Colloidal ZnO nanocrystals in dimethylsulfoxide: a new synthesis, optical, photo- and electroluminescent properties.

Stable colloidal solutions of zinc oxide in dimethylsulfoxide were synthesized via interaction between zinc(II) acetate and tetraalkylammonium hydroxides (alkyl-ethyl, propyl, butyl, and pentyl). Colloids of ZnO emit photoluminescence in a broad band with a maximum at 2.3-2.4 eV with quantum yields of up to 9-10% at room temperature and 15-16% at 80 K. The photoluminescence is supposed to originate from the radiative recombination of conduction band electrons with holes captured by deep traps having corresponding states in the band gap 1.0-1.2 eV above the valence band edge. The size of colloidal ZnO nanocrystals depends on the duration and temperature of the post-synthesis treatment and varies in the range of 3-6 nm. Growth of the ZnO nanocrystals can be terminated at any moment of the thermal treatment by freezing the colloidal solution or by addition of tetraethyl orthosilicate which hydrolyses forming core-shell ZnO@SiO2 particles. ZnO nanocrystals introduced into polyethyleneimine films can be used as an active component of an LED emitting at an applied voltage higher than 13 V.

Thermodynamics of organic chemical hydration: QSPR models using physicochemical HYBOT descriptors.

Stable and predictive quantitative structure-property relationship (QSPR) models of thermodynamics of chemical hydration (changes in Gibbs energy, DeltaG(air/water), enthalpy, DeltaH(air/water) and entropy DeltaS(air/water)) were obtained on the basis of physicochemical descriptors calculated by the HYBOT program. The structurally diverse training set (n = 151) and test set (n = 37) included 13 mono-functional chemical classes. The applied HYBOT descriptors comprise molecular polarizability alpha (as a volume-related term), the sum of partial negative charges on all atoms in a molecule SigmaQ(-) (as an electrostatic term) and the sum of H-bond acceptor and donor factors SigmaC(a) and SigmaC(d) (as H-bond terms). Final equations for changes in Gibbs energy and enthalpy provided good statistical criteria and standard deviations on the level of errors of experimental determinations. All four above-mentioned terms essentially contribute to hydration enthalpy and each of them increases negative values of enthalpy. Hydration Gibbs energy predominantly depends on hydrogen bonding between solute and water molecules. Steric and electrostatic terms act in opposite directions and partly compensate each other. Changes in entropy correlate with increasing H-bond acceptor ability, whereas the other three descriptors exhibit inverse correlations.