and Au6 clusters: Superatomic molecules bearing an SP3‐hybrid Au6 core

The octahedral Au₆ core is explored for the formation of novel SP³‐hybrid superatomic molecules by considering and Au₆ clusters (X= F, Cl, Br, I). The bonding between the four capping atoms and the Au₆ core requires a combination of 1S and 1P shells of the core leading to a set of four equivalent hybrid orbitals. Thus, combining the superatom concept with both the Lewis structure model and VSEPR theory contributes to the rationalization of structure and bonding in metal clusters. For example, our results consider the Au₆ clusters as analogues of the simplest perhalogenated hydrocarbon, CX₄.     

Pharmacological interactions of essential oil constituents on the viability of micro-organisms

Complex interactions between numerous components of essential oils often contribute to the pharmacological effect and therapeutic outcome. To further elucidate these interactions, several essential oil constituents (EOCs) were combined in different ratios and their inhibitory effects on the growth of bacteria and yeast determined using the minimum inhibitory concentration (MIC) microplate assay. When combined and tested against Candida albicans, (+)-beta-pinene interacted antagonistically with (-)-menthone (sigmaFIC(T) = 9.80), but synergistically with 1,8-cineole (sigmaFIC(T) = 0.35). Against Escherichia coli, the combination of E- and Z-(+/-)-nerolidol and geranyl acetate displayed an additive interaction (sigmaFIC(T) = 1.04); while a variable interaction was observed between E- and Z-(+/-)-nerolidol and eugenol with antagonism and synergy being observed at different ratios of each EOC. The combination of either carvacrol or eugenol with an antimicrobial agent (ciprofloxacin or amphotericin B) resulted in synergistic interactions against all microorganisms tested. These favourable results further support the use of essential oil constituents as adjuvants in the development of a new generation of phytopharmaceuticals that can be used in combination with synthetic drugs against drug-resistant microorganisms.     

Microbial transformation of marine halogenated sesquiterpenes

The sesquiterpene pacifenol is one of the main constituents of the red alga Laurencia claviformis. Earlier work on the semisynthetic derivatives of pacifenol afforded a series of halogenated sesquiterpenes. The aim of the present work was to obtain new hydroxylated derivatives of halogenated sesquiterpenes by means of microbial transformation using Aspergillus niger, Gibberella fujikuroi and Mucor plumbeus. The best results were obtained with M. plumbeus. The microbiological transformation by M. plumbeus of pacifenol, and two semisynthetic derivatives, is described. The structures of the new compounds obtained were determined by spectroscopic means.     

Local Well-Posedness for Membranes in the Light Cone Gauge

In this paper we consider the classical initial value problem for the bosonic membrane in light cone gauge. A Hamiltonian reduction gives a system with one constraint, the area preserving constraint. The Hamiltonian evolution equations corresponding to this system, however, fail to be hyperbolic. Making use of the area preserving constraint, an equivalent system of evolution equations is found, which is hyperbolic and has a well-posed initial value problem. We are thus able to solve the initial value problem for the Hamiltonian evolution equations by means of this equivalent system. We furthermore obtain a blowup criterion for the membrane evolution equations, and show, making use of the constraint, that one may achieve improved regularity estimates.     

Hydrogen‐bonded nucleophile effects in ANS: the reactions of 1‐chloro and 1‐fluoro‐2,4‐dinitrobenzene with 2‐guanidinobenzimidazole, 1‐(2‐aminoethyl)piperidine and N‐(3‐aminopropyl)morpholine in aprotic solvents

