Mechanistic Aspects of Quantum Dot Based Probing of Cu (II) Ions: Role of Dendrimer in Sensor Efficiency

Selective quenching of luminescence of quantum dots (QDs) by Cu2+ ions vis-à-vis other physiologically relevant cations has been reexamined. In view of the contradiction regarding the mechanism, we have attempted to show why Cu2+ ions quench QD-luminescence by taking CdS and CdTe QDs with varying surface groups. A detailed study of the solvent effect and also size dependence on the observed luminescence has been carried out. For a 13% decrease in particle diameter (4.3 nm →3.7 nm), the quenching constant increased by a factor of 20. It is established that instead of surface ligands of QDs, conduction band potential of the core facilitates the photo-induced reduction of Cu (II) to Cu (I) thereby quenching the photoluminescence. Taking the advantage of biocompatibility of dendrimer and its high affinity towards Cu2+ ions, we have followed interaction of Cu2+-PAMAM and also dendrimer with the CdTe QDs. Nanomolar concentration of PAMAM dendrimer was found to quench the luminescence of CdTe QDs. In contrast, Cu2+-PAMAM enhanced the fluorescence of CdTe QDs and the effect has been attributed to the binding of Cu2+-PAMAM complex to the CdTe particle surface. The linear portion of the enhancement plot due to Cu2+-PAMAM can be used for determination of Cu2+ ions with detection limit of 70 nM.

[1]  B. Imperiali,et al.  Exploiting Polypeptide Motifs for the Design of Selective Cu(II) Ion Chemosensors , 1998 .

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

[3]  A. Saha,et al.  Size dependent interaction of biofunctionalized CdS nanoparticles with tyrosine at different pH. , 2005, Chemical communications.

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

[5]  Wallace S. Brey,et al.  Physical Chemistry and Its Biological Applications , 1978 .

[6]  James R. Dewald,et al.  A New Class of Polymers: Starburst-Dendritic Macromolecules , 1985 .

[7]  A. Wachnik The physiological role of copper and the problems of copper nutritional deficiency. , 1988, Die Nahrung.

[8]  S. Basu,et al.  Characterization of the triplet charge-transfer state of 4-amino-N-methylphthalimide in aprotic and protic media by laser flash photolysis , 1997 .

[9]  B. Tang,et al.  Highly luminescent water-soluble CdTe nanowires as fluorescent probe to detect copper(II). , 2005, Chemical communications.

[10]  William A. Goddard,et al.  Starburst Dendrimers: Molecular‐Level Control of Size, Shape, Surface Chemistry, Topology, and Flexibility from Atoms to Macroscopic Matter , 1990 .

[11]  Kaushik Patel,et al.  Q-CdS Photoluminescence Activation on Zn2+ and Cd2+ Salt Introduction , 2001 .

[12]  W. Goddard,et al.  Poly(amidoamine) Dendrimers: A New Class of High Capacity Chelating Agents for Cu(II) Ions , 1999 .

[13]  J. Reymond,et al.  A fluorescent metal sensor based on macrocyclic chelation , 2001 .

[14]  Di Li,et al.  Luminescent CdTe quantum dots and nanorods as metal ion probes , 2005 .

[15]  D. Pang,et al.  Functionalized CdSe quantum dots as selective silver ion chemodosimeter. , 2004, The Analyst.

[16]  H. Ploehn,et al.  Platinum ion uptake by dendrimers: an NMR and AFM study. , 2004, Inorganic chemistry.

[17]  R. Marchelli,et al.  Dansylated Polyamines as Fluorescent Sensors for Metal Ions: Photophysical Properties and Stability of Copper(II) Complexes in Solution. , 2001 .

[18]  Z. Rosenzweig,et al.  Luminescent CdS quantum dots as selective ion probes. , 2002, Analytical chemistry.

[19]  J. Lakowicz Principles of fluorescence spectroscopy , 1983 .

[20]  Sameer Sapra,et al.  Evolution of the electronic structure with size in II-VI semiconductor nanocrystals , 2004 .

[21]  H. Matsumoto,et al.  Size Dependent Fluorescence Quenching of CdS Nanocrystals Caused by TiO2 Colloids as a Potential-Variable Quencher , 1995 .

[22]  F. Wilkinson,et al.  MECHANISM OF QUENCHING OF TRIPLET STATES BY MOLECULAR OXYGEN : BIPHENYL DERIVATIVES IN DIFFERENT SOLVENTS , 1999 .

[23]  A. Bard,et al.  Electrochemistry of CdS nanoparticles: a correlation between optical and electrochemical band gaps. , 2001, Journal of the American Chemical Society.

[24]  Arthur J. Nozik,et al.  Synthesis and Characterization of Surface-Modified Colloidal CdTe Quantum Dots , 1993 .

[25]  J. Matthew Mauro,et al.  Self-Assembly of CdSe−ZnS Quantum Dot Bioconjugates Using an Engineered Recombinant Protein , 2000 .

[26]  A. Saha,et al.  pH dependent interaction of biofunctionalized CdS nanoparticles with nucleobases and nucleotides: A fluorimetric study , 2007 .

[27]  Igor L. Medintz,et al.  Multiplexed toxin analysis using four colors of quantum dot fluororeagents. , 2004, Analytical chemistry.

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

[29]  Alex V. Isarov and,et al.  Optical and Photochemical Properties of Nonstoichiometric Cadmium Sulfide Nanoparticles: Surface Modification with Copper(II) Ions , 1997 .

[30]  A. Sutherland,et al.  Quantum dots as luminescent probes in biological systems , 2002 .

[31]  A. Saha,et al.  Surface-functionalized cadmium chalcogenide nanocrystals : A spectroscopic investigation of growth and photoluminescence , 2007 .