Strain induced strengthening of soft thermoplastic polyurethanes under cyclic deformation

We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU.     

Comparison of different injection modes in edible oil minor components analysis

Waxes and fatty acid alkyl esters are minor components used as official parameters to control the authenticity and quality of a high‐value olive oil product. A poor measurement can lead to a misleading classification of the oil. The official method requires their analysis together by capillary gas chromatography equipped with a flame ionization detector and an on‐column injector to avoid discrimination and thermal degradation. The degradation can occur to a different extent if different (and not properly optimized) injectors are used. However, other injection techniques, such as programmed‐temperature vaporizer, are much more versatile and more widespread. The aim of the present work was to compare the performance of a programmed‐temperature vaporizer injector, in on‐column and splitless mode, with the on‐column injector to analyze alkyl esters and waxes. Discrimination among high‐boiling compounds was evaluated, as well as the occurrence of thermal degradation, especially of sterols and diterpene alcohol (phytyl and geranylgeraniol) esters. A proper optimization of a programmed‐temperature vaporizer injection, with particular attention to the liner selection, was proven to provide comparable results to the traditional on‐column injection. A performance comparison was carried out both on standard mixtures and on real oil samples.     

Fast electrodeposition of zinc onto single zinc nanoparticles

The zinc deposition reaction onto metallic zinc has been investigated at the single particle level through the electrode-particle collision method in neutral solutions, and in respect of its dependence on the applied potential and the ionic strength of a sulphate-containing solution. Depending on the concentration of sulphate ions in solution, different amounts of metallic zinc were deposited on the single Zn nanoparticles. Specifically, insights into the electron transfer kinetics at the single particles were obtained, indicating an electrically early reactant-like transition state, which is consistent with the rate-determining partial de-hydration/de-complexation process. Such information on the reaction kinetics at the nanoscale is of vital importance for the development of more efficient and long-lasting nanostructured Zn-based negative electrodes for Zn-ion battery applications.

     

Mycotoxins in spices and culinary herbs from Italy and Tunisia

Abstract

Spices and aromatic herbs can be contaminated with mycotoxins, since of their preharvest, postharvest, and storage conditions. In this study, 112 samples of different spices and aromatic herbs were evaluated for their mycotoxins content by HPLC-MS/MS in order to highlight their possible risk linked with human use. The results showed that mycotoxins were occasionally detected only in samples of coriander, laurel, mint, rosemary, and verbena. In both geographical origins a different contamination was detected. Among the investigated mycotoxins, AFB2, AFG1, AFG2, T2 and HT2 were detected, whereas none of the samples contained AFB1 and FB1. The co-occurrence of two toxins were observed for some samples of rosemary and verbena. This study indicates that it is essential minimize the toxins in agriculture, industry, and food-product manufacturing for the consumer health protection.     

Exploring multiple‐cumulative trapping solid‐phase microextraction for olive oil aroma profiling

Headspace solid‐phase microextraction is a solvent‐free sample preparation technique that is based on the equilibrium among a three‐phase system, i.e., sample‐headspace‐fiber. A compromise between sensitivity and extraction time is usually needed to optimize the sample throughput, especially when a large number of samples are analyzed, as usually the case in cross‐samples studies. This work explores the capability of multiple‐cumulative trapping solid‐phase microextraction on the characterization of the aroma profiling of olive oils, exploiting the automation capability of a novel headspace autosampler. It was shown that multiple‐cumulative solid‐phase microextraction has the potential to improve the overall sensitivity and burst the level of information for cross‐sample studies by using cumulative shorter extraction times.     

Investigation of free and conjugated seleno‐amino acids in wheat bran by hydrophilic interaction liquid chromatography with tandem mass spectrometry

An analytical method for determining seleno‐methionine, methyl‐seleno‐cysteine, and seleno‐cystine in wheat bran was developed and validated. Four different extraction procedures were evaluated to simultaneously extract endogenous free and conjugated seleno‐amino acids in wheat bran in order to select the best extraction protocol in terms of seleno amino acid quantitation. The extracted samples were subjected to a clean‐up by a reversed phase/strong cation exchange solid‐phase extraction and analyzed by chiral hydrophilic interaction liquid chromatography‐tandem mass spectrometry. The optimized extraction protocol was employed to validate the methodology. Process efficiency ranged from 58 to 112% and trueness from 73 to 98%. Limit of detection and limit of quantification were lower than 1 ng/g. Four wheat bran samples were analyzed for both total Se and single seleno‐amino acids determination. The results showed that Se‐ seleno‐methyl‐l selenocysteine was the major seleno‐amino acid in wheat bran while seleno‐methionine and seleno‐cysteine were both minor species.     

Evaluating the impact of average cost based contracts on the industrial sector in the European emission trading scheme

The degradation of the competitiveness of part of the European industry is progressively emerging as one of the possible consequences of the combination of the European Emission Trading Scheme (EU-ETS) and the restructuring of the electricity sector. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)