Fluorescent Biomolecules Capped ZnSe Quantum Dots and Their Photocatalytic Activities.

The preparation of semiconductor Quantum Dots (QDs) with controllable size, shape and doping remains a biggest challenge, especially the size below 10 nm. To date, only scarce attempts have been made on the synthesis of ZnSe QDs using biomolecule-assisted hydrothermal approach. Hence the current research work examines the influence of some amino acids namely L-cysteine, methionine and tyrosine as stabilizing agents in the synthesis of ZnSe nanocrystals. The ZnSe QDs exhibited strong absorption and photoluminescence properties in the region from 200-600 nm. Spectroscopic and structural properties of the as-synthesized biomolecule-capped ZnSe QDs were characterized by UV-vis absorption spectrophotometer, FT-IR, fluorescence spectrophotometer, X-ray diffractometer, Scanning Electron Microscope and EDX analysis. The stabilizing agents have played a crucial role in preparing ZnSe QDs and in determining the photoluminescence properties. The luminescence intensity was enhanced significantly when amino-acid-capped ZnSe QDs were illuminated by UV light compared to visible light. The as-synthesised ZnSe QDs were capable of effectively degrading an organic azo dye Azophlexin, under direct sunlight irradiation and exhibited good stability during photocatalytic experiments which can be attributed to the small size of amino acid capped ZnSe. The degradation mechanism is discussed. The absorbance and FT-IR measurements confirmed the biocompatibility and water-solubility of the pure ZnSe and capped ZnSe QDs.

Homogeneous solvation controlled photoreduction of cobalt(III) complexes in aqueous 2-methyl-2-propanol solutions linear solvation energy relationship and cyclic voltammetric analyses.

The effect of solvent participation on the ligand-to-metal charge transfer (LMCT, L-->Co(III)) reduction of the of Co(III)(en)(2)Br(RC(6)H(4)NH(2))(2+) where R=m-OCH(3), p-F, H, m-CH(3), p-CH(3,)p-OC(2)H(5) and p-OCH(3) were examined in aqueous 2-methyl-2-propanol (Bu(t)OH) solutions. The change in the reduction behavior of Co(III) centre was also examined through cyclic voltammetric studies. The observed reduction in quantum yield due to LMCT excitation can mainly be accounted using linear solvation energy relationship (LSER) comprising model correlation equations. These consist of empirical parameters such as Grunwald-Winstein's solvent ionizing power, Y, Dimroth-Richardt's solvent micro-polarity parameter, E(T)(N), Gutmann's donor number, DN(N), along with Kamlet-Taft's solvatochromic parameters (hydrogen bond acceptor acidity/basicity alpha/beta and solvent dipolarity/polarizability, pi*). The origin of solvent effect is found to be due to microscopic interaction between the solvent donor and the nitrogen-bound hydrogen of the ligand. Cyclic voltammograms show an irreversible reduction of Co(III) in DMF using Glassy Carbon Electrode, GCE, the redox peaks for the aniline complexes appear at -0.20 and 0.525V. Irradiation of the complexes with UV light (lambda=254nm) in binary mixtures produce Co(II)(aq) and the concentration of this species are highly dependent on x(alc) (x(alc)=mole fraction of alcohol). The observed quantum yield (logPhi(Co(II))) is found to be linearly related to mole fraction of organic co-solvent added in the mixture, therefore, logPhi(Co(II))=26.41 x 10(-2) when x(2)=0.0094 and 43.75 x 10(-2) when x(2)=0.076 for a typical complex Co(III)(en)(2)Br(p-OCH(3)C(6)H(4)NH(2))(2+) in aqueous 2-methyl-2-propanol at 300K. Cyclic voltammetry and LSER analyses illustrate the variation of reduction property of Co(III) by the aryl ligand and homogeneous solvation of the excited state of the complex Co(III)(en)(2)Br(RC(6)H(4)NH(2))(2+) in H(2)O/Bu(t)OH mixtures.