Role of radicals in UV‐initiated postplasma grafting of poly‐ε‐caprolactone: An electron paramagnetic resonance study

Electron paramagnetic resonance (EPR) measurements were performed on poly‐ε‐caprolactone (PCL) films at different stages of the postplasma‐grafting process. PCL films prepared by solvent casting (SC) or electrospinning (ESP) yield very similar EPR spectra after Ar‐plasma treatment and subsequent exposure to air, but the EPR signal is much stronger in the PCL‐ESP films. The free radicals appear to be mainly, and possibly exclusively, oxygen centered. The radicals generated by UV irradiation in PCL‐ESP films were studied in situ with EPR, using a UV‐LED (λ = (285 ± 5) nm). Their EPR spectrum is distinctly different from the plasma‐induced signal, indicative of carbon‐centered radicals, and appears to be independent of the plasma pretreatment. UV‐induced homolytic splitting of (hydro)peroxide bonds was not observed. Both the plasma‐ and UV‐induced radicals decay at room temperature (RT), even in an inert atmosphere. This study demonstrates the potential of electrospun films and UV‐LEDs for the study of plasma‐ and UV‐generated free radicals with EPR in polyesters, and raises questions with respect to the validity of some generally accepted molecular mechanisms underpinning the postplasma grafting technique for polyesters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Quasi-elementary <Emphasis Type="Italic">H</Emphasis>-Azumaya Algebras Arising from Generalized (Anti) Yetter-Drinfeld Modules

Let H be a Hopf algebra with bijective antipode, α, β ∈ Aut _Hopf (H) and M a finite dimensional (α, β)-Yetter-Drinfeld module. We prove that End(M) endowed with certain structures becomes an H-Azumaya algebra, and the set of H-Azumaya algebras of this type is a subgroup of BQ(k, H), the Brauer group of H.     

Slow-fast Bogdanov-Takens bifurcations

In this paper we study perturbations from planar vector fields having a line of zeros and representing a singular limit of Bogdanov-Takens (BT) bifurcations. We introduce, among other precise definitions, the notion of slow-fast BT-bifurcation and we provide a complete study of the bifurcation diagram and the related phase portraits. Based on geometric singular perturbation theory, including blow-up, we get results that are valid on a uniform neighborhood both in parameter space and in the phase plane.     

Distortion of the Poisson Bracket by the Noncommutative Planck Constants

In this paper we introduce a kind of “noncommutative neighbourhood” of a semiclassical parameter corresponding to the Planck constant. This construction is defined as a certain filtered and graded algebra with an infinite number of generators indexed by planar binary leaf-labelled trees. The associated graded algebra (the classical shadow) is interpreted as a “distortion” of the algebra of classical observables of a physical system. It is proven that there exists a q-analogue of the Weyl quantization, where q is a matrix of formal variables, which induces a nontrivial noncommutative analogue of a Poisson bracket on the classical shadow.     

H NMR and C-IRMS analyses of acetic acid from vinegar, O-IRMS analysis of water in vinegar: International collaborative study report

An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the ²H/¹H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the ¹³C/¹²C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the ¹⁸O/¹⁶O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations.The precision parameters of the method for measuring δ¹³C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 ‰, and the average reproducibility (R) was 0.91‰. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the ²H/¹H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (δ¹³C and δ¹⁸O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring δ¹⁸O were found to be similar to the values previously obtained for other methods applied to wine and fruit juices: the average repeatability was 0.15‰, and the average reproducibility was 0.59‰. The above values are proposed as repeatability and reproducibility limits in the current state of the art.On the basis of this satisfactory inter-laboratory precision and on the accuracy demonstrated by a spiking experiment, the authors recommend the adoption of the three isotopic determinations included in this study as official methods for controlling the authenticity of vinegar.