Thermal analysis as a tool for investigations in metal oxide chemistry

Applications of thermoanalytical methods for the controlled preparation of metal oxides from various initial compounds (‘precursors’) as well as for investigations of physical properties and the chemical behaviour of oxidic phases as function of temperature and atmosphere are presented. Studies elucidating the course of such processes yield important contributions to the understanding of the reactivity of solids in general. Moreover, they are, e.g. in the field of heterogeneous catalysis, of practical relevance. It is shown, however, that the capability of mere thermal analysis suffers from limitations which have to be overcome by using additional, independent methods such as X-ray diffraction as well as light and electron microscopy.     

Hyperfine quantum beat spectroscopy of a polyatomic molecule in a weak magnetic field with polarized light

Resolved Zeeman splittings in molecular quantum beats are used for the first time to assign hyperfine components of a triplet sublevel of a polyatomic     

Birkhoff coordinates for KdV on phase spaces of distributions

The purpose of this paper is to extend the construction of Birkhoff coordinates for the KdV equation from the phase space of square integrable 1-periodic functions with mean value zero to the phase space of mean value zero distributions from the Sobolev space endowed with the symplectic structure More precisely, we construct a globally defined real-analytic symplectomorphism where is a weighted Hilbert space of sequences supplied with the canonical Poisson structure so that the KdV Hamiltonian for potentials in is a function of the actions alone.     

Hydride transfer reactivity of tetrakis(trimethylphosphine)(hydrido)(nitrosyl)molybdenum(0)

The tetrakis(trimethylphosphine) molybdenum nitrosyl hydrido complex trans-Mo(PMe(3))(4)(H)(NO) (2) and the related deuteride complex trans-Mo(PMe(3))(4)(D)(NO) (2a) were prepared from trans-Mo(PMe(3))(4)(Cl)(NO) (1). From (2)H T(1 min) measurements and solid-state (2)H NMR the bond ionicities of 2a could be determined and were found to be 80.0% and 75.3%, respectively, indicating a very polar Mo--D bond. The enhanced hydridicity of 2 is reflected in its very high propensity to undergo hydride transfer reactions. 2 was thus reacted with acetone, acetophenone, and benzophenone to afford the corresponding alkoxide complexes trans-Mo(NO)(PMe(3))(4)(OCHR'R') (R' = R' = Me (3); R' = Me, R' = Ph (4); R' = R' = Ph (5)). The reaction of 2 with CO(2) led to the formation of the formato-O-complex Mo(NO)(OCHO)(PMe(3))(4) (6). The reaction of with HOSO(2)CF(3) produced the anion coordinated complex Mo(NO)(PMe(3))(4)(OSO(2)CF(3)) (7), and the reaction with [H(Et(2)O)(2)][BAr(F)(4)] with an excess of PMe(3) produced the pentakis(trimethylphosphine) coordinated compound [Mo(NO)(PMe(3))(5)][BAr(F)(4)] (8). Imine insertions into the Mo-H bond of 2 were also accomplished. PhCH[double bond, length as m-dash]NPh (N-benzylideneaniline) and C(10)H(7)CH=NPh (N-1-naphthylideneaniline) afforded the amido compounds Mo(NO)(PMe(3))(4)[NR'(CH(2)R')] (R' = R' = Ph (9), R' = Ph, R' = naphthyl (11)). 9 could not be obtained in pure form, however, its structure was assigned by spectroscopic means. At room temperature 11 reacted further to lose one PMe(3) forming 12 (Mo(NO)PMe(3))(3)[N(Ph)CH(2)C(10)H(6))]) with agostic stabilization. In a subsequent step oxidative addition of the agostic naphthyl C-H bond to the molybdenum centre occurred. Then hydrogen migration took place giving the chelate amine complex Mo(NO)(PMe(3))(3)[NH(Ph)(CH(2)C(10)H(6))] (15). The insertion reaction of 2 with C(10)H(7)N=CHPh led to formation of the agostic compound Mo(NO)(PMe(3))(3)[N(CH(2)Ph)(C(10)H(7))] (10). Based on the knowledge of facile formation of agostic compounds the catalytic hydrogenation of C(10)H(7)N=CHPh and PhN=CHC(10)H(7) with 2 (5 mol%) was tested. The best conversion rates were obtained in the presence of an excess of PMe(3), which were 18.4% and 100% for C(10)H(7)N=CHPh and PhN=CHC(10)H(7), respectively.     

Crystal structure of an NPNA-repeat motif from the circumsporozoite protein of the malaria parasite Plasmodium falciparum

A crystal structure is reported of the peptide Ac-Ala-Asn-Pro-Asn-Ala-NH2, representing the immunodominant region of the major surface protein on the malaria parasite; the NPNA motif adopts a type-I beta-turn, which is stabilized by hydrogen bonding between the CO of Asn2 and the NH of Ala5 as well as between the O(delta) of Asn2 and the NH of Asn4.     

h-BN/Ru(0 0 0 1) nanomesh: A 14-on-13 superstructure with 3.5 nm periodicity

The structure of epitaxially grown hexagonal boron nitride (h-BN) on the surface of a Ru(0 0 0 1) single crystal was investigated using surface X-ray diffraction, which showed the system to form a commensurate 14-on-13 superstructure. This result disagrees with previous reports on superstructures of the same system and arguments based on simple thermal expansion coefficient calculations. We argue that the larger observed superstructure forms because of the strong bonding of h-BN to Ru. In comparison to h-BN/Rh(1 1 1) it can accommodate more induced lateral in-plane strain- or lock-in energy over larger regions (referred to as the holes) within the superstructure, which itself can consequently become larger.     

Regularization in quantum field theory from the causal point of view

The causal approach to perturbative quantum field theory is presented in detail, which goes back to a seminal work by Henri Epstein and Vladimir Jurko Glaser in 1973 [12]. Causal perturbation theory is a mathematically rigorous approach to renormalization theory, which makes it possible to put the theoretical setup of perturbative quantum field theory on a sound mathematical basis. Epstein and Glaser solved this problem for a special class of distributions, the time-ordered products, that fulfill a causality condition, which itself is a basic requirement in axiomatic quantum field theory. In their original work, Epstein and Glaser studied only theories involving scalar particles. In this review, the extension of the method to theories with higher spin, including gravity, is presented. Furthermore, specific examples are presented in order to highlight the technical differences between the causal method and other regularization methods, like, e.g. dimensional regularization.     

Controllability of quasi-linear Hamiltonian NLS equations

We prove internal controllability in arbitrary time, for small data, for quasi-linear Hamiltonian NLS equations on the circle. We use a procedure of reduction to constant coefficients up to order zero and HUM method to prove the controllability of the linearized problem. Then we apply a Nash–Moser–Hörmander implicit function theorem as a black box.