Universal additive effect of temperature on the rheology of amorphous solids

Extensive measurements of macroscopic stress in a 2D Lennard-Jones glass, over a broad range of temperatures (T) and strain rates (γ), demonstrate a very significant decrease of the flowing stress with T, even much below the glass transition. A detailed analysis of the interplay between loading, thermal activation, and mechanical noise leads us to propose that over a broad (γ, T) region, the effect of temperature amounts to a mere lowering of the strains at which plastic events occur, while the athermal avalanche dynamics remains essentially unperturbed. Up to the vicinity of the glass transition, temperature is then shown to correct the athermal stress by a (negative) additive contribution which presents a universal form, thus bringing support to and extending an expression proposed by Johnson and Samwer [Phys. Rev. Lett. 95, 195501 (2005)].     

Bifurcation analysis of a generalized Gause model with prey harvesting and a generalized Holling response function of type III

In this paper we study a generalized Gause model with prey harvesting and a generalized Holling response function of type III: . The goal of our study is to give the bifurcation diagram of the model. For this we need to study saddle-node bifurcations, Hopf bifurcation of codimension 1 and 2, heteroclinic bifurcation, and nilpotent saddle bifurcation of codimension 2 and 3. The nilpotent saddle of codimension 3 is the organizing center for the bifurcation diagram. The Hopf bifurcation is studied by means of a generalized Liénard system, and for b=0 we discuss the potential integrability of the system. The nilpotent point of multiplicity 3 occurs with an invariant line and can have a codimension up to 4. But because it occurs with an invariant line, the effective highest codimension is 3. We develop normal forms (in which the invariant line is preserved) for studying of the nilpotent saddle bifurcation. For b=0, the reversibility of the nilpotent saddle is discussed. We study the type of the heteroclinic loop and its cyclicity. The phase portraits of the bifurcations diagram (partially conjectured via the results obtained) allow us to give a biological interpretation of the behavior of the two species.     

Synthesis of functionalized diarylmethanes via a copper-catalyzed cross-coupling of arylmagnesium reagents with benzylic phosphates

A combination of copper chloride, triethyl phosphite, and tetrabutylammonium iodide is a very efficient catalytic system for the synthesis of polyfunctionalized diarylmethanes, using the cross-coupling reaction of arylmagnesium halides with benzylic phosphates. The antibiotic Trimethoprim has been prepared using this Cu(I)-catalyzed cross-coupling in 52% overall yield (four steps).     

An inhomogeneous,anisotropic, elastically modified Gibbs­Thomson law as singular limit of a diffuse interface model

We consider the sharp interface limit of a diffuse phase-field model with prescribed total mass taking into account a spatially inhomogeneous, anisotropic interfacial energy and an elastic energy. The main aim is to establish a weak formulation of an inhomogeneous, anisotropic, elastically modified Gibbs-Thomson law in the sharp interface limit. To this end we pass to the limit in the weak formulation of the Euler-Lagrange equation of the diffuse phase-field energy. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Azetidine‐Containing Alkaloids Produced by a Quorum‐Sensing Regulated Nonribosomal Peptide Synthetase Pathway in Pseudomonas aeruginosa

Pseudomonas aeruginosa displays an impressive metabolic versatility, which ensures its survival in diverse environments. Reported herein is the identification of rare azetidine‐containing alkaloids from P. aeruginosa PAO1, termed azetidomonamides, which are derived from a conserved, quorum‐sensing regulated nonribosomal peptide synthetase (NRPS) pathway. Biosynthesis of the azetidine motif has been elucidated by gene inactivation, feeding experiments, and biochemical characterization in vitro, which involves a new S‐adenosylmethionine‐dependent enzyme to produce azetidine 2‐carboxylic acid as an unusual building block of NRPS. The mutants of P. aeruginosa unable to produce azetidomonamides had an advantage in growth at high cell density in vitro and displayed rapid virulence in Galleria mellonella model, inferring functional roles of azetidomonamides in the host adaptation. This work opens the avenue to study the biological functions of azetidomonamides and related compounds in pathogenic and environmental bacteria.     

Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts

The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO₂ utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO₂ catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided.     

In Situ Investigations of Mechanochemical One‐Pot Syntheses

We present an in situ triple coupling of synchrotron X‐ray diffraction with Raman spectroscopy, and thermography to study milling reactions in real time. This combination of methods allows a correlation of the structural evolution with temperature information. The temperature information is crucial for understanding both the thermodynamics and reaction kinetics. The reaction mechanisms of three prototypical mechanochemical syntheses, a cocrystal formation, a C?C bond formation (Knoevenagel condensation), and the formation of a manganese‐phosphonate, were elucidated. Trends in the temperature development during milling are identified. The heat of reaction and latent heat of crystallization of the product contribute to the overall temperature increase. A decrease in temperature occurs via release of, for example, water as a by‐product. Solid and liquid intermediates are detected. The influence of the mechanical impact could be separated from temperature effects caused by the reaction.