Einkristall-Strukturen eines Donator-Akzeptor-substituierten Cyclopentadiens,seines Kations und seines dimeren Anions: Verschiedenartige Störungen eines Kohlenstoff-Fünfringes

Single-Crystal Structures of a Donor-Acceptor-Substituted Cyclopentadiene, Its Cation and Its Anion Dimer: Different Distortion of a Five-Membered Carbon Ring 1,4-Dimethyl-2,3,4,6-tetrahydro-1 H-cyclopentapyrazine-5,7-dicarbonitrile, its molecular cation, and its dimer dianion, generated by hydride abstraction or deprotonation, and crystallized, differ remarkably in their structures: the five-membered ring in the neutral compound is of (Z)-butadiene-type, whereas, in the tetrafluorborate salt, a peripheric NCCCCCN⊕ cyanine distortion occurs and in the sodium derivatives, solvated by either one or two 1,2-dimethoxyethane molecules, a cyclopentadienyl anion is formed. The structural perturbations induced by changing molecular charges are rationalized by extensive MNDO calculations, which on geometry optimization, reproduce the experimental structures and, in addition, provide charge distributions, further confirming the n_N/π and π/π interactions already recognizable from the structural parameters.     

Probing the mechanism of Prins cyclisations and application to the synthesis of 4-hydroxytetrahydropyrans

Trapping intermediates on the Prins cyclisation pathway with carbon-based nucleophiles has given further insight into factors affecting the acid-mediated reactions of homoallylic alcohols with aldehydes, enabling the design of efficient syntheses of 4-hydroxy-2,6-disubstituted tetrahydropyrans.     

Simulation study of the coil-globule transition of a polymer in solvent

Molecular dynamics simulations are used to study the coil-globule transition for a system composed of a bead-spring polymer immersed in an explicitly modeled solvent. Two different versions of the model are used, which are differentiated by the nature of monomer-solvent, solvent-solvent, and nonbonded monomer-monomer interactions. For each case, a model parameter lambda determines the degree of hydrophobicity of the monomers by controlling the degree of energy mismatch between the monomers and solvent particles. We consider a lambda-driven coil-globule transition at constant temperature. The simulations are used to calculate average static structure factors, which are then used to determine the scaling exponents of the system in order to determine the theta-point values lambdatheta separating the coil from the globule states. For each model we construct coil-globule phase diagrams in terms of lambda and the particle density rho. The results are analyzed in terms of a simple Flory-type theory of the collapse transition. The ratio of lambdatheta for the two models converges in the high density limit exactly to the value predicted by the theory in the random mixing approximation. Generally, the predicted values of lambdatheta are in reasonable agreement with the measured values at high rho, though the accuracy improves if the average chain size is calculated using the full probability distribution associated with the polymer-solvent free energy, rather than merely using the value obtained from the minimum of the free energy.     

The determination of microgram amounts of sulphur in nitrate or chloride solutions

It is shown that μg quantities of sulphate can be “collected” with barium chromate when the latter is precipitated from solutions at a pH of about 1. The sulphate in this precipitate can be converted to hydrogen sulphide when the precipitate is treated at red heat with a mixture of hydrogen and hydrogen chloride vapour. The above procedure has been made the basis of a method for determining traces of sulphur, down to about 0.2 p.p.m. on a 10 g sample, when the hydrogen sulphide is determined absorptiometrically as Lauth's violet.     

Determination of hydroxy-s-triazines in water using HPLC or GC-MS

Two methods are described for the routine determination of triazine degradation products in water. After solid phase extraction by means of RP-C₁₈ cartridges, the separation and detection were carried out using either HPLC (for hydroxy-atrazine [OHA], hydroxy-simazine [OHS], hydroxy-propazine [OHP], hydroxy-terbutylazine [OHT] and hydroxy-desethylatrazine [OHDEA]) or GC-MS (only for OHA, OHS, OHP and OHT after methylation with diazomethane). The HPLC set-up is described for detecting the hydroxy-triazines, including hydroxy-desisopropylatrazine (OHDIA), hydroxy-desethyldesisopropylatrazine (OHDEDIA) and cyanuric acid (CA). The average recoveries at concentration levels between 50 ng/L and 1 g/L ranged from 35% to 43% for GC-MS (n=5) and from 53% to 75% for HPLC (n=5) with the exception of hydroxy-desethylatrazine which has been recovered with only 21%. Hydroxy-desisopropylatrazine, hydroxy-desethyldesisopropylatrazine and cyanuric acid could not be enriched on RPC₁₈. The determination limit of the investigated compounds has to be set between 90 and 100 ng/L for both methods for OHS, OHA, OHP and OHT.     

Integrated Systems for Water Cleavage by Visible Light; Sensitization of TiO2 Particles by Surface Derivatization with Ruthenium Complexes

Irradiation of acidic (pH 2) solutions of RuL₃²⁺ 2Cl^? (L = diisopropyl 2,2′-bipyridine-4,4′ -dicarboxylate) in the presence of TiO₂ at 100°C leads to the loss of one bipyridyl ligand and the chemical fixation of RuL₂ at the surface of teh TiO₂ particles through formation of Ru-O-Ti bonds. These surface complexes are very stable and shift the absorption onset of TiO₂ beyond 600 mm. Efficient sensitization H₂-generation is achieved with this system beginning in the wave length domain between 590 and 665 nm. Preliminary water cleavage experiments with bifunctional TiO₂/Pt/RuO₂ redox catalyst are reported.     

Magnetic quantum dots: synthesis, spectroscopy, and magnetism of Co2+ - and Ni2+-doped ZnO nanocrystals

We report a method for the preparation of colloidal ZnO-diluted magnetic semiconductor quantum dots (DMS-QDs) by alkaline-activated hydrolysis and condensation of zinc acetate solutions in dimethyl sulfoxide (DMSO). Mechanistic studies reveal that Co(2+) and Ni(2+) dopants inhibit nucleation and growth of ZnO nanocrystals. In particular, dopants are quantitatively excluded from the critical nuclei but are incorporated nearly isotropically during subsequent growth of the nanocrystals. The smaller nanocrystal diameters that result upon doping are explained by the Gibbs-Thompson relationship between lattice strain and crystal solubility. We describe methods for cleaning the nanocrystal surfaces of exposed dopants and for redispersion of the final DMS-QDs. Homogeneous substitutional doping is verified by high-resolution low-temperature electronic absorption and magnetic circular dichroism (MCD) spectroscopies. A "giant Zeeman effect" is observed in the band gap transition of Co(2+):ZnO DMS-QDs. MCD and Zeeman spectroscopies are used to quantify the magnitude of the p-d exchange interaction (N(0)beta) that gives rise to this effect. N(0)beta values of -2.3 +/- 0.3 eV (-18 500 cm(-1)) for Co(2+):ZnO and -4.5 +/- 0.6 eV (-36 300 cm(-1)) for Ni(2+):ZnO have been determined. Ligand-to-metal charge-transfer transitions are observed in the MCD spectra of both Co(2+):ZnO and Ni(2+):ZnO DMS-QDs and are analyzed in the context of an optical electronegativity model. The importance of these charge-transfer states in determining N(0)beta is discussed. Ferromagnetism with T(C) > 350 K is observed in aggregated nanocrystals of Co(2+):ZnO that unambiguously demonstrates the existence of intrinsic high-T(C) ferromagnetism in this class of DMSs.