidal semiconductor hetero-junctions , 2003 .

[12]  A. Bard,et al.  Scanning Tunneling Microscopy, Tunneling Spectroscopy, and Photoelectrochemistry of a Film of Q-CdS Particles Incorporated in a Self-Assembled Monolayer on a Gold Surface , 1995 .

[13]  N. Cade,et al.  Electrochemical enzyme sensor for formaldehyde operating in the gas phase , 1996 .

[14]  A. Henglein,et al.  Small-particle research: physicochemical properties of extremely small colloidal metal and semiconductor particles , 1989 .

[15]  I. Willner,et al.  Organization of Au Colloids as Monolayer Films onto ITO Glass Surfaces: Application of the Metal Colloid Films as Base Interfaces To Construct Redox-Active Monolayers , 1995 .

[16]  L. Demers,et al.  Structure and Dynamics in Alkanethiolate Monolayers Self-Assembled on Gold Nanoparticles: A DSC, FT-IR, and Deuterium NMR Study , 1997 .

[17]  Liming Sun,et al.  Determination of nano-molar levels of formaldehyde in drinking water using flow-injection system with immobilized formaldehyde dehydrogenase after off-line solid-phase extraction , 1999 .

[18]  Charles M. Lieber,et al.  One-dimensional nanostructures: Chemistry, physics & applications , 1998 .

[19]  M. L. Curri,et al.  ZnO Nanocrystals by a Non-hydrolytic Route: Synthesis and Characterization , 2003 .

[20]  Marina Scarpa,et al.  Potentiometric detection of formaldehyde in air by an aldehyde dehydrogenase FET , 1996 .

[21]  Antonia Mallardi,et al.  Development of a novel enzyme/semiconductor nanoparticles system for biosensor application , 2002 .

[22]  A. El'skaya,et al.  A cell biosensor specific for formaldehyde based on pH-sensitive transistors coupled to methylotrophic yeast cells with genetically adjusted metabolism. , 1993, Analytical biochemistry.

[23]  P. Cozzoli,et al.  Low-temperature synthesis of soluble and processable organic-capped anatase TiO2 nanorods. , 2003, Journal of the American Chemical Society.

[24]  A. Bard,et al.  Fabrication and characterization of self-assembled spherical gold ultramicroelectrodes. , 1997, Analytical chemistry.

[25]  J. Lehotay,et al.  HPLC Determination of Trace Levels of Aliphatic Aldehydes C1 - C4 in River and Tap Water Using On-Line Preconcentration , 1994 .

[26]  Barry Dellinger,et al.  Sampling and ion chromatographic determination of formaldehyde and acetaldehyde , 1981 .

[27]  Judith Rishpon,et al.  An electrochemical biosensor for formaldehyde , 2000 .

[28]  A. Alivisatos,et al.  Semiconductor nanocrystals covalently bound to metal surfaces with self-assembled monolayers , 1992 .

[29]  T. Nakanishi,et al.  Construction of Semiconductor Nanoparticle Layers on Gold by Self-Assembly Technique , 1997 .

[30]  A. Alivisatos.  Perspectives on the Physical Chemistry of Semiconductor Nanocrystals , 1996 .

[31]  R. Smalley,et al.  The future of the fullerenes , 1998 .

[32]  A. Alivisatos.  Semiconductor Clusters, Nanocrystals, and Quantum Dots , 1996, Science.

[33]  Matsuhiko Nishizawa,et al.  Characterization of Covalently Immobilized Q-CdS Particles on Au(111) by Scanning Tunneling Microscopy and Tunneling Spectroscopy with High Reproducibility , 1997 .

[34]  M. L. Curri,et al.  Colloidal oxide nanoparticles for the photocatalytic degradation of organic dye , 2003 .

[35]  G. S. Wilson,et al.  Rotating ring-disk enzyme electrode for biocatalysis kinetic studies and characterization of the immobilized enzyme layer , 1980 .

[36]  A. Alivisatos,et al.  Nanocrystals: Building blocks for modern materials design , 1997 .

[37]  Mary Lynn Grayeski,et al.  New chemiluminescent derivatizing agent for the analysis of aldehydes and ketones by high-performance liquid chromatography with peroxyoxalate chemiluminescence , 1987 .

[38]  C. Koval,et al.  Electrochemistry of the ruthenium(3+,2+) couple attached to graphite electrodes , 1978 .

[39]  D. Balding,et al.  HLA Sequence Polymorphism and the Origin of Humans , 2006 .

[40]  E. Hall,et al.  An enzyme electrode with response independent of the thickness of the enzyme layer , 1996 .

[41]  C. Martelet,et al.  Development of highly selective and stable potentiometric sensors for formaldehyde determination. , 2000, Biosensors & bioelectronics.

[42]  G. R. Möhlmann,et al.  Formaldehyde Detection in Air by Laser-Induced Fluorescence , 1985 .

[43]  T. Dumas,et al.  Determination of formaldehyde in air by gas chromatography , 1982 .

[44]  P. Dasgupta,et al.  Fast fluorometric flow injection analysis of formaldehyde in atmospheric water. , 1987, Environmental science & technology.

[45]  Eugenii Katz,et al.  Application of bifunctional reagents for immobilization of proteins on a carbon electrode surface: Oriented immobilization of photosynthetic reaction centers , 1994 .