Molecular structure, vinyl rotation barrier, and vibrational dynamics of 2,6-dichlorostyrene. A theoretical and experimental research

The molecular structure of 2,6-dichlorostyrene has been analyzed at MP2 and DFT levels using different basis sets concluding in a nonplanar geometry. The influence of either the level of theory or the nature of the substituent has been assessed. The vinyl-phenyl torsion barrier has also been investigated as a function of level of theory. The ultimate factors responsible for the torsion barrier have been studied using two different partitioning schemes, i.e., the total electronic potential energy and the natural bond orbital, NBO. A topological analysis of the electron density within the atom-in-molecule, AIM, theory predicts soft intramolecular chlorine (ring)-hydrogen (vinyl) contacts when the system becomes planar. A first complete vibrational study has been performed using theoretical data and experimental vibrational frequencies from IR, Raman and, for the first time, inelastic neutron scattering, INS, spectra. The new assignment proposed is based on a scaled quantum mechanical, SQM, force field and the wavenumber linear scaling, WLS, approach.     

Dissipation rates of procymidone and azoxystrobin in greenhouse grown lettuce and under cold storage conditions

The dissipation of two fungicides (procymidone and azoxystrobin) was evaluated in greenhouse grown lettuce and under cold storage conditions. Lettuce samples were collected from an experimental greenhouse during a five week period, in which two consecutive applications of these pesticides were performed. Gas chromatography (GC) with electron-capture detection (ECD) was used to study the disappearance of these compounds in lettuce. Confirmation analysis of pesticides was carried out by capillary gas chromatography coupled with mass spectrometry in the selected ion monitoring (SIM) mode. The disappearance rates of these compounds on lettuces in field after two applications were described as pseudo-first-order kinetics with strong correlation between residue concentration and time (r was in all cases higher than 0.983). The half-lives for first and second applications were of 5.31 and 4.65 days for procymidone and 6.23 and 4.87 days for azoxystrobin, respectively. When procymidone and azoxystrobin were applied two times during cultivation, at maximum recommended dose, the residues of both pesticides were below maximum residue limits (MRLs) after the established preharvest intervals. After 21 days under cold and darkness storage conditions, dissipation of procymidone and azoxystrobin was not observed.     

Galois theory and commutators

We prove that the relative commutator with respect to a subvariety of a variety of Ω-groups introduced by the first author can be described in terms of categorical Galois theory. This extends the known correspondence between the Fröhlich–Lue and the Janelidze–Kelly notions of central extension. As an example outside the context of Ω-groups we study the reflection of the category of loops to the category of groups where we obtain an interpretation of the associator as a relative commutator.     

Synthesis,structural and spectral properties of Au complexes: luminescence properties and their non‐covalent DNA binding studies

Gold complexes of 1,3‐ bis‐pyridylimidazolium chloride ( L1 ), 1,3‐bis‐[2,6‐diisopropylphenyl]imidazolium chloride ( L2 ) and 1,3‐bis‐[benzyl]benzimidazolium chloride ( L3 ) were synthesized and characterized by analytical methods. For the complexes, electronic spectral results show that there is a marked difference in the band feature observed in the spectra, ascribed to the greater relativistic effect of gold. In fluorescence studies, the complexes develop emission bands in the visible region (400–600 nm) after excitation at around 350 nm. Au complex–DNA binding was studied, and it was observed that genomic DNA isolated from the U373‐GB cell line was fragmented and in some cases degraded by the Au complexes. Furthermore, the intensity of the DNA band increased when concentration of the metal complex was augmented. This study shows that the DNA cleavage is mediated by the Au complex. Copyright © 2013 John Wiley & Sons, Ltd.     

Measuring the pollutant transport capacity of dissolved organic matter in complex matrixes

Dissolved organic matter (DOM) facilitated transport in contaminated groundwater was investigated through the measurement of the binding capacity of landfill leachate DOM (Vejen, Denmark) towards two model pollutants (pyrene and phenanthrene). Three different methods for measuring binding capacity were used and evaluated, head-space solid-phase micro-extraction (HS-SPME), enhanced solubility (ES) and fluorescence quenching (FQ). It was concluded that for samples with complex matrixes it was possible to measure the net effect of the DOM binding capacity and the salting out effect of the matrix. It was further concluded that DOM facilitated transport should be taken into account for non-ionic PAHs with lg?K?_OW above 5, at DOM concentrations above 250?mg?C/L. The total DOM concentration was found to be more important for the potential of facilitated transport than differences in the DOM binding capacity.     

pH-Dependent Chalcogenopyrylium Dyes as Potential Sensitizers for Photodynamic Therapy: Selective Retention in Tumors by Exploiting pH Differences between Tumor and Normal Tissue

Ideal photosensitizers have long-wavelength absorption and strong tumor selectivity with rapid clearance from normal tissues. The telluroselenopyrylium dye 1 that absorbs light at 795 nm (epsilon = 285,000 M-1 cm-1) has a novel property that enhances the tumor specificity and normal tissue clearance. After intralesional injection to both tumors and surrounding skin, it disappeared from the normal skin of BALB/c mice faster than it did from subcutaneously implanted Colon 26 tumors, which resulted in therapeutic selectivity. In vivo reflectance spectroscopy showed that the half-life in tumor was about 50 min while in skin it was around 12 min. This phenomenon appears to be related to the pH differences in normal skin versus tumor, because the rates of drug hydrolysis in solution were shown to be sensitive to changes in pH. Inhibition of tumor regrowth following intratumoral photosensitizer administration depended on both light dose and drug dose, as well as the time interval between dye injection and irradiation; selectivity depended on the time interval. Although treatment parameters were not optimized efficacy was superior to systemic Photofrin under our standard conditions. We discuss how new, more optimal, photosensitizers can be designed that use rates of hydrolysis to exploit the differences in pH between normal tissue and tumor.     

Determining the temperature from incomplete boundary data

An iterative procedure for determining temperature fields from Cauchy data given on a part of the boundary is presented. At each iteration step, a series of mixed well‐posed boundary value problems are solved for the heat operator and its adjoint. A convergence proof of this method in a weighted L²‐space is included, as well as a stopping criteria for the case of noisy data. Moreover, a solvability result in a weighted Sobolev space for a parabolic initial boundary value problem of second order with mixed boundary conditions is presented. Regularity of the solution is proved. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photo-induced catalytic partial oxidation of citronellol with assistance of phthalocyanines

Attention was paid to the role of sulfonated phthalocyanines as efficient photocatalysts in the photo-induced partial oxidation of citronellol. Performance of the singlet oxygen species inducing the formation of citronellol hydroperoxides was studied in detail. The involved reactions may be of great importance in the catalytic production of rose oxide — a highly appreciated component of many synthetic fragrances.