PHOTOCHEMISTRY OF PESTICIDES, 71. REGIOSELECTIVE PHOTODIMERIZATION OF o,o-DIETHYL-o-(3-CHLORO-4-METHYLCOUMARIN-7-YL)-THIOPHOSPHATE (COUMAPHOS)

Abstract

UV-irradiation (λ > 313 nm) of o,o-diethyl-o-(3-chloro-4-methyl-coumarin-7-yl)-thiophosphate (Coumaphos; 1) in chloroform results in an regioselective dimerization reaction to afford the head-to-tail anti-dimer 2. The structure of 2 is established by single crystal x-ray diffraction. Singlet oxygen does not affect the formation of 2.     

The Potential of O‐MMT as a Reinforcing Filler for Uncured and Dynamically Cured PVC/XNBR Composites

Organic montmorillonite modified with quaternary ammonium (O‐MMT) was compounded with uncured and dynamically cured poly(vinyl chloride)/carboxylated nitrile butadiene rubber (PVC/XNBR) composites, using a Brabender Plasticorder at 130°C and 50 rpm rotor speed. The reinforcing efficiency of the O‐MMT was investigated in the uncured PVC/XNBR composite and the dynamically cured PVC/XNBR counterpart. Mixing and dynamic curing of the composites were monitored by typical torque‐time curves derived from a Brabender internal mixer. The torque‐time curves revealed that the dynamic curing process was successful and the incorporation of O‐MMT has no adverse effect on the processibility of the composites. It has been found that the introduction of crosslinks within the rubbery phase in the presence of the O‐MMT has further improved the tensile properties. DMA studies revealed that dynamically cured composite with O‐MMT showed higher storage modulus than the composite without O‐MMT. Furthermore, a one‐step tensile modulus vs. temperature curve and a related one peak tensile loss modulus vs. temperature curve were obtained, consequently, both are characteristics of a miscible polymers system. Further evidence on the composite miscibility was purchased by thermal scans from DSC, which showed a single glass transition temperature of PVC/XNBR composites. This claim was further supported by ATR‐IR spectra which revealed that hydrogen bonding is extensively involved in PVC/XNBR composites. This evidence unveiled the exact nature of the specific interactions responsible for miscibility and hence, enhanced mechanical properties. Furthermore, we proved in our studies the reinforcing role played by layered clay due to better dispersion, as well as improved interactions.     

Structure and photoconductive behaviour of a sanidic liquid crystal

A series of [1]benzothieno[3,2-b][1]benzothiophene-2,7-dicarboxylate derivatives consisting of a flat, conjugated aromatic moiety containing sulphur hetero-atoms and substituted by terminal chains - ethyl, decyl, Z-4-decenyl or 2-(2-butoxyethoxy)ethyl - has been synthesized. These materials exhibit a smectic liquid crystalline phase, the stability of which was found to be strongly dependent on the length and the nature of the terminal chains. In the mesophase, the molecular arrangement within the smectic layer is characterized by a local stacking of the rigid parts similar to that found in discotic columnar systems. Finally, clear photoconductive behaviour was found in mechanically aligned samples of these liquid crystals.     

Determination of the total purity of a high-purity silver material to be used as a primary standard for element determination

A candidate material for the use as primary standard for silver determination was characterized with respect to total purity. Except the radioactive elements and He, all possible impurities were considered. Based on glow discharge mass spectrometry, inductively coupled plasma-mass spectrometry and carrier gas hot extraction measurements, the demonstrated total purity and its standard uncertainty is w(Ag) = (99.999 52 ± 0.000 11) %. The purity value and its uncertainty is dominated by the contributions from the measurements of the nonmetallic impurities, namely S, N, C and O.     

Catalytic Activation of Imines by Chalcogen Bond Donors in a Povarov [4+2] Cycloaddition Reaction

Recently, chalcogen bonding has been investigated in more detail in organocatalysis and the scope of activated functionalities continues to increase. Herein, the activation of imines in a Povarov [4+2] cycloaddition reaction with bidentate cationic chalcogen bond donors is presented. Tellurium-based Lewis acids show superior properties compared to selenium-based catalysts and inactive sulfur-based analogues. The catalytic activity of the chalcogen bonding donors increases with weaker binding anions. Triflate, however, is not suitable due to its participation in the catalytic pathway. A solvent screening revealed a more efficient activation in less polar solvents and a pronounced effect of solvent (and catalyst) on endo : exo diastereomeric ratio. Finally, new chiral chalcogen bonding catalysts were applied but provided only racemic mixtures of the product.     

Arene Ruthenium(II) Complexes Bearing the κ-P or κ-P,κ-S Ph2P(CH2)3SPh Ligand

Neutral [Ru(η⁶-arene)Cl₂{Ph₂P(CH₂)₃SPh-κP}] (arene = benzene, indane, 1,2,3,4-tetrahydronaphthalene: 2a, 2c and 2d) and cationic [Ru(η⁶-arene)Cl(Ph₂P(CH₂)₃SPh-κP,κS)]X complexes (arene = mesitylene, 1,4-dihydronaphthalene; X = Cl: 3b, 3e; arene = benzene, mesitylene, indane, 1,2,3,4-tetrahydronaphthalene, and 1,4-dihydronaphthalene; X = PF₆: 4a–4e) complexes were prepared and characterized by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy and also by single-crystal X-ray diffraction analyses. The stability of the complexes has been investigated in DMSO. Complexes have been assessed for their cytotoxic activity against 518A2, 8505C, A253, MCF-7 and SW480 cell lines. Generally, complexes exhibited activity in the lower micromolar range; moreover, they are found to be more active than cisplatin. For the most active ruthenium(II) complex, 4b, bearing mesitylene as ligand, the mechanism of action against 8505C cisplatin resistant cell line was determined. Complex 4b induced apoptosis accompanied by caspase activation.     

Comment on "Wide-field coherent anti-Stokes Raman scattering microscopy with non-phase-matching illumination"

We comment on a Letter by Toytman et al. [Opt. Lett.32, 1941 (2007)] in which a novel setup for wide-field imaging in coherent anti-Stokes Raman scattering (CARS) microscopy is demonstrated. There the authors state that our phase-matching implementation of a wide-field CARS system [Appl. Phys. Lett.84, 816 (2004); New J. Phys.8, 36 (2006)] suffers from a strong background from the bulk medium. However, our results show quite the contrary, i.e., that our setup provides a very good signal contrast, due to an almost vanishing background level from the bulk solvent.