Distinguishing between abstraction and addition as the first step in the reaction of a nitroxyl radical with cyclohexene

An unambiguous method for distinguishing between abstraction-addition and addition-abstraction mechanisms (and mixtures thereof) in the reaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl with a specifically deuterated cyclohexene, 1,2-dideuteriocyclohexene, is demonstrated.     

Bergman and Calderón Projectors for Dirac Operators

For a Dirac operator $D_{\bar{g}}$ over a spin compact Riemannian manifold with boundary $(\bar{X},\bar{g})$ , we give a new construction of the Calderón projector on $\partial\bar{X}$ and of the associated Bergman projector on the space of L ² harmonic spinors on $\bar{X}$ , and we analyze their Schwartz kernels. Our approach is based on the conformal covariance of $D_{\bar{g}}$ and the scattering theory for the Dirac operator associated with the complete conformal metric $g=\bar{g}/\rho^{2}$ where ρ is a smooth function on $\bar{X}$ which equals the distance to the boundary near $\partial\bar{X}$ . We show that $\frac{1}{2}(\operatorname{Id}+\tilde{S}(0))$ is the orthogonal Calderón projector, where $\tilde{S}(\lambda)$ is the holomorphic family in {?(λ)≥0} of normalized scattering operators constructed in Guillarmou et al. (Adv. Math., 225(5):2464–2516, 2010), which are classical pseudo-differential of order 2λ. Finally, we construct natural conformally covariant odd powers of the Dirac operator on any compact spin manifold.     

Effects of tris(pyrazolyl)borato ligand substituents on dioxygen activation and stabilization by copper compounds

Dinuclear [Cu2(mu-O)2(Tp(R,R')2] complexes, analogues of the active site of oxyhemocyanin, are theoretically studied, and the effect of the substituents of the tris(pyrazolyl)borate ligands, Tp(R,R'), is analyzed. Density functional theory calculations reveal that the type of bridging oxygen, peroxo, or bisoxo is strongly influenced by the nature and position of the R substituents because of variable substituent...bridging oxygen interactions, as well as electronic effects. The electronic effects of ligands at the 5 position are not significant, but peroxo complexes are favored by electron-withdrawing groups at the 3 position while bisoxo ones are strongly sterically disfavored.     

A glimpse of deductive systems in algebra

The concept of a deductive system has been intensively studied in algebraic logic, per se and in connection with various types of filters. In this paper we introduce an axiomatization which shows how several resembling theorems that had been separately proved for various algebras of logic can be given unique proofs within this axiomatic framework. We thus recapture theorems already known in the literature, as well as new ones. As a by-product we introduce the class of pre-BCK algebras.     

Synthesis, structure and catalase-like activity of dimanganese(III) complexes of 1,5-bis(X-salicylidenamino)pentan-3-ol (X = 3- and 5-methyl). Influence of phenyl-ring substituents on catalytic activity

The diMn(III) complexes [Mn2(5-Me-salpentO)(mu-MeO)(mu-AcO)(H2O)Br] (1) and [Mn2(3-Me-salpentO)(mu-MeO)(mu-AcO)(MeOH)2]Br (2), where salpentOH = 1,5-bis(salicylidenamino)pentan-3-ol, were synthesised and structurally characterized. The two complexes include a bis(micro-alkoxo)(micro-acetato) triply-bridged diMn(III) core with an Mn...Mn separation of 2.93-2.94 A, the structure of which is retained upon dissolution. Complexes 1 and 2 show catalytic activity toward disproportionation of H2O2, with first-order dependence on the catalyst, and saturation kinetics on [H2O2], in methanol and DMF. In DMF, the two complexes are able to disproportionate at least 1500 eq. of H2O2 without significant decomposition, while in methanol, they rapidly lose activity with formation of a non-coupled Mn(II) species. Electrospray ionisation mass spectrometry, EPR and UV/vis spectroscopy used to monitor the reaction suggest that the major active form of the catalyst occurs in the Mn2(III) oxidation state during cycling. The correlation between log(k(cat)) and the redox potentials of 1, 2 and analogous complexes of other X-salpentOH derivatives indicates that, in this series, the oxidation of the catalyst is probably the rate-limiting step in the catalytic cycle. It is also noted that formation of the catalyst-peroxide adduct is more sensitive to steric effects in DMF than in methanol. Overall, kinetics and spectroscopic studies of H2O2 dismutation by these complexes converge at a catalytic cycle that involves the Mn2(III) and Mn2(IV) oxidation states.     

Magnetic anisotropy of [Mo(CN)7]4- anions and fragments of cyano-bridged magnetic networks

Quantum chemistry calculations of CASSCF/CASPT2 level together with ligand field analysis are used for the investigation of magnetic anisotropy of [Mo(CN)7]4- complexes. We have considered three types of heptacyano environments: two ideal geometries, a pentagonal bipyramid and a capped trigonal prism, and the heptacyanomolybdate fragment of the cyano-bridged magnetic network K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O. At all geometries the first excited Kramers doublet is found remarkably close to the ground one due to a small orbital energy gap in the ligand field spectrum, which ranges between a maximal value in the capped trigonal prism (800 cm(-1)) and zero in the pentagonal bipyramid. The small value of this gap explains (i) the axial form of the g tensor and (ii) the strong magnetic anisotropy even in strongly distorted complexes. Comparison with available experimental data for the g tensor of the mononuclear precursors reveals good agreement with the present calculations for the capped trigonal prismatic complex and a significant discrepancy for the pentagonal bipyramidal one. The calculations for the heptacyanomolybdate fragment of K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O give g(perpendicular)/g(parallel) approximately 0.5 and the orientation of the local anisotropy axis close to the symmetry axis of an idealized pentagonal bipyramid. These findings are expected to be important for the understanding of the magnetism of anisotropic Mo(III)-Mn(II) cyano-bridged networks based on the [Mo(CN)7]4- building block.     

Monitoring Methylmalonic Aciduria by NMR Urinomics

The paper reports on monitoring methylmalonic aciduria (MMA)-specific and non-specific metabolites via NMR urinomics. Five patients have been monitored over periods of time; things involved were diet, medication and occasional episodes of failing to comply with prescribed diets. An extended dataset of targeted metabolites is presented, and correlations with the type of MMA are underlined. A survey of previous NMR studies on MMA is also presented.