Towards in Silico Liquid Crystals. Realistic Transition Temperatures and Physical Properties for n‐Cyanobiphenyls via Molecular Dynamics Simulations

We study the important n‐cyanobiphenyl (with n= 4–8) series of mesogens, using modelling and molecular dynamics simulations. We are able to obtain spontaneously ordered nematics upon cooling isotropic samples of 250 molecules. By using the united‐atom force field developed herein, we show that the experimental isotropic–nematic transition temperatures are reproduced within 4 K, allowing a molecular‐level interpretation of the odd–even effect along the series. Other properties, like densities, orientational order parameters and NMR residual dipolar couplings are also reproduced well, demonstrating the feasibility of predictive in silico modelling of nematics from the molecular structure.     

Enantioselective Extraction of Dinitrophenyl Amino Acids Mediated by Lipophilic Deoxyguanosine Derivatives: Chiral Discrimination by Self-Assembly

The transfer of potassium salts of dinitrophenyl amino acids from water to chloroform by the lipophilic guanosine derivative 1 takes place enantioselectively. Depending on the K⁺: 1 ratio, G-quartets of 1 self-assemble into octamers ( O ) or polymers.     

Independent electron theory of multiple ionization of xenon by intense laser pulses

The intensity dependence of the multiphoton ionization spectra of Xe atoms has been investigated with an improved accuracy and well-controlled laser parameters. In particular, we have examined the ionization rates for X³⁺, X²⁻, X⁺ as functions of the laser intensity and the pressure in the target chamber. The apparatus used for these measurements is characterized by a high-energy resolution (better than 200 meV) and a completely digital acquisition system. The time-of-flight spectra clearly show the contributions of the different isotopes present in Xe gas. The laser pulses have been characterized with great accuracy by monitoring the energy, pulse width and divergence shot by shot. The ionization rates of the different ions have been used for testing the basic assumption of the Geltman theory of multiple ionization based on the single electron ionization model. We have found that for the small intensity range investigated the quantity (dXe ⁺/dI)·(dXe ³⁺/dI)/(dXe ²⁺/dI)² appears to be quite close to the value 0.5 predicted by this model.     

Enzyme Production by Solid Substrate Fermentation of <Emphasis Type="Italic">Pleurotus ostreatus</Emphasis> and <Emphasis Type="Italic">Trametes versicolor</Emphasis> on Tomato Pomace

A process of solid state fermentation (SSF) on tomato pomace was developed with the white-rot fungi Pleurotus ostreatus and Trametes versicolor, using sorghum stalks as support. Operative parameters (humidity, water activity, and size of substrate particles) guaranteeing a good colonization of tomato pomace by both fungi were defined and conditions for production at high titers of the industrially relevant enzymes laccase, xylanase and protease were identified. Significant laccase activity levels (up to 36 U g⁻¹ dry matter) were achieved without any optimization of culture conditions, neither by nutrient addition nor by O₂ enrichment. Furthermore, protease activity levels up to 34,000 U g⁻¹ dry matter were achieved, being higher than those reported for the fungi typically considered as the best protease producers such as Aspergillus strains. Moreover, as one of the most significant results of this study, analysis of P. ostreatus tomato SSF samples by zymogram revealed two bands with laccase activity which had not been detected so far.     

Oxygenic polyoxometalates: a new class of molecular propellers

The oxygen evolving catalyst [Ru(4)(μ-OH)(2)(μ-O)(4)(H(2)O)(4)(γ-SiW(10)O(36))(2)](10-) effects H(2)O(2) dismutation at rates (k = 36.8 ± 1.4 M(-1) s(-1)), one/two order of magnitude higher compared to related tetra-substituted Cu, Fe, Mn, Ni and even Co polyoxometalates, thus providing localised oxygen gas bursts to power nano-propulsion of composite materials.     

Nondestructive analyses of carbonate rocks: applications and potentiality for museum materials

The preciousness of historical artifacts leads to the performance of nondestructive and/or microdestructive analyses, especially when the archeological finds are stored in museums. The PXRF spectrometry represents a powerful technique for the chemometric study of the materials, in alternative to the more usual destructive X‐ray‐based methods. A large set of limestones belonging to several formations cropping out in the Hyblean area (south‐eastern Sicily, Italy) was analyzed by means of a PXRF instrument. The main goal was to test the PXRF potentiality for the discrimination of rocks with similar features and to create a chemical database of carbonate rocks, which were commonly used in the past in the manufacturing of sculptures and stone artifacts. Fluorescence data were processed by means of multivariate statistical analysis. In particular, principal components analysis and linear discriminant analysis were applied. The results allowed us to classify the samples belonging to different formations and to distinguish different rock typologies within each formation. Finally, the investigation showed that the analytical PXRF data can be suitable for a substantial characterization of stone materials and this could be extended to museum materials belonging to cultural heritage. Copyright © 2012 John Wiley & Sons, Ltd.     

Conformational studies of ethylene glycol and its two methyl ether derivatives

As a theoretical analysis of the conformational equilibria of ethylene glycol, methoxyethanol and dimethoxyethane, the energy of each stable conformational isomer (rotamer) of these molecules was calculated for various temperatures and solvent dielectric constants. Classical semi-empirical potential functions were used. Besides intrinsic potentials for rotation about single bonds, intramolecular dispersion and repulsive interaction, dipole-dipole interaction and hydrogen bonding energies were included. Interaction with the solvent was considered only in terms of a continuous dielectric medium interacting with the local dipoles and quadrupoles of the molecule. For each rotamer, the dihedral angles giving the lowest energy were determined. From the energies of each rotamer, Boltzmann distributions of populations were obtained, and total concentrations were calculated in various physically distinguishable states, e.g. those with and without internal hydrogen bonds, or those in which the central C-C bond takes a trans or a gauche conformation. It is shown that the equilibrium constants, K _HB and K _TG, for these two cases are not identical. While changes in the dielectric constant may alter strongly the geometries and energies of individual rotamers, their effect on the average geometries and on the two equilibrium constants is small. The same is true of temperature changes, and is due to the presence of several rotamers in each of the physical states considered. Thus the small temperature dependence of some observed physical properties is shown to be consistent with the distribution of molecules over several conformational states. In solution, the fraction of ethylene glycol molecules with two free OH groups (i.e. without an intramolecular hydrogen bond) is predicted to be at least 20 per cent. This shows that the presence of three-dimensional hydrogen-bonded structures in the liquid, which we propose, is possible in principle.