Expanding the Scope of Atropisomeric Monodentate P‐Donor Ligands in Asymmetric Catalysis: Hydrogen‐Transfer Reduction of α,β‐Unsaturated Acid Derivatives by Rhodium/Ph‐binepine Catalysts

A range of α,β‐unsaturated acids and esters have been selectively reduced to the corresponding saturated acid derivatives by hydrogen transfer. As the reducing agent, formic acid was used in the presence of Rh^I complexes formed with the powerful chiral ligand Ph‐binepine ( 1 ), an axially chiral binaphthalene‐type monodentate P‐donor ligand. Very high stereoselectivities (up to 97% ee) were obtained in the case of itaconic acid ( 2a ).     

Reactive oxygen species (ROS) generation inhibited by aporphine and phenanthrene alkaloids semi-synthesized from natural boldine

Four phenanthrene and one aporphine alkaloids semi-synthesized from boldine were evaluated for their inhibitory effect on reactive oxygen species (ROS) generation. ROS generation by neutrophils stimulated with N-formyl-methionyl-leucyl-phenylalanine was inhibited in a concentration dependent manner. Alkaloids exerted similar inhibitory effect in the hypoxanthine-xanthine oxidase system than in stimulated neutrophils, which could be attributed to a direct ROS scavenging activity. None of the alkaloids assayed had any effect on xanthine oxidase activity. Therefore the synthesized alkaloids might constitute an alternative therapy in inflammation disorders in which ROS generation is involved.     

Ab initio molecular electrostatic potentials

The ab initio isopotential map of guanine is given and compared to that of adenine. It shows that in contrast to the situation in adenine, the most basic site of guanine is N₇ with a secondary potential minimum at O₆. These results as well as those concerning the secondary out-of-plane attractive regions over the NH₂ group and C₈ H bonds of the two molecules are discussed in connection with the available experimental knowledge concerning the bonding of alkylating carcinogens and mutagens.     

Infrared studies of small azobenzene peptides: unexpectedly slow reactions on the time range of minutes

Infrared absorption experiments on light-triggered azobenzene peptides have been performed below and above the freezing point of the solvent dimethyl sulfoxide (DMSO). Even 20 K below the freezing point, illumination of the azobenzene chromophore resulted in IR absorption changes indicative of light-induced structural rearrangements of the peptide. In addition, new conformational states could be found at low temperature, which involve the formation of additional hydrogen bonds. In one sample the new low-temperature state survived melting and reheating and disappeared at 298 K only on the time scale of 10 min. The observations indicate that at low temperatures the peptide, together with traces of water present in the sample, forms a shell in the vicinity of the chromophore that facilitates internal motion even in the rigid cage of frozen DMSO.     

A rheological phase diagram of additives for cement formulations

A detailed rheological study of aqueous solutions of methylhydroxyethylcellulose has been carried out in the presence of different acrylate-based graft polymer used as additive contents. Both polymer components are used in cement formulations to improve the flow performances of the concretes, but no physicochemical studies can be easily found in the literature. The content of the graft polymer has been varied between 0.1 and 2.7 wt% in an aqueous solution with a fixed content of 6.5 wt% of methylhydroxyethylcellulose. Creep curves were performed at different stresses in order to build up the flow curves for the various solutions. We found that the addition of the graft polymer triggers a phase transition, which is made more dramatic by the presence of an external flow. A “flow-phase diagram” has been obtained, which could be used as a guide for determining the critical conditions for the onset of the flow-induced instability.     

Order conditions for partitioned Runge-Kutta methods

We illustrate the use of the recent approach by P. Albrecht to the derivation of order conditions for partitioned Runge-Kutta methods for ordinary differential equations.     

Food Industry Byproducts as Starting Material for Innovative,Green Feed Formulation: A Sustainable Alternative for Poultry Feeding

Rising global populations and enhanced standards of living in so-called developing countries have led to an increased demand of food, in particular meat, worldwide. While increasing the production of broiler meat could be a potential solution to this problem, broiler meat is plagued by health concerns, such as the development of antimicrobial resistance and lower meat quality. For this reason, the supplementation of poultry feed with vitamins and antioxidant compounds, such as polyphenols, has become an attractive prospect for research in this sector. Such supplements could be obtained by extraction of agricultural byproducts (in particular, grape pomaces and artichoke leaves and bracts), thus contributing to reductions in the total amount of waste biomass produced by the agricultural industry. In this review, the effects of poultry feed supplementation with bioactive extracts from grape pomace (skins and/or seeds), as well as extracts from artichoke leaves and bracts, were explored. Moreover, the various methods that have been employed to obtain extracts from these and other agricultural byproducts were listed and described, with a particular focus on novel, eco-friendly extraction methods (using, for example, innovative and biocompatible solvents like Deep Eutectic Solvents (DESs)) that could reduce the costs and energy consumption of these procedures, with similar or higher yields compared to standard methods.     

The effect of particle size and migration on the formation of flow-induced structures in viscoelastic suspensions

Flow-induced structures in suspensions containing spheres in viscoelastic suspending media were investigated by microscopy and rheo-optical methods. Suspensions of monodisperse polystyrene spheres with diameters ranging from 1.2 to 2.8 μm and dispersed in aqueous solutions of hydroxypropylcellulose were studied in simple shear flows. Optical microscopy observations as well as small-angle light-scattering (SALS) experiments were performed using a parallel plate geometry. In agreement with previous work, necklaces of particles aligned in the flow direction were observed when shearing faster then a critical shear rate, which was found to be independent of particle size. In contrast to earlier work, however, the role of particle migration was found to be of prime importance. Particles were shown to migrate toward the plates where the particles assembled and aligned in strings running in the flow direction. For the smallest particles (1 μm diameter), the formation of particle doublets or short strings along the vorticity direction was observed at low shear rates, which flipped to an orientation into the flow direction and grew into longer strings at higher shear rates. SALS experiments were used to quantify the degree of alignment and its dependence on particle size, shear rate, and gap. For the system under investigation, the degree of alignment was found to increase with increasing shear rate and particle size and with decreasing gap. The present results suggest that, depending on the details of the suspending medium and the size and nature of the suspended particles, the formation of aligned structures is affected by the relative magnitude of the colloidal and hydrodynamic forces and the kinetics of string formation versus the kinetics of migration.     

Computing the characteristic values of partial retarded functional differential equations

The stability of an equilibrium point of a dynamical system is determined by the position in the complex plane of the so-called characteristic values of the linearization around the equilibrium. This work presents an approach for the computation of characteristic values of partial differential equations of evolution involving time delay, based on a coupled pseudospectral-spectral method. Convergence of computed values is of infinite order with respect to the pseudospectral discretization and of finite order with respect to the spectral one. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On an equilibrium problem with complementarity constraints formulation of pay-as-clear electricity market with demand elasticity

We consider a model of pay-as-clear electricity market based on a Equilibrium Problem with Complementarity Constraints approach where the producers are playing a noncooperative game parameterized by the decisions of regulator of the market (ISO). In the proposed approach the bids are assumed to be convex quadratic functions of the production quantity. The demand is endogenously determined. The ISO problem aims to maximize the total welfare of the market. The demand being elastic, this total welfare take into account at the same time the willingness to pay of the aggregated consumer, as well as the cost of transactions. The market clearing will determine the market price in a pay-as-clear way. An explicit formula for the optimal solution of the ISO problem is obtained and the optimal price is proved to be unique. We also state some conditions for the existence of equilibria for this electricity market with elastic demand. Some numerical experiments on a simplified market model are also provided.