Enzyme-Polymers Conjugated to Quantum-Dots for Sensing Applications

In the present research, the concept of developing a novel system based on polymer-enzyme macromolecules was tested by coupling carboxylic acid functionalized poly(vinyl alcohol) (PVA-COOH) to glucose oxidase (GOx) followed by the bioconjugation with CdS quantum-dots (QD). The resulting organic-inorganic nanohybrids were characterized by UV-visible spectroscopy, infrared spectroscopy, Photoluminescence spectroscopy (PL) and transmission electron microscopy (TEM). The spectroscopy results have clearly shown that the polymer-enzyme macromolecules (PVA-COOH/GOx) were synthesized by the proposed zero-length linker route. Moreover, they have performed as successful capping agents for the nucleation and constrained growth of CdS quantum-dots via aqueous colloidal chemistry. The TEM images associated with the optical absorption results have indicated the formation of CdS nanocrystals with estimated diameters of about 3.0 nm. The “blue-shift” in the visible absorption spectra and the PL values have provided strong evidence that the fluorescent CdS nanoparticles were produced in the quantum-size confinement regime. Finally, the hybrid system was biochemically assayed by injecting the glucose substrate and detecting the formation of peroxide with the enzyme horseradish peroxidase (HRP). Thus, the polymer-enzyme-QD hybrid has behaved as a nanostructured sensor for glucose detecting.

[1]  L. C. Clark,et al.  ELECTRODE SYSTEMS FOR CONTINUOUS MONITORING IN CARDIOVASCULAR SURGERY , 1962 .

[2]  Weiwei Guo,et al.  Utilizing a CdTe quantum dots-enzyme hybrid system for the determination of both phenolic compounds and hydrogen peroxide. , 2008, Analytical chemistry.

[3]  N. Evans,et al.  Fluorescence-based glucose sensors. , 2005, Biosensors & bioelectronics.

[4]  Gurmeet Singh,et al.  Formation of water-soluble and biocompatible TOPO-capped CdSe quantum dots with efficient photoluminescence , 2009, Journal of materials science. Materials in medicine.

[5]  Louis E. Brus,et al.  Electron-electron and electron-hole interactions in small semiconductor crystallites : The size dependence of the lowest excited electronic state , 1984 .

[6]  Hui Jiang,et al.  Enzyme-quantum dots architecture for highly sensitive electrochemiluminescence biosensing of oxidase substrates. , 2007, Chemical communications.

[7]  Manuela F. Frasco,et al.  Semiconductor Quantum Dots in Chemical Sensors and Biosensors , 2009, Sensors.

[8]  Fangqiong Tang,et al.  Enzyme biosensor based on NAD-sensitive quantum dots. , 2010, Biosensors & bioelectronics.

[9]  F. Caruso,et al.  Photoelectrochemical behaviour of CdS “Q-state” semiconductor particles in 10,12-nonacosadiynoic acid polymer langmuir-blodgett films , 1999 .

[10]  A. Mansur,et al.  Biocompatibility of nanostructured chitosan/ poly(vinyl alcohol) blends chemically crosslinked with genipin for biomedical applications. , 2010, Journal of biomedical nanotechnology.

[11]  Jae-Joon Lee,et al.  A Comprehensive Review of Glucose Biosensors Based on Nanostructured Metal-Oxides , 2010, Sensors.

[12]  J. González,et al.  Synthesis and characterization of CdS quantum dots with carboxylic-functionalized poly (vinyl alcohol) for bioconjugation , 2011 .

[13]  H. Mansur,et al.  Preparation and characterization of chitosan/poly(vinyl alcohol) chemically crosslinked blends for biomedical applications , 2009 .

[14]  H. S. Wolff,et al.  iRun: Horizontal and Vertical Shape of a Region-Based Graph Compression , 2022, Sensors.

[15]  Hungsun Son,et al.  Highly stable and sensitive glucose biosensor based on covalently assembled high density Au nanostructures. , 2011, Biosensors & bioelectronics.

[16]  Thomas Laurell,et al.  Microfluidic biosensing systems. Part I. Development and optimisation of enzymatic chemiluminescent micro-biosensors based on silicon microchips. , 2004, Lab on a chip.

[17]  J. Tauc,et al.  States in the gap , 1972 .

[18]  A. Mansur,et al.  Biomolecule-quantum dot systems for bioconjugation applications. , 2011, Colloids and surfaces. B, Biointerfaces.

[19]  T. Xia,et al.  Understanding biophysicochemical interactions at the nano-bio interface. , 2009, Nature materials.

[20]  Shao-jie Wang,et al.  Synthesis, characterization and optical properties of hybridized CdS-PVA nanocomposites , 2007 .

[21]  Yogeswaran Umasankar,et al.  Nanomaterials - Acetylcholinesterase Enzyme Matrices for Organophosphorus Pesticides Electrochemical Sensors: A Review , 2009, Sensors.

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

[23]  Rosario Pereiro,et al.  Bioanalytics and biolabeling with semiconductor nanoparticles (quantum dots) , 2007 .

[24]  Jie Yin,et al.  Preparation and characterization of polyvinyl alcohol-capped CdSe nanoparticles at room temperature. , 2002, Journal of colloid and interface science.

[25]  R P Mason,et al.  The horseradish peroxidase-catalyzed oxidation of 3,5,3',5'-tetramethylbenzidine. Free radical and charge-transfer complex intermediates. , 1982, The Journal of biological chemistry.

[26]  Robert C. Wolpert,et al.  A Review of the , 1985 .

[27]  J. Lakowicz,et al.  Emission Spectral Properties of Cadmium Sulfide Nanoparticles with Multiphoton Excitation. , 2002, The journal of physical chemistry. B.

[28]  Igor L. Medintz,et al.  Quantum dot bioconjugates for imaging, labelling and sensing , 2005, Nature materials.

[29]  Yadong Yin,et al.  Colloidal nanocrystal synthesis and the organic–inorganic interface , 2005, Nature.

[30]  Rodolfo J. Romañach,et al.  Atomic force measurements of 16-mercaptohexadecanoic acid and its salt with CH , 2005 .

[31]  A. Alivisatos,et al.  Reaction chemistry and ligand exchange at cadmium-selenide nanocrystal surfaces. , 2008, Journal of the American Chemical Society.

[32]  A. Henglein,et al.  Photochemistry of colloidal semiconductors. Onset of light absorption as a function of size of extremely small CdS particles , 1986 .

[33]  Ralf Schweins,et al.  Enzymatic activity of lipase-nanoparticle conjugates and the digestion of lipid liquid crystalline assemblies. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[34]  C. Schmidt,et al.  Variation of cadmium sulfide nanoparticle size and photoluminescence intensity with altered aqueous synthesis conditions , 2005 .

[35]  Haoting Lu,et al.  H2O2-sensitive quantum dots for the label-free detection of glucose. , 2010, Talanta.

[36]  H. Mansur.  Quantum dots and nanocomposites. , 2010, Wiley interdisciplinary reviews. Nanomedicine and nanobiotechnology.

[37]  Simon Biggs,et al.  Photoelectrochemical properties of ‘Q-state’ CdS particles in arachidic acid Langmuir–Blodgett films , 1995 .

[38]  A. Mansur,et al.  CdSe quantum dots stabilized by carboxylic-functionalized PVA: Synthesis and UV–vis spectroscopy characterization , 2011 .