Vinyl nosylates as partner in copper and silver co-catalyzed Sonogashira cross-coupling reactions

Vinyl nosylates, readily obtained from β-dicarbonyl derivatives, could be efficiently engaged in Sonogashira cross-coupling reactions, either cocatalyzed by copper or silver salts. The para-nitrobenzenesulfonate (nosylate) group allows this coupling to be performed under very mild conditions (room temperature). These new leaving group and mild conditions could be applied to the synthesis of acetylenic coumarinyl derivatives and to the total synthesis of an acetylenic monoterpene natural product, named cleviolide.     

Genotoxicity and Cytotoxicity of 4-Nonylphenol Ethoxylate on Lymphocytes as Assessed by the Comet Assay

Surfactants, which are prevalent at industrial sites and in the environment generally, are potential risk factors in human carcinogenesis. The widespread industrial use of surfactants such as 4-alkylphenol ethoxylates and their prevalence in many cleaning products have provoked studies about surfactant concentrations in water and their toxicity levels. Up to now, these substances have mainly been tested on aquatic organisms. Though tests on human cell lines are rare. The alkaline Comet assay was performed to evaluate the genotoxicity of 4-nonylphenol ethoxylate, a biodegradable product of 4-alkylphenol ethoxylate, in human lymphocytes. Concentrations tested ranged from 0.15 to 150 µg/mL. Test concentrations of 10 to 15 µg/mL caused an increase level of DNA migration in human cells, but without inducing excessive toxicity (viability > 80%). Though induced levels of DNA migration starting at concentrations of 30 µg/mL may have been due to excessive levels of cytotoxicity (viability < 70%). Based on these data, 4-nonylphenol ethoxylate can induce DNA damage in human lymphocytes but at higher concentrations than are normally found in river or drinking water. However, considering the prevalence of surfactants, the measured genotoxicity of these substances is of concern. Further investigations on human target cells are necessary to evaluate the carcinogenic impact of surfactants and reconsider their environmental acceptance.     

Topography of Nucleic Acid Helices in Solutions

A number of reporter molecules of the structure R-(CH₂)_n-N⁺(CH₃)₂(CH₂)_mN⁺(CH₃)₃·2Br^?, where R is a chromophore absorbing in the 300–500 mp region, have been synthesized. The effect of DNA and RNA on the absorption, induced circular dichroism, and proton magnetic resonance spectra is reported. A red shift and a hypochromic effect on the absorption spectra of the bound chromophore is observed. In all cases where R is an “unsymmetrical” 4-nitroaniline chromophore, it is found that DNA and RNA induce an opposite CD in the absorption band of the bound reporter molecules. These results together with PMR studies are interpreted in terms of the structure of the nucleic acid systems in solutions.     

Expedient and Diastereodivergent Assembly of Terpenoid Decalin Subunits having Quaternary Stereocenters through Organocatalytic Robinson Annulation of Nazarov Reagent

We report an expedient approach to highly functionalized cis‐ and trans‐decalines that could function as key structural subunits toward the synthesis of various classes of terpenoids. Key to the strategy is an organocatalyzed Robinson annulation reaction of the Nazarov reagent that affords chiral enone building blocks with high enantioselectivities. The quaternary carbon stereogenic center can direct the subsequent reactions and allow the rapid and diastereoconvergent assembly of complex decalines with contiguous stereocenters.     

Study of flame-retardant finishing of cellulose fibres: Organic–inorganic hybrid versus conventional organophosphonate

The aim of this study was to introduce a non-formaldehyde inorganic–organic hybrid sol–gel flame-retardant precursor (SiOP) containing phosphorous, nitrogen, and silicon and to compare its functional properties with those of the conventional formaldehyde-containing organic flame-retardant agent, organophosphonate (OP). SiOP was used at concentrations of 2%, 4%, and 8%, and OP was used at a concentration of 200 g/dm³. Both agents were applied to 100% cotton (CO) woven fabric by the pad-dry-cure method under the appropriate conditions. The presence of the SiOP and OP coatings on the CO fabric was confirmed by scanning electron microscopy, energy dispersive X-ray spectroscopy and Fourier-transform infrared spectroscopy. The results of the vertical tests of flammability and the thermogravimetric analyses showed that the presence of the SiOP coating changed the thermal degradation pathway of the CO fabric and resulted in an increase in the thermo-oxidative stability of the cellulose fibres. The thermo-oxidative stability was enhanced by the addition of higher amount of dry solids. At comparable dry solids contents, OP preserved significantly greater flame retardancy and thermo-oxidative stability than did SiOP. These results indicated that the SiOP precursor could not act as an effective alternative to the OP agent in the flame-retardant protection of CO fabric.