Characterization of O2 (1Δg)-derived oxidation products of tryptophan: A combination of tandem mass spectrometry analyses and isotopic labeling studies

The fragmentation mechanisms of singlet oxygen [O(2) ((1)Delta(g))]-derived oxidation products of tryptophan (W) were analyzed using collision-induced dissociation coupled with (18)O-isotopic labeling experiments and accurate mass measurements. The five identified oxidized products, namely two isomeric alcohols (trans and cis WOH), two isomeric hydroperoxides (trans and cis WOOH), and N-formylkynurenine (FMK), were shown to share some common fragment ions and losses of small neutral molecules. Conversely, each oxidation product has its own fragmentation mechanism and intermediates, which were confirmed by (18)O-labeling studies. Isomeric WOH lost mainly H(2)O + CO, while WOOH showed preferential elimination of C(2)H(5)NO(3) by two distinct mechanisms. Differences in the spatial arrangement of the two isomeric WOHs led to differences in the intensities of the fragment ions. The same behavior was also found for trans and cis WOOH. FMK was shown to dissociate by a diverse range of mechanisms, with the loss of ammonia the most favored route. MS/MS analyses, (18)O-labeling, and H(2)(18)O experiments demonstrated the ability of FMK to exchange its oxygen atoms with water. Moreover, this approach also revealed that the carbonyl group has more pronounced oxygen exchange ability compared with the formyl group. The understanding of fragmentation mechanisms involved in O(2) ((1)Delta(g))-mediated oxidation of W provides a useful step toward the structural characterization of oxidized peptides and proteins.     

Production of slow protonium in vacuum

We descrbe how protonium, the quasi-stable antiproton-proton bound system, has been synthesized following the interaction of antiprotons with the molecular ion in a nested Penning trap environment. From a careful analysis of the spatial distributions of antiproton annihilation events in the ATHENA experiment, evidence is presented for protonium production with sub-eV kinetic energies in states around n = 70, with low angular momenta. This work provides a new two-body system for studies using laser spectroscopic techniques.      

Structural and hyperfine properties of Mn and Co-incorporated akaganeites

The structural and hyperfine properties of pure and substituted akaganeites prepared in the presence of Mn, Co and urea are presented and discussed. In all samples, the chloride content increased with the increase in the urea concentration of the parent solution, and a small Mn-for-Fe or Co-for-Fe substitution occurred. In pure akaganeites, the increase of urea concentration provoked an enlargement of the unit cell volume and a decrease of the crystallinity of the synthesised oxides. The incorporation of Mn and Co provoked changes in cell parameters and an increase in the crystallinity of the samples. The hyperfine parameters for both iron sites of the akaganeites remained practically unchanged, and the spectral areas of the iron sites located close to the chlorides decreased for the doped samples. The recoilless f-factor increased for the substituted akaganeites, indicating an increase in the strength of the atomic bonding of the iron ions.     

A frictional mortar contact approach for the analysis of large inelastic deformation problems

A multibody frictional mortar contact formulation (Gitterle et al., 2010) is extended for the simulation of solids undergoing finite strains with inelastic material behavior. The framework includes the modeling of finite strain inelastic deformation, the numerical treatment of frictional contact conditions and specific finite element technology. Several well-established and recent models are employed for each of these building blocks to capture the distinct physical aspects of the deformation behavior. The approach is based on a mortar formulation and the enforcement of contact constraints is realized with dual Lagrange multipliers. The introduction of nonlinear complementarity functions into the frictional contact conditions combined with the global equilibrium leads to a system of nonlinear equations, which is solved in terms of the semi-smooth Newton method. The resulting method can be interpreted as a primal–dual active set strategy (PDASS) which deals with contact nonlinearities, material and geometrical nonlinearities in one iterative scheme. The consistent linearization of all building blocks of the framework yields a robust and highly efficient approach for the analysis of metal forming problems. The effect of finite inelastic strains on the solution behavior of the PDASS method is examined in detail based on the complementarity parameters. A comprehensive set of numerical examples is presented to demonstrate the accuracy and efficiency of the approach against the traditional node-to-segment penalty contact formulation.     

The effect of point mutation on the equilibrium structural fluctuations of ferric Myoglobin

The ultrafast equilibrium fluctuations of the Fe(III)-NO complex of a single point mutation of Myoglobin (H64Q) have been studied using Fourier Transform 2D-IR spectroscopy. Comparison with data from wild type Myoglobin (wt-Mb) shows the presence of two conformational substates of the mutant haem pocket where only one exists in the wild type form. One of the substates of the mutant exhibits an almost identical NO stretching frequency and spectral diffusion dynamics to wt-Mb while the other is distinctly different in both respects. The remarkably contrasting dynamics are largely attributable to interactions between the NO ligand and a nearby distal side chain which provides a basis for understanding the roles of these side chains in other ferric haem proteins.     

The Method of Images applied to the grounded sphere: The problem of the ground wire

The Method of Images poses an important difficulty when used to solve the problem of a charge in the presence of a grounded conducting sphere. This arises from the fact that the sum of the inducing charge and the image charge is different from zero. As a consequence, there is a monopole field far from the system, and any ground wire physically connected to the sphere will carry an electric current, changing the initial balance of charges until a new equilibrium is reached. The approach taken in this paper assumed an infinite straight wire connecting the sphere to ground. The charge distribution over the surface of the conductors was calculated, and the results analyzed. It was shown that the thinner the wire, the lower will be its total charge, and the closer will be the calculated charge density at the surface of the sphere to the conventional solution by the Method of Images.     

Nanoscale mapping of plasmon resonances of functional multibranched gold nanoparticles

The optical response of multibranched gold nanoparticles is studied by means of electron energy-loss spectroscopy (EELS) in aberration corrected STEM mode. In every case the plasmon response is constant and variations in the maxima positions were found to be dependent on the branches aspect ratio. The good spatial resolution combined with the high energy resolution (0.18 eV) of the monochromated electron beam allows mapping the different plasmonic modes along the entire nanoparticles ranging from 0.7 eV up to 2.25 eV.     

Convex Quantum Logic

In this work we study the convex set of quantum states from a quantum logical point of view. We consider an algebraic structure based on the convex subsets of this set. The relationship of this algebraic structure with the lattice of propositions of quantum logic is shown. This new structure is suitable for the study of compound systems and shows new differences between quantum and classical mechanics. These differences are linked to the nontrivial correlations which appear when quantum systems interact. They are reflected in the new propositional structure, and do not have a classical analogue. This approach is also suitable for an algebraic characterization of entanglement and it provides a new entanglement criteria.