The kinetics of the reactions of 2,4‐dinitrofluorobenzene (DNFB) and 2,4‐dinitrochlorobenzene (DNClB) with 2‐guanidinobenzimidazole (2‐GB) at 40 ± 0.2 °C in dimethylsulphoxide (DMSO), toluene, and in toluene–DMSO mixtures, and with 1‐(2‐aminoethyl)piperidine (2‐AEPip) and N‐(3‐aminopropyl)morpholine (3‐APMo) in toluene at 25 ± 0.2 °C were studied under pseudo first‐order conditions. For the reactions of 2‐GB carried out in pure DMSO, the second‐order rate coefficients were independent of the amine concentration. In contrast, the reactions of 2‐GB with DNFB in toluene, showed a kinetic behaviour consistent with a base‐catalysed decomposition of the zwitterionic intermediate. These results suggest an intramolecular H‐bonding of 2‐GB in toluene, which is not present in DMSO. To confirm this interpretation the reactions were studied in DMSO–toluene mixtures. Small amounts of DMSO produce significant increase in rate that is not expected on the basis of the classical effect of a dipolar aprotic medium; the effect is consistent with the formation of a nucleophile/co‐solvent mixed aggregate. For the reactions of 3‐APMo with both substrates in toluene, the second‐order rate coefficients, k_A, show a linear dependence on the [amine]. 3‐APMo is able to form a six‐membered ring by an intramolecular H‐bond which prevents the formation of self‐aggregates. In contrast, a third order was observed in the reactions with 2‐AEPip: these results can be interpreted as a H‐bonded homo‐aggregate of the amine acting as a better nucleophile than the monomer. Most of these results can be well explained within the frame of the ‘dimer nucleophile’ mechanism. Copyright © 2010 John Wiley & Sons, Ltd.     

Scalar potential without cubic term in 3-3-1 models without exotic electric charges

A detailed study of the criteria for stability of the scalar potential, and the proper electroweak symmetry breaking pattern in some 3-3-1 models without exotic electric charges is presented. In this paper we concentrate in a scalar sector with three Higgs scalar triplets, with a potential that does not include the cubic term, due to the presence of a discrete symmetry. For the analysis we use, and improve, a method previously developed to study the scalar potential in the two-Higgs-doublet extension of the standard model. Our main result is to show the consistency of those 3-3-1 models without exotic electric charges.     

Hydrogen‐bonding controls the solid‐state and enantiomeric comformations of the amino alcohol ligand 2‐[(2‐hydroxyethyl)amino]cyclohexanol

The crystal structure of the title compound, C₈H₁₇NO₂, consists of (R,R) and (S,S) enantiomeric pairs packed in adjacent double layers which are characterized by centrosymmetric hydrogen‐bonded dimers, generated via N—H...O and O—H...O interactions, respectively. Intermolecular interactions, related to acceptor and donor molecule chirality, link the achiral double layers into tubular columns, which consist of a staggered hydrophilic inner core surrounded by a hydrophobic cycloalkyl outer surface and extend in the [011] direction.     

Determination of the Mechanical Properties of Powdered Agricultural Products and Sugar

Grain, forage cereals and different types of flour are commonly stored in silos. Their behavior within these structures is mainly governed by their mechanical properties. Since their advent, numerical methods have increasingly been used in silo design. However, the results obtained using these methods strongly depend on the variables employed to define the materials stored. Since the literature provides little information on the variables required for modeling the behavior of agricultural powdered materials, the goals of the present work were to: i) provide values for the different variables that are needed when designing silos using numerical methods (e.g., the Poisson ratio, the dilatancy angle and the modulus of elasticity, etc.), and ii) investigate the suitability of tests used in soil mechanics for powdered materials (e.g., the direct shear and the oedometric and triaxial test). Recommended values for these variables are proposed.     

Influence of ligand structure and molecular geometry on the properties of d polypyridinic transition metal complexes

Different strategies to improve the excited state properties of polypyridinic complexes by varying ligand structure and molecular geometry are described. Bidentate and tetradentate ligands based on fragments as dipyrido[3,2-a:2′,3′-c]phenazine, dppz, and pyrazino[2,3-f][1,10]-phenanthroline, ppl, have been used. Quinonic residues were fused to these basic units to improve acceptor properties. Photophysical studies were performed in order to test theoretical predictions.