Assignment of the EPR spectrum of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) superoxide spin adduct

[structure: see text] Spin trapping consists of using a nitrone or a nitroso compound to "trap" an unstable free radical as a long-lived nitroxide that can be characterized by electron paramagnetic resonance (EPR) spectroscopy. The formation of DMPO-OOH, the spin adduct resulting from trapping superoxide (O(2)(*)(-)) with 5,5-dimethyl-1-pyrroline N-oxide (DMPO), has been exploited to detect the generation of superoxide in a wide variety of biological and chemical systems. The 12-line EPR spectrum of DMPO-OOH has been either reported or mentioned in more than a thousand papers. It has been interpreted as resulting from the following couplings: A(N) approximately 1.42 mT, A(H)beta approximately 1.134 mT, and A(H)gamma(1H) approximately 0.125 mT. However, the DMPO-OOH EPR spectrum has an asymmetry that cannot be reproduced when the spectrum is calculated considering a single species. Recently, it was proposed that the 0.125 mT splitting was misassigned and actually results from the superimposition of two individual EPR spectra associated with different conformers of DMPO-OOH. We have prepared 5,5-dimethyl-[3,3-(2)H(2)]-1-pyrroline N-oxide (DMPO-d(2)), and we showed that the EPR spectrum of the corresponding superoxide spin adduct is composed of only six lines, in agreement with the assignment of the 0.125 mT splitting to a gamma-splitting from a hydrogen atom bonded to carbon 3 of DMPO. This result was supported by DFT calculations including water solvation, and the asymmetry of the DMPO-OOH EPR spectrum was nicely reproduced assuming a chemical exchange between two conformers.     

Analysis of tamoxifen and its main metabolites in plasma samples of breast cancer survivor female athletes: Multivariate and chemometric optimization

A sensitive method based on liquid chromatography combined with a diode array detector was developed and validated to simultaneously determine tamoxifen, and its active metabolites N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen in human plasma samples. The green and sustainable vortex-assisted dispersive liquid-phase microextraction technique based on the natural hydrophobic deep eutectic solvent was used for the extraction and preconcentration of the analytes. Chemometrics and multivariate analysis were used to optimize the independent variables including the type and volume of deep eutectic solvent, extraction time, and ionic strength. Under optimal conditions, calibration curves were linear in a suitable range with the lower limits of quantification (0.8–10.0 μg/L), which covered the relevant concentrations of the analytes in plasma samples for a clinical study. Intra- and interday precision evaluated at three concentrations for the analytes were lower than 8.2 and 12.1%, respectively. Accuracy was in the range of 94.9–104.7%. The applicability of the developed method on human plasma samples illustrated the range 45.1–72.8, 98.4–128.3, 0.9–1.2, and 2.7–6.1 μg/L for tamoxifen, N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen, respectively. The validated method can be effective for the pharmacokinetics, pharmacodynamics, and therapeutic drug monitoring studies of tamoxifen and its main metabolites in biological fluids.     

Localization for a Matrix-valued Anderson Model

We study localization properties for a class of one-dimensional, matrix-valued, continuous, random Schrödinger operators, acting on $L^2(\mathbb R)\otimes \mathbb C^NWe study localization properties for a class of one-dimensional, matrix-valued, continuous, random Schr?dinger operators, acting on , for arbitrary N ≥ 1. We prove that, under suitable assumptions on the Fürstenberg group of these operators, valid on an interval , they exhibit localization properties on I, both in the spectral and dynamical sense. After looking at the regularity properties of the Lyapunov exponents and of the integrated density of states, we prove a Wegner estimate and apply a multiscale analysis scheme to prove localization for these operators. We also study an example in this class of operators, for which we can prove the required assumptions on the Fürstenberg group. This group being the one generated by the transfer matrices, we can use, to prove these assumptions, an algebraic result on generating dense Lie subgroups in semisimple real connected Lie groups, due to Breuillard and Gelander. The algebraic methods used here allow us to handle with singular distributions of the random parameters.      

Exact exponent for the number of persistent spins in the zero-temperature dynamics of the one-dimensional Potts model

For the zero-temperature Glauber dynamics of theq-state Potts model, the fractionr(q, t) of spins which never flip up to timet decays like a power lawr(q, t)t ^–(q) when the initial condition is random. By mapping the problem onto an exactly soluble one-species coagulation model (A+AA) or alternatively by transforming the problem into a free-fermion model, we obtain the exact expression of (q) for all values ofq. The exponent (q) is in general irrational, (3)=0.53795082..., (4)=0.63151575..., ..., with the exception ofq=2 andq=, for which (2)=3/8 and ()=1.     

Supercuspidal Gelfand pairs

If G is a totally disconnected group and H is a closed subgroup then, according to the Gelfand-Kazhdan Lemma, if the double coset space H?G/H is preserved by an antiautomorphism of G of order two then (G,H) must be a Gelfand pair in the sense that Hom_H(π,1) has dimension at most one for each irreducible, admissible representation π of G. Under certain rather general restrictions, we show that if the symmetry property holds only for almost all double cosets, then (G,H) is a supercuspidal Gelfand pair in the sense that for all irreducible, supercuspidal representations π of G. There exist examples of supercuspidal Gelfand pairs which are not Gelfand pairs.     

Linear stability of scroll waves

A full linear stability of a straight scroll wave in an excitable medium is presented. The five eigenmode branches which correspond to deformation in the third dimension of the five main modes of two-dimensional (2D) spiral dynamics are found to play a dominant role. For untwisted scroll waves, modulations in the third dimension have stabilizing or destabilizing effects on the different modes depending on the parameter regimes, in partial agreement with previous predictions. The influence of twist on the different branches is investigated. In particular, the sproing instability is seen to arise from the twist-induced deformation of the translation branches above a threshold twist.     

Highly β-Selective Glycosylation Reactions for the Synthesis of ω-Functionalized Alkyl β-Maltoside as a Co-crystallizing Detergent

Russian Journal of Organic Chemistry - Methods have been reported for the preparation of ω-functionalized alkyl maltoside and glycoside detergents via a simple and inexpensive synthetic route....     

Hydrogen production by steam reforming of glycerol over Ni/Ce/Cu hydroxyapatite-supported catalysts

Hydroxyapatite-supported Ni-Ce-Cu catalysts were synthesised and tested to study their potential for use in the steam reforming of glycerol to produce hydrogen. The catalysts were prepared by the deposition-precipitation method with variable nickel, cerium, and copper loadings. The performance of the catalysts was evaluated in terms of hydrogen yield at 600°C in a tubular fixed-bed microreactor. All catalysts were characterised by the BET surface area, XRD, TPR, TEM, and FE-SEM techniques. The reaction time was 240 min in a fixed-bed reactor at 600°C and atmospheric pressure with a water-to-glycerol feed molar ratio of 8: 1. It was found that the Ni-Ce-Cu (3 mass %-7.5 mass %-7.5 mass %) hydroxyapatite-supported catalyst afforded the highest hydrogen yield (57.5 %), with a glycerol conversion rate of 97.3 %. The results indicate that Ni/Ce/Cu/hydroxyapatite has great potential as a catalyst for hydrogen production by steam reforming of glycerol.