Review : Auto-oxidation of aliphatic polyamides

The literature on oxidation kinetics of polyamides and model compounds has been reviewed in order to try to extract suitable information for non-empirical kinetic modeling. Polyamide characteristics are systematically compared to polyolefin ones, these latter being more extensively studied. From kinetic analysis point of view, it is shown that oxidation attacks predominantly a amino methylenes of which C eH bond is considerably weaker than the other methylenes. As a result, propagation by H abstraction is considerably faster in polyamides than in polyethylene for instance. Termination by radical combination is also very fast. Another cause of PA oxidizability is the instability of a amino hydroperoxides linked to the inductive effect of nitrogen. This instability is responsible for many key features of oxidation kinetics especially the absence of induction period. The main stable oxidation products are imides resulting from disproportionation processes meanwhile chain scissions resulting from rearrangements of a amino alkyls by b-scission are also significant process although their yield appears lower than in polyolefins

A general kinetic model for the photothermal oxidation of polypropylene

A general kinetic model for the photothermal oxidation of polypropylene has been derived from the basic auto-oxidation mechanistic scheme in which the main sources of radicals are the thermolysis and photolysis of the most unstable species, i.e hydroperoxides. Thermolysis is a uni- or bi-molecular reaction whose rate constant obeys an Arrhenius law. In contrast, photolysis is exclusively a unimolecular reaction and its rate constant is independent of temperature. According to the quantum theory, this latter is proportional to the energy absorbed by photosensitive species and thus, accounts for the impact of UV-light intensity and wavelength on the global oxidation kinetics. The validity of this model has been checked on iPP films homogeneously oxidized in air over a wide range of temperatures and UV-light sources. It gives access to the concentration changes of: (i) primary (hydroperoxides) and secondary (carbonyls) oxidation products, (ii) double bonds, (iii) chain scissions and crosslinking nodes, but also to the subsequent changes in molecular masses. These calculations are in full agreement with the photolysis results reported by Carlsson and Wiles in the 70s [1–3]. However, the model seems to be only valid for UV-light energies equivalent to about 10 suns as upper boundary, presumably because of multiphotonic excitations or chromophores photosensitization (i.e. termolecular photo-physical reactions), both enhanced at high irradiances

Time-resolved fluorescence observation of di-tyrosine formation in horseradish peroxidase upon ultrasound treatment leading to enzyme inactivation

The application of ultrasound to a solution can induce cavitional phenomena and generate high localised temperatures and pressures. These are dependent of the frequency used and have enabled ultrasound application in areas such as synthetic, green and food chemistry. High frequency (100 kHz to 1 MHz) in particular is promising in food chemistry as a means to inactivate enzymes, replacing the need to use periods of high temperature. A plant enzyme, horseradish peroxidase, was studied using time-resolved fluorescence techniques as a means to assess the effect of high frequency (378 kHz and 583 kHz) ultrasound treatment at equivalent acoustic powers. This uncovered the fluorescence emission from a newly formed species, attributed to the formation of di-tyrosine within the horseradish peroxidase structure caused by auto-oxidation, and linked to enzyme inactivation

Quality characteristics of edible linseed oil

In this review the quality properties of linseed oil for food uses are discussed as well as factors affecting this quality. Linseed oil has a favourable fatty acid composition with a high linolenic acid content. Linseed oil contains nearly 60% á-linolenic acid, compared with 25% for plant oils generally. The content of linolenic acid and omega-3 fatty acids is reported to be high in linseed grown in northern latitudes. The composition of fatty acids, especially unsaturated fatty acids, reported in different studies varies considerably for linseed oil. This variation depends mainly on differences in the examined varieties and industrial processing treatments. The fatty acid composition leads also to some problems, rancidity probably being the most challenging. Some information has been published concerning oxidation and taste, whereas only a few studies have focused on colour or microbiological quality. Rancidity negatively affects the taste and odour of the oil. There are available a few studies on effects of storage on composition of linseed oil. In general, storage and heat promote auto-oxidation of fats, as well as decrease the amounts of tocopherols and vitamin E in linseed oil. Several methods are available to promote the quality of the oil, including agronomic methods and methods of breeding as well as chemical, biotechnological and microbiological methods. Time of harvesting and weather conditions affect the quality and yield of the oil

