Phase transitions induced by shock compression on a gypsum mineral: X-ray and micro-Raman analysis

As a part of systematic researches of phase transitions induced by shock compression in phosphates, silicates, germanates and sulfates, in this article we report preliminary results obtained from shock recovery experiments on powders of a gypsum mineral. The shock experiment was performed in a light gas gun until a pressure close to 14?GPa reached. The experimental techniques employed to analyze the shock effects on recovered samples were: Scanning Electron Microscopy (SEM), X-ray Powder Diffraction (XRD) and Micro-Raman Spectroscopy (MRS). The SEM observations show a high plasticity in the impacted sample composed mainly by gypsum and bassanite quantified by Rietveld analysis of the XRD. The results indicate the partial dehydration of gypsum as a result of impact. The MRS analysis suggests the presence of micro-mixtures of gypsum, bassanite and anhydrite heterogeneously distributed throughout the recovered sample.     

Water solvent effects using continuum and discrete models: The nitromethane molecule,CH3NO2

The first three valence transitions of the two nitromethane conformers (CH₃NO₂) are two dark n → π* transitions and a very intense π → π* transition. In this work, these transitions in gas‐phase and solvated in water of both conformers were investigated theoretically. The polarizable continuum model (PCM), two conductor‐like screening (COSMO) models, and the discrete sequential quantum mechanics/molecular mechanics (S‐QM/MM) method were used to describe the solvation effect on the electronic spectra. Time dependent density functional theory (TDDFT), configuration interaction including all single substitutions and perturbed double excitations (CIS(D)), the symmetry‐adapted‐cluster CI (SAC‐CI), the multistate complete active space second order perturbation theory (CASPT2), and the algebraic‐diagrammatic construction (ADC(2)) electronic structure methods were used. Gas‐phase CASPT2, SAC‐CI, and ADC(2) results are in very good agreement with published experimental and theoretical spectra. Among the continuum models, PCM combined either with CASPT2, SAC‐CI, or B3LYP provided good agreement with available experimental data. COSMO combined with ADC(2) described the overall trends of the transition energy shifts. The effect of increasing the number of explicit water molecules in the S‐QM/MM approach was discussed and the formation of hydrogen bonds was clearly established. By including explicitly 24 water molecules corresponding to the complete first solvation shell in the S‐QM/MM approach, the ADC(2) method gives more accurate results as compared to the TDDFT approach and with similar computational demands. The ADC(2) with S‐QM/MM model is, therefore, the best compromise for accurate solvent calculations in a polar environment. © 2015 Wiley Periodicals, Inc.     

Ultrafast electrocyclic ring opening of 7-dehydrocholesterol in solution: the influence of solvent on excited state dynamics

Broadband UV-visible femtosecond transient absorption spectroscopy and steady-state integrated fluorescence were used to study the excited state dynamics of 7-dehydrocholesterol (provitamin D(3), DHC) in solution following excitation at 266 nm. The major results from these experiments are: (1) The excited state absorption spectrum is broad and structureless spanning the visible from 400 to 800 nm. (2) The state responsible for the excited state absorption is the initially excited state. Fluorescence from this state has a quantum yield of ～2.5 × 10(-4) in room temperature solution. (3) The decay of the excited state absorption is biexponential, with a fast component of ～0.4-0.65 ps and a slow component 1.0-1.8 ps depending on the solvent. The spectral profiles of the two components are similar, with the fast component redshifted with respect to the slow component. The relative amplitudes of the fast and slow components are influenced by the solvent. These data are discussed in the context of sequential and parallel models for the excited state internal conversion from the optically excited 1(1)B state. Although both models are possible, the more likely explanation is fast bifurcation between two excited state geometries leading to parallel decay channels. The relative yield of each conformation is dependent on details of the potential energy surface. Models for the temperature dependence of the excited state decay yield an intrinsic activation barrier of ～2 kJ/mol for internal conversion and ring opening. This model for the excited state behavior of DHC suggests new experiments to further understand the photochemistry and perhaps control the excited state pathways with optical pulse shaping.     

Raman spectra of hybrid materials based on carbon nanotubes and Cs3PMo12O40

A route for the synthesis of hybrid materials using multiwalled carbon nanotubes (MWCNTS) and Cs₃PMo₁₂O₄₀ was confirmed. The Cs₃PMo₁₂O₄₀ salt was synthesized from H₃PMo₁₂O₄₀·14H₂O and CsCl. All compounds were characterized by Raman spectroscopy. The synthesis method can produce a chemically stable Cs₃PMo₁₂O₄₀ molecule and pure and oxidized MWCNTS. Raman spectroscopy showed that the chemical interaction between MWCNTS and Cs₃PMo₁₂O₄₀ was essentially of electrostatic nature. Raman spectra obtained with different wavelengths showed thermal decomposition of H₃PMo₁₂O₄₀·14H₂O (raw materials) from laser heating process. On the contrary, the synthesized compound (i.e. Cs₃PMo₁₂O₄₀) was stable under the experimental conditions.     

