Photo- and thermal-oxidation of polyethylene: Comparison of mechanisms and influence of unsaturation content

The behaviour of polyethylene with different contents in vinyl and t-vinylene groups have been studied by photooxidation with λ ≥ 300 nm light or by thermooxidation at a temperature of 100 °C. The oxidation was studied by infrared spectroscopy and it was shown that the same oxidation products were obtained, but with different relative concentrations depending on the conditions of ageing, i.e. photochemical or thermal conditions. The mechanisms by which the oxidation products are formed were recalled. The differences between photo- and thermo-oxidation were evidenced on the basis of the stability of ketones that do not accumulate in photochemical conditions, as a result of Norrish reactions. The influence of the initial amount of unsaturated groups on the rates of oxidation was characterized. It was shown that the concentration of unsaturations had no effect on the rate of photooxidation but dramatically influenced the stability in thermooxidative conditions.     

Synthesis of orthogonally protected azepane β-amino ester enantiomers

A simple and convenient route is presented for the preparation of regio- and stereoisomers of novel azepane β-amino esters, starting from bicyclic β-lactam isomers. The synthetic procedure consists of dihydroxylation of the olefinic bond of the alicyclic amino esters, followed by NaIO₄-mediated cleavage of the diol intermediate and reductive ring closure, which furnishes novel regioisomeric 5-aminoazepane-4-carboxylate and 3-aminoazepane-4-carboxylates. This method also allows the preparation of amino esters with an azepane skeleton in enantiomerically pure form.     

Metabolic compartmentalization in the human cortex and hippocampus: evidence for a cell- and region-specific localization of lactate dehydrogenase 5 and pyruvate dehydrogenase

Background  

For a long time now, glucose has been thought to be the main, if not the sole substrate for brain energy metabolism. Recent data nevertheless suggest that other molecules, such as monocarboxylates (lactate and pyruvate mainly) could be suitable substrates. Although monocarboxylates poorly cross the blood brain barrier (BBB), such substrates could replace glucose if produced locally.     

Comparison of separation performances of amylose- and cellulose-based stationary phases in the high-performance liquid chromatographic enantioseparation of stereoisomers of β-lactams

High-performance liquid chromatographic methods were developed for the separation of the enantiomers of 19 β-lactams. The direct separations were performed on chiral stationary phases containing either amylose tris(3,5-dimethylphenylcarbamate), (Kromasil® AmyCoat? column) or cellulose tris(3,5-dimethylphenylcarbamate), (Kromasil® CelluCoat? column) as chiral selector. The different methods were compared in systematic chromatographic examinations. The separations were carried out with good selectivity and resolution. The AmyCoat? and CelluCoat? columns appear to be highly complementary. The best separations of bi- and tricyclic β-lactam stereoisomers were obtained with the AmyCoat? column, while the 4-aryl-substituted β-lactams were better separated on the CelluCoat? column. The elution sequence was determined in all cases; no general rule could be established.     

Study of the high temperature reactions of a hindered aryl phosphite (Hostanox PAR 24) used as a processing stabiliser in polyolefins

The processing stabilising performance of various phosphorous antioxidants in polyolefins is affected significantly by their chemical composition. In order to explore the mechanism of stabilisation, the reactions of a hindered aryl phosphite [tris(2,4-di-tert-butylphenyl)phosphite (DTBPP), Hostanox PAR 24] were investigated at temperatures corresponding to polyethylene processing. The thermal and thermo-oxidative stability of the additive was determined by differential scanning calorimetric (DSC) and thermogravimetric methods. DTBPP was heat treated under argon and oxygen at 200 and 240 °C. The stabiliser was reacted at 200 °C with azobisisobutyronitrile (AIBN) in oxygen-free environment (carbon centred radicals) and under oxygen (peroxy radicals), with dicumyl peroxide (DCP) in oxygen atmosphere (oxy radicals), and with cumene hydroperoxide (CHP) under argon. The reaction products were identified by FT-IR, HPLC and HPLC-MS. The results revealed that besides the known reactions of hindered aryl phosphites, thermal decomposition and recombination reactions also take place above the melting point of the antioxidant. DTBPP does not react with molecular oxygen, but its decomposition is accelerated by oxygen and especially by radicals. Accordingly, the heat-stability of phosphorous stabilisers also has to be taken into account in their application, as it is one of the factors which influence the processing stabilisation of polyolefins.     