Requirement of a Plasmid-Encoded Catalase for Survival of \u3cem\u3eRhizobium etli\u3c/em\u3e CFN42 in a Polyphenol-Rich Environment

Nitrogen-fixing bacteria collectively called rhizobia are adapted to live in polyphenol-rich environments. The mechanisms that allow these bacteria to overcome toxic concentrations of plant polyphenols have not been clearly elucidated. We used a crude extract of polyphenols released from the seed coat of the black bean to simulate a polyphenol-rich environment and analyze the response of the bean-nodulating strain Rhizobium etli CFN42. Our results showed that the viability of the wild type as well as that of derivative strains cured of plasmids p42a, p42b, p42c, and p42d or lacking 200 kb of plasmid p42e was not affected in this environment. In contrast, survival of the mutant lacking plasmid p42f was severely diminished. Complementation analysis revealed that the katG gene located on this plasmid, encoding the only catalase present in this bacterium, restored full resistance to testa polyphenols. Our results indicate that oxidation of polyphenols due to interaction with bacterial cells results in the production of a high quantity of H2O2, whose removal by the katG-encoded catalase plays a key role for cell survival in a polyphenol-rich environment

Trans-1,2-disiloxybenzocyclobutene, an adequate partner for the auto-oxisation: EPR/spin trapping and theoretical studies

International audienceThe auto-oxidation of trans-1,2-disiloxybenzocyclobutene was found to be very efficient, giving endoperoxide in quantitative yield. Each step of the mechanism of spin-forbidden addition of triplet oxygen O2 was studied by both EPR/spin trapping and theoretical studies

Investigation on Fires in Coal Mines and Approach for Prevention – Case Study

Coal absorbs oxygen even at lower temperatures than the ambient temperature and they start heating up. This heating without any external source of supply of heat generally leads to due to auto-oxidation, also called spontaneous heating of coal.Due to auto-oxidation, we are faced with many dangerous problems. Therefore the assessment of this problem has become necessary and hence we are trying to calculate and predict how susceptible or prone any coal might be towards spontaneous heating before its use in any industry. As a Mining Engineer some steps towards the prevention were noted from the observations of earlier investigators and some suggestions are made from our findings which may reduce the possibilities of tendencies towards auto-oxidation and also to find some suitable way to minimize the threat caused due to this spontaneous heating

Effects of organic plant oils and role of oxidation on nutrient utilization in juvenile rainbow trout (Oncorhynchus mykiss)

The study compared the effect of four either fresh or force oxidized organic plant oils in diets for juvenile rainbow trout (Oncorhynchus mykiss) in which 47% of conventional LT fish meal protein was substituted by a mixture of 3 organic plant protein concentrates. Fish oil was completely substituted with either organic linseed oil; rape seed oil; sunflower oil or grape seed oil and evaluated based on feed intake, feed utilization, growth and digestibility. None of the plant oils affected feed intake and growth parameters. Organic plant oils had all a positive effect on lipid digestibility as compared with the fish oil based control diet, despite the very different FA profiles. The organic vegetable oils did not undergo autoxidation, as opposed to the fish oil control for which lipid digestibility was significantly negative influenced

Ambient-temperature co-oxidation catalysts

Oxidation catalysts which operate at ambient temperature were developed for the recombination of carbon monoxide (CO) and oxygen (O2) dissociation products which are formed during carbon dioxide (CO2) laser operation. Recombination of these products to regenerate CO2 allows continuous operation of CO2 lasers in a closed cycle mode. Development of these catalyst materials provides enabling technology for the operation of such lasers from space platforms or in ground based facilities without constant gas consumption required for continuous open cycle operation. Such catalysts also have other applications in various areas outside the laser community for removal of CO from other closed environments such as indoor air and as an ambient temperature catalytic converter for control of auto emissions