Parametrizing PCM to obtain solvation free energies from group contributions

A parametrization methodology for evaluating the solvation free energy, using the polarizable continuum model implemented in Gamess software, is presented in a formulation which makes use of a group contribution conception to construct the cavities. The systems studied include alkanes, alcohols, aldehydes and ketones embeded in a continuous medium simulating the water as the solvent. For each family, the CH2, OH, and C=O moieties of atoms are put together in single spheres forming a group. The cavities are constructed in two different ways, one for the electrostatic component and the other for nonelectrostatic contributions, i.e., the cavitation, dispersion, and repulsion components of free energy of solvation. A multivariate analysis is performed to obtain an assembly of variables, for each homologous series, able to give the results which are close to experiment. The analysis is addressed in order to (i) compare the theoretical free energy of solvation with the experimental trends of the solutes in aqueous media, when the chain is increased, (ii) compare the behavior of each component of free energy with the increasing CH2 number, (iii) investigate the influence of the oxygen atom on the components, and (iv) quantify the relative contribution of each component to the final free energy of solvation for some homologous series.     

Multilevel and density functional electronic structure calculations of proton affinities and gas-phase basicities involved in biological phosphoryl transfer

Five multilevel model chemistries (CBS-QB3, G3B3, G3MP2B3, MCG3/3, and MC-QCISD/3) and seven hybrid density functional methods (PBE0, B1B95, B3LYP, MPW1KCIS, PBE1KCIS, and MPW1B95) have been applied to the calculation of gas-phase basicity and proton affinity values for a series of 17 molecules relevant to the study of biological phosphoryl transfer. In addition, W1 calculations were performed on a subset of molecules. The accuracy of the methods was assessed and the nature of systematic errors was explored, leading to the introduction of a set of effective bond enthalpy and entropy correction terms. The multicoefficient correlation methods (MCG3/3 and MC-QCISD), with inclusion of specific zero-point scale factors, slightly outperform the other multilevel methods tested (CBS-QB3, G3B3, and G3MP2B3), with significantly less computational cost, and in the case of MC-QCISD, slightly less severe scaling. Four density functional methods, PBE1KCIS, MPW1B95, PBE0, and B1B95 perform nearly as well as the multilevel methods. These results provide an important set of benchmarks relevant to biological phosphoryl transfer reactions.     

Effects of pressure on maghemite nanoparticles with a core/shell structure

The magnetic property and intraparticle structure of the γ phase of Fe₂O₃ (maghemite) nanoparticles with a diameter (D) of 5.1±0.5 nm were investigated through AC and DC magnetic measurements and powder X-ray diffraction (XRD) measurements at pressures (P) up to 27.7 kbar. Maghemite originally exhibits ferrimagnetic ordering below 918 K, and has an inverse-spinel structure with vacancies. Maghemite nanoparticles studied here consist of a core with structural periodicity and a disordered shell without the periodicity, and core shows superparamagnetism. The DC and AC susceptibilities reveal that the anisotropy energy barrier (ΔE/k_B) and the effective value of the core moment decrease against the initial pressure (P≤3.8 kbar), recovering at P≥3.8 kbar. The change of ΔE/k_B with P is qualitatively identical with that of the core moment, suggesting a down-and-up fluctuation of the number of Fe³⁺ ions constituting the core at the pressure threshold of about 4 kbar. This phenomenon was confirmed by the analysis of the XRD measurement using Scherrer’s formula. The core volume decreased for P≤2.5 kbar, whereas at higher pressure the core was restructured. For 2.5≤P≤10.7 kbar, the volume shrinkage of particle hardly occurs. There, ΔE/k_B is approximately proportional to the volume associated to the ordered fraction of the nanoparticles as seen from XRD, V_core. From this dependence it is possible to separate the core/shell contribution to ΔE/k_B and estimate core and surface anisotropy constants. As for the structural experiments, similar experimental data have been obtained for D=12.8±3.2 nm as well.     

Negative c-axis magnetoresistance in graphite

We have studied the c-axis interlayer magnetoresistance (ILMR), Rc(B) in graphite. The measurements have been performed on strongly anisotropic highly oriented pyrolytic graphite (HOPG) and single crystalline Kish graphite samples in magnetic field up to B=9 T, and the temperature interval 2 K?T?300 K. We have observed negative magnetoresistance, dRc/dB<0, for B‖c-axis for both samples above a certain field Bm(T)>5.4 T and 0.2 T for HOPG and Kish graphite, respectively. The results can be understood consistently by assuming that ILMR is related to a tunneling between zero-energy Landau levels of quasi-two-dimensional Dirac fermions, in a close analogy with the behavior reported for α-(BEDT-TTF)₂I₃ [N. Tajima, et al., Phys. Rev. Lett. 102 (2009) 176403], another multilayer Dirac electron system.     

Heterochromatin and rDNA 5S and 45S sites as reliable cytogenetic markers for castor bean (Ricinus communis,Euphorbiaceae)

The increasing need for renewable energy resources has led to higher demands for biofuel, a scenario where the castor bean (Ricinus communis L.) seed oil represents a promising source of raw material. Despite that, information regarding the genome organization of R. communis is still scarce, impairing the application of modern biotechnological and breeding procedures. The present work brings the first evaluation of the mitotic chromosomes of this species, including 10 potentially interesting accessions for cultivation in semi-arid environments aiming at the biofuel production. The approach included standard staining, fluorochrome staining (CMA/DAPI), fluorescent in situ hybridization (FISH) with rDNA 5S and 45S, as well as silver impregnation. All accessions were diploid with 2n = 2x = 20, displaying mainly metacentric chromosomes, with CMA-positive bands (GC-rich) in all pairs of the complement. After silver impregnation, one to 14 nucleoli were observed, while the FISH with rDNA 45S revealed two large sites and a variety of minor dots, and the DNAr 5S hybridized in a single pair. The observed features were discussed and compared with literature data regarding pachytene bivalents.     

Stable hypersurfaces via the first eigenvalue of the anisotropic Laplacian operator

In this paper we provide a characterization for stable hypersurfaces with constant anisotropic mean curvature immersed in the Euclidean space \(\mathbb {R}^{n+1}\) through the analysis of the first eigenvalue of the anisotropic Laplacian operator.     

Fixed points of endomorphisms over special confluent rewriting systems

Cayley graphs of monoids defined through special confluent rewriting systems are known to be hyperbolic metric spaces which admit a compact completion given by irreducible finite and infinite words. In this paper, we prove that the fixed point submonoids for endomorphisms of these monoids which are boundary injective (or have bounded length decrease) are rational, with similar results holding for infinite fixed points. Decidability of these properties is proved, and constructibility is proved for the case of bounded length decrease. These results are applied to free products of cyclic groups, providing a new generalization for the case of infinite fixed points.     

Engel words and the Restricted Burnside Problem

The following theorem is proved. For any positive integers n and k there exists a number s = s(n, k) depending only on n and k such that the class of all groups G satisfying the identity ^n 1{\left(\left[x_1, {}_ky_1\right] \cdots \left[x_s, {}_ky_s\right]\right)^n \equiv 1} and having the verbal subgroup corresponding to the kth Engel word locally finite is a variety.