Uptake and biological responses to nano-Fe versus soluble FeCl3 in excised mussel gills

Nano-Fe particle uptake was experimentally examined in vitro using excised gills and blood cells of the edible blue mussel Mytilus sp. Whole gills were exposed to both Fe₂O₃ nanoparticles and a solution of the hydrated FeCl₃ salt, for up to 12 h, and blood cells for 30 min. Equimolar Fe⁺³ in the nano- and the soluble form was estimated under the assumption of dense spherical particles accommodating the same number of Fe⁺³ as in the dissolved salt solution, namely: 1,000 μg L⁻¹ Fe₂O₃ equivalent to 100 μg L⁻¹ FeCl₃·6H₂O. Putative toxic impact of nano-Fe in gill epithelia and blood cells was assessed by an array of techniques including light- and electron microscopy, biomarkers for oxidative stress (lipid peroxidation levels), neurotoxic effects (acetylcholinesterase activity) and cytotoxicity (neutral red retention). Total and filtered fractions (20 and 200 nm, respectively) of Fe were analysed by ICP-OES. Our results provide evidence for the following: (1) much of both the soluble (95%) and the nano-Fe (90%) were removed from the water column within 12 h; (2) dissolved- and nano-Fe seemed to follow different routes of uptake within the gill epithelium; (3) both nano-Fe and soluble FeCl₃ caused similar impairment of lysosomal stability in circulating blood cells; (4) lipid peroxidation in gills exposed to the two distinct forms of Fe was increased, while acetylcholinesterase activity was unaffected. In these short-term in vitro studies, there appears to be little difference in toxic response between exposure to the Fe salt and the nano-Fe indicating that, in this case, the nanoparticles do not invoke special properties affecting biological function in gills. However, with the use of nano-Fe as a food additive, clearly longer-term in vivo studies are warranted.     

A new enzymatic strategy for the preparation of (2R,3S)-3-phenylisoserine: a key intermediate for the Taxol side chain

Burkholderia cepacia lipase PS-IM catalysed the hydrolysis of racemic ethyl 3-amino-3-phenyl-2-hydroxypropionate with excellent enantioselectivity (E >200), when the reaction was performed with added H₂O as a nucleophile, in iPr₂O, at 50 °C. The hydrolysis of the less reactive enantiomeric ethyl 3-amino-3-phenyl-2-hydroxypropionate with 18% HCl afforded the corresponding enantiomerically pure (2R,3S)-3-amino-3-phenyl-2-hydroxypropionic acid hydrochloride, a key intermediate for the Taxol side chain.     

A new strategy for the preparation of heterocyclic β-amino esters: orthogonally protected β-amino esters with a piperidine skeleton

A simple strategy is presented for the introduction of a nitrogen atom into the carbocycle of an aminocyclopentenecarboxylic ester via dihydroxylation of the olefinic bond, followed by NaIO₄-mediated cleavage of the diol intermediate and ring expansion, resulting in new regioisomeric 3-amino-4-piperidinecarboxylic acid derivatives. This method permits the preparation of amino esters with a piperidine skeleton in enantiomerically pure form.     

New type of drift tubes for gas-discharge detectors operating in vacuum: Production technology and quality control

A device for fabricating thin-wall (straw) drift tubes using polyethylene terephthalate film 36 μm thick by ultrasonic welding is described together with the technique for controlling their quality. The joint width amounts to 0.4–1.0 mm. The joint breaking strength is 31.9 kg/mm². The argon leakage from a tube of volume 188.6 cm³ under a pressure gradient of 1.0 atm does not exceed 0.3 × 10^–3 cm³/min, which is mainly related to the absence of metallization in the joint vicinity. The high strength, the low tensile creep due to the absence of glued layers, the small value of gas leakage makes the new tubes capable of reliable and long-term operation in vacuum, which is confirmed by the operation of 7168 straw tubes for two years in the NA62 experiment.