Short synthesis of new salacinol analogues and their evaluation as glycosidase inhibitors

Versatile synthesis of some analogues of the naturally-occurring α-glucosidase inhibitor salacinol (1), involving thioanhydro alditol moieties with erythro, d,l-threo, xylo, ribo, d-arabino and d-manno configurations is described. Nucleophilic attack at the least-hindered carbon atom of an l- or d-protected erythritol cyclic sulfate by the thioanhydro alditol sulfur atom yielded the desired zwitterionic compounds. In addition, the preparation of the cyclic sulfates of 2,4-O-benzylidene-d-erythritol and 2,4-O-isopropylidene-l-erythritol was improved. Enzyme inhibition tests showed that most of the new compounds were weak but specific inhibitors, while good inhibitory activity was found for a six-membered ring analogue (β-glucosidase: K_i=16 μM).     

Acquired biodegradability of polyethylenes containing pro-oxidant additives

Biodegrability of high density polyethylene film (HDPE) and low density polyethylene film (LDPE) both containing a balance of antioxidants and pro-oxidants was studied with defined microbial strains particularly with Rhodococcus rhodochrous and Nocardia asteroides in mineral medium. After an abiotic pre-treatment consisting of photooxidation and thermo-oxidation corresponding to about 3 years of outdoor weathering the samples were inoculated, incubated up to 200 days and during the period their metabolic activities were followed by measuring adenosine triphosphate content. Simultaneously the cultures were also monitored by optical microscopy and FTIR spectroscopy. The first initial phase of fast growth caused by the presence of low molecular extractable compounds was followed by a long period of stabilized metabolic activity suggesting that microorganisms continued to gain energy from the substrate but evidently at a much slower rate. Complementary analysis performed at the end of incubation revealed that during the experiment time biodegradation processes probably affected surface layer of materials only.     

Can Polyethylene be a Photo(bio)Degradable Synthetic Polymer?

Abstract

A polymeric system based on LDPE would be qualified as a “photo(bio)degradable synthetic polymer” for use as films or thin systems in plasticulture and later in packaging where severe specific criteria should be respected. The evolution of such a system in environmental conditions should present three phases. In Phase I, corresponding to storage and use, in the presence of physicochemical and biological aggression, chemical evolution should be very limited and resistance to any microorganism should be observed. In Phase II a rapid abiotic degradation should occur until the complete destruction of physical (mechanical) properties and spontaneous fragmentation of the thin systems into more and more divided parts. Phase III corresponds to bioassimilation of heavily transformed (oxidized) solid particles. Phase I should be predicted and controlled on the basis of artificial photoaging or thermoaging experiments. Depending on the desired lifetime of the system, nonaccelerated, accelerated, or ultra-accelerated photoaging techniques could be used. The earliest fragmentation, which should be observed in Phase II, should be predicted within the same experiment. The prediction of the long-term fate of the polymeric materials should be based not only on the variations of physical properties but on a full analysis of the chemical evolution, i.e., determination of the major final transformed groups of the macromolecular chains (and especially the acidic end groups) and the molar mass distribution. In a recent BRITE-EURAM European contract, we developed an experimental protocol for the control of Phase III based on the use of pure cultures of strains from collections or selected adapted wild strains (from industrial polyethylene site dumpings) which had been examined. Abiotically oxidized LDPE was the only carbon source in a starving mineral medium. Bioerodibility caused by the carboxylic acid formed throughout abiotic degradation has been observed.     

Safran

Ohne Zusammenfassung     

Strong supramolecular-based magnetic exchange in pi-stacked radicals. Structure and magnetism of a hydrogen-bonded verdazyl radical:hydroquinone molecular solid.

The X-ray crystal structure and magnetic properties of a molecular crystal consisting of 1,5-dimethyl-3-(2-pyridyl)-6-oxoverdazyl radical and hydroquinone (pyvd:hq) are presented. The structure contains a two-dimensional network of hydrogen bonds involving the hydroquinones and the pyridine ring of the pyvd radical. The radicals adopt an unusual head-over-tail (antiparallel) pi-stacked array perpendicular to the hydrogen-bonded planes. The variable-temperature magnetic susceptibility data can be modeled using a one-dimensional antiferromagnetic chain model, with J = -58 cm(-1). The strength of the magnetic coupling is very unusual because there are no close intermolecular radical-radical contacts to provide conventional pathways for magnetic interactions. A pathway for coupling is proposed involving the mediation of magnetic exchange interactions between radical centers by the pyridine rings. Density functional calculations on the pyvd radical, as well as aggregates thereof based on the X-ray structure, have been employed in attempts to understand the possible mechanisms by which the strong magnetic interactions are achieved.