Preparation and characterization of thiacalix[4]arene coated water-soluble CdSe/ZnS quantum dots as a fluorescent probe for Cu2+ ions.
Highly fluorescent water-soluble CdSe/ZnS (core/shell) quantum dots (QDs) as a fluorescent Cu2+ ion probe were synthesized using thiacalix[4]arene carboxylic acid (TCC) as a surface coating agent. Hydrophobic trioctylphosphine oxide (TOPO) capped CdSe/ZnS QDs were overcoated with TCC in tetrahydrofuran at room temperature, and deprotonation of the carboxyl groups of TCC resulted in the formation of water-soluble QDs. The surface structure of the QDs was characterized by using transmission electron microscopy (TEM) and fluorescence correlation spectroscopy (FCS). TEM images showed that TCC-coated QDs were monodispersed with the particle size (core-shell moiety) of approximately 5 nm. Hydrodynamic diameter of the TCC-coated QDs was determined to be 8.9 nm by FCS, showing that the thickness of the surface organic layer of the QDs was approximately 2 nm. These results indicate that the surface layer of TCC-coated QDs forms a bilayer structure consisting of TOPO and TCC molecules. TCC-coated CdSe/ZnS QDs were highly fluorescent (quantum yield, 0.21) compared to the QDs surface-modified with mercaptoacetic acid and mercaptoundecanoic acid. Fluorescence of the TCC-coated QDs was effectively quenched by Cu2+ ions even in the presence of other transition metal ions such as Cd2+, Zn2+, Co2+, Fe2+, and Fe3+ ions in the same solution. The Stern-Volmer plot for the fluorescence quenching by Cu2+ ions showed a linear relationship up to 30 microM of Cu2+ ions. The ion selectivity of TCC-coated QDs was determined by measurements of fluorescence responses towards biologically important transition metal ions (50 microM) including Fe2+, Fe3+, Co2+>Zn2+, Cd2+. The fluorescence of TCC-coated QDs was almost insensitive to other biologically important ions such as Na+, K+, Mg2+, and Ca2+, suggesting that TCC-coated QDs can be used as a fluorescent Cu2+ ion probe for biological samples. A possible quenching mechanism by Cu2+ ions was also discussed on the basis of a Langmuir-type adsorption isotherm.
Jin
Takashi
T
Research Institute for Electronic Science, Hokkaido University, Sapporo 060-0812, Japan. jin@imd.es.hokudai.ac.jp
Fujii
Fumihiko
F
Yamada
Eiji
E
Nodasaka
Yoshinobu
Y
Kinjo
Masataka
M
D019187:Cadmium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002863:Chromogenic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000032:analysis* / Q000737:chemistry; D005456:Fluorescent Dyes / Q000138:chemical synthesis / Q000737:chemistry*; D007477:Ions; D010636:Phenols / Q000737:chemistry*; D045663:Quantum Dots; D018036:Selenium Compounds / Q000737:chemistry*; D012995:Solubility; D013440:Sulfides / Q000737:chemistry*; D013499:Surface Properties; D014867:Water / Q000737:chemistry; D017967:Zinc Compounds / Q000737:chemistry*
D019187:Cadmium Compounds; D002863:Chromogenic Compounds; D005456:Fluorescent Dyes; D007477:Ions; D010636:Phenols; D018036:Selenium Compounds; D013440:Sulfides; D017967:Zinc Compounds; C500450:thiacalix(4)arene; D014867:Water; D003300:Copper; C058667:cadmium selenide; C031238:zinc sulfide