Epoxide Hydrolase‐Catalysed Kinetic Resolution of a Spiroepoxide,a Key Building Block of Various 11‐Heterosteroids

Two microbial epoxide hydrolases – i.e., Aspergillus niger (AnEH) and Rhodococcus erythropolis (the so‐called “Limonene EH”: LEH) were used to achieve, for the first time, the biocatalysed hydrolytic kinetic resolution (BHKR) of spiroepoxide rac‐ 1 . This compound is a strategic key building block allowing the synthesis of 11‐heterosteroids. Interestingly enough, the two enzymes exhibited opposite and therefore complementary enantioselectivity allowing us to isolate the residual (R,R)‐ 1 (from AnEH) and the residual (S,S)‐ 1 (from LEH) in nearly enantiopure forms (>98 %). Their absolute configurations were determined by X‐ray crystallography. An opposite regioselectivity of the oxirane ring opening for both enantiomers of substrate 1 , determined using H₂¹⁸O labelling and chiral GC‐MS analysis, was also observed, corresponding to an attack at the less substituted carbon atom using AnEH, and at the most substituted carbon atom using LEH. A chemical process‐improving methodology was also developed. This allowed us to obtain both enantiomers of the substrate in high enantiomeric purity (99 %) and optimised quantity. In the case of the AnEH, the use of a biphasic (water/isooctane) reaction medium allowed us to increase the global substrate concentration up to 200 g/ L. The preparation of both enantiomers of 1 clearly paves the way to the preparative scale synthesis and biochemical evaluation of the corresponding 11‐heterosteroid enantiomers.     

Experimental study of inlet manifold water injection on combustion and emissions of an automotive direct injection Diesel engine

This paper describes an experimental study conducted on a modern high speed common-rail automotive Diesel engine in order to evaluate the effects on combustion and pollutant emissions of water injected as a fine mist in the inlet manifold.     

Hybrid‐Bridged Silsesquioxane as Recyclable Metathesis Catalyst Derived from a Bis‐Silylated Hoveyda‐Type Ligand

The synthesis of a bis‐silylated Hoveyda‐type monomer is described as well as the preparation of several organic‐inorganic hybrid materials derived from it by a sol‐gel process (with and without tetraethyl orthosilicate) and by anchoring to MCM‐41. The resulting materials were treated with second generation Grubbs' catalyst to generate second generation Hoveyda–Grubbs‐type alkylideneruthenium complexes covalently bonded to the silica matrix. These materials are recyclable catalysts for the ring‐closing metathesis reaction of dienes and enynes.     

Nexus 2010: Relationships between Architecture and Mathematics

The eighth edition of the international, interdisciplinary Nexus conference on architecture and mathematics took place from Sunday 13 June through Tuesday 15 June 2010, in Porto, Portugal.     

Atomic force microscopy study of the antibacterial effects of chitosans on Escherichia coli and Staphylococcus aureus

Chitosan has been reported to be a non-toxic, biodegradable antibacterial agent. The aim of this work was to elucidate the relationship between the molecular weight of chitosan and its antimicrobial activity upon two model microorganisms, one Gram-positive (Staphylococcus aureus) and one Gram-negative (Escherichia coli). Atomic force microscopy (AFM) imaging was used to obtain high-resolution images of the effect of chitosans on the bacterial morphology. The AFM measurements were correlated with viable cell numbers, which show that the two species reacted differently to the high- and low-molecular-weight chitosan derivatives. The images obtained revealed not only the antibacterial effects, but also the response strategies used by the bacteria; cell wall collapse and morphological changes reflected cell death, whereas clustering of bacteria appeared to be associated with cell survival. In addition, nanoindentation experiments with the AFM revealed mechanical changes in the bacterial cell wall induced by the treatment. The nanoindentation results suggested that despite little modification observed in the Gram-positive bacteria in morphological studies, cell wall damage had indeed occurred, since cell wall stiffness was reduced after chitooligosaccharide treatment.     

Learning directed probabilistic logical models: ordering-search versus structure-search

We discuss how to learn non-recursive directed probabilistic logical models from relational data. This problem has been tackled before by upgrading the structure-search algorithm initially proposed for Bayesian networks. In this paper we show how to upgrade another algorithm for learning Bayesian networks, namely ordering-search. For Bayesian networks, ordering-search was found to work better than structure-search. It is non-obvious that these results carry over to the relational case, however, since there ordering-search needs to be implemented quite differently. Hence, we perform an experimental comparison of these upgraded algorithms on four relational domains. We conclude that also in the relational case ordering-search is competitive with structure-search in terms of quality of the learned models, while ordering-search is significantly faster.     

Improved magnetic trapped field in thin-wall YBCO single-domain samples by high-pressure oxygen annealing

Oxygen high pressure (up to 16 MPa) has been introduced in the oxygen-annealing step necessary to make the YBa₂Cu₃O_x phase superconducting (change x from 6 to about 7). It enables a displacement in the equilibrium phase diagram towards higher temperatures, which means the possibility to achieve the same final oxygen content as the one at low temperature, but with the benefit of higher diffusion rates. Initial development made on thin bars (1.5–3 mm thick) has confirmed the interest of using a high pressure of oxygen. TEM observations have shown an increase of twin density associated with higher Jc. This is in agreement with other works claiming the possibility of higher Jc by twin engineering, and more precisely by twin refinement while annealing at high temperature. We report the successful application of this process without any adjustment to so-called thin-wall single-domain samples. These samples are obtained by growing a crystal on a pellet already shaped with an array of holes. The advantage is that, as far as diffusion processes are concerned, the typical length is not anymore the diameter of the sample, but the thickness of the walls between holes. The trapped field of 16 mm diameter Y123 thin-wall single-domain samples was doubled (0.6 T vs. 0.3 T at 77 K) in a rather short annealing time (about 3 days). Microstructures as well as magneto-optical observations of plain and thin-wall samples evidenced a reduction of cracks in the thin-wall samples. Improved performances were confirmed by further characterizations performed from 77 down to 20 K using the pulse-field facilities of the LNCMP at Toulouse.     

Blinded by anger or feeling the love: How emotions influence advice taking.

Across 2 experiments, the authors demonstrate that emotional states influence how receptive people are to advice. The focus of these experiments is on incidental emotions, emotions triggered by a prior experience that is irrelevant to the current situation. The authors demonstrate that people who feel incidental gratitude are more trusting and more receptive to advice than are people in a neutral emotional state, and people in a neutral state are more trusting and more receptive to advice than are people who feel incidental anger. In these experiments, greater receptivity to advice increased judgment accuracy. People who felt incidental gratitude were more accurate than were people in a neutral state, and people in a neutral state were more accurate than were people who felt incidental anger. The results offer insight into how people use advice, and the authors identify conditions under which leaders, policy makers, and advisors may be particularly influential. (PsycINFO Database Record (c) 2010 APA, all rights reserved)