Scoring by intermolecular pairwise propensities of exposed residues (SIPPER): a new efficient potential for protein-protein docking

A detailed and complete structural knowledge of the interactome is one of the grand challenges in Biology, and a variety of computational docking approaches have been developed to complement experimental efforts and help in the characterization of protein-protein interactions. Among the different docking scoring methods, those based on physicochemical considerations can give the maximum accuracy at the atomic level, but they are usually computationally demanding and necessarily noisy when implemented in rigid-body approaches. Coarser-grained knowledge-based potentials are less sensitive to details of atomic arrangements, thus providing an efficient alternative for scoring of rigid-body docking poses. In this study, we have extracted new statistical potentials from intermolecular pairs of exposed residues in known complex structures, which were then used to score protein-protein docking poses. The new method, called SIPPER (scoring by intermolecular pairwise propensities of exposed residues), combines the value of residue desolvation based on solvent-exposed area with the propensity-based contribution of intermolecular residue pairs. This new scoring function found a near-native orientation within the top 10 predictions in nearly one-third of the cases of a standard docking benchmark and proved to be also useful as a filtering step, drastically reducing the number of docking candidates needed by energy-based methods like pyDock.     

Particle creation by loop black holes

We study the black hole particle production in a regular spacetime metric obtained in a minisuperspace approach to loop quantum gravity. In different previous papers the static solution was obtained and shown to be singularity-free and self-dual. In this paper expanding a previous study of the black hole dynamics we repeat the Hawking analysis which leads to a thermal flux of particles at the future infinity. The evaporation time is infinite and the unitarity is recovered due to the regularity of the spacetime and to the characteristic behavior of the surface gravity.     

Fundamental symmetries studies with cold trapped francium atoms at ISAC

Francium combines a heavy nucleus (Z = 87) with the simple atomic structure of alkalis and is a very promising candidate for precision tests of fundamental symmetries such as atomic parity non-conservation measurements. Fr has no stable isotopes, and the ISAC radioactive beam facility at TRIUMF, equipped with an actinide target, promises to provide record quantities of Fr atoms, up to 10¹⁰/s for some isotopes. We discuss our plans for a Fr on-line laser trapping facility at ISAC and experiments with samples of cold Fr atoms. We outline our plans for a measurement of the nuclear anapole moment – a parity non-conserving, time-reversal conserving moment that arises from weak interactions between nucleons – in a chain of Fr isotopes. Its measurement is a unique probe for neutral weak interactions inside the nucleus.      

Transport and fluctuations during electrode biasing on TJ-II

Edge polarization experiments were carried out on TJ-II using an electrode. It has been found that the plasma response is different at densities below and above the threshold value to trigger the spontaneously development of E × B sheared flows. At low densities, the edge plasma potential is fully controlled by external biasing, while at higher densities it is determined not only by external biasing but also by the electric fields spontaneous developed. Although an improvement in particle confinement is observed for both polarities, a larger increase is observed for negative electrode bias. Presented at the Workshop “Electric Fields, Structures and Relaxation in Edge Plasmas”, Tarragona, Spain, July 3–4, 2005.     

Exploring the dynamics of calix[4]pyrrole: effect of solvent and fluorine substitution

Molecular dynamics simulations show that calix[4]pyrrole (CP) and octafluorocalix[4]pyrrole (8F-CP) are extremely flexible molecules. CP mainly adopts the 1,3-alternate conformation in all the solvents, although the percentage of alternative conformations increases in polar solvents, especially those with good hydrogen-bonding acceptor properties. However, in the case of 8F-CP, the cone conformation is the most populated in some solvents. Transitions between conformers are common and fast, and both CP and 8F-CP can adopt the cone conformation needed for optimum interaction with anions more easily than would be predicted on the basis of previous gas-phase calculations. Furthermore, the present studies show that when a fluoride anion is specifically placed initially in close proximity to CP and 8F-CP in their respective 1,3-alternate conformations, an extremely fast change to the cone conformation is observed in both cases. The results suggest that preorganization does not represent a major impediment to anion-binding for either CP or 8F-CP, and that ion-induced conformational changes can follow different mechanisms depending on the solvent and the chemical substituents present on the calix[4]pyrrole beta-pyrrolic positions.