Properties of Reactive Oxygen Species by Quantum Monte Carlo

The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of Chemistry, Biology and Atmospheric Science. Nevertheless, the electronic structure of such species is a challenge for ab-initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as $N^3-N^4$, where $N$ is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles

Elevation correction of ERA-Interim temperature data in complex terrain

Air temperature controls a large variety of environmental processes, and is an essential input parameter for land surface models, for example in hydrology, ecology and climatology. However, meteorological networks, which can provide the necessary information, are commonly sparse in complex terrains, especially in high mountainous regions. In order to provide temperature data in an adequate temporal and spatial resolution for local scale applications a new elevation correction method has been developed that is able to downscale 3-hourly ERA-Interim temperature data. The scheme is based on model internal vertical lapse rates derived from different ERA-Interim pressure levels and has been validated for twelve meteorological stations in the German and Swiss Alps. The method was also compared with two other statistical, lapse rate based correction approaches. The results indicate that the use of model internal ERA-Interim lapse rates can significantly improve the downscaling performance when compared to the standard procedure of using fixed lapse rates

Selection for inpatient rehabilitation after severe stroke: What factors influence rehabilitation assessor decision making?

Objectives: This study aimed to identify factors that assessors considered important in decision-making regarding suitability for inpatient rehabilitation after acute severe stroke.Design: Multi-site prospective observational cohort study. Subjects: Consecutive acute, severe stroke patients and their assessors for inpatient rehabilitation. Methods: Rehabilitation assessors completed a questionnaire, rating the importance (10 point visual analogue scale) and direction (positive, negative or neutral) of 15 patient related and 2 organisational items potentially affecting their decision regarding patients’ acceptance to rehabilitation. Results: Of the 75 patients referred to rehabilitation and included in this study 61 (81.3%) were accepted for inpatient rehabilitation. The items considered to be most important in the decision to accept the patient for rehabilitation were pre-morbid cognition, pre-morbid mobility and pre-morbid communication. For those not accepted the most important items were current mobility, social support and current cognition. Factor analysis revealed 3 underlying factors, interpreted as post-stroke status, pre-morbid status, and social attributes, accounting for 61.8% of the total variance. All were independently associated with acceptance for rehabilitation (p < 0.05). Conclusions: This study highlights the importance of pre-morbid function and social factors in addition to post-stroke function in the decision making process for acceptance to rehabilitation following severe stroke. Future models for selection for rehabilitation should consider inclusion of these factors

Influence of damping on the excitation of the double giant resonance

We study the effect of the spreading widths on the excitation probabilities of the double giant dipole resonance. We solve the coupled-channels equations for the excitation of the giant dipole resonance and the double giant dipole resonance. Taking Pb+Pb collisions as example, we study the resulting effect on the excitation amplitudes, and cross sections as a function of the width of the states and of the bombarding energy.Comment: 8 pages, 3 figures, corrected typo

Angular Forces Around Transition Metals in Biomolecules

Quantum-mechanical analysis based on an exact sum rule is used to extract an semiclassical angle-dependent energy function for transition metal ions in biomolecules. The angular dependence is simple but different from existing classical potentials. Comparison of predicted energies with a computer-generated database shows that the semiclassical energy function is remarkably accurate, and that its angular dependence is optimal.Comment: Tex file plus 4 postscript figure

Rates of Dinitrogen Fixation and the Abundance of Diazotrophs in North American Coastal Waters Between Cape Hatteras and Georges Bank

We coupled dinitrogen (N2) fixation rate estimates with molecular biological methods to determine the activity and abundance of diazotrophs in coastal waters along the temperate North American Mid-Atlantic continental shelf during multiple seasons and cruises. Volumetric rates of N2 fixation were as high as 49.8 nmol N L(sup -1) d(sup -1) and areal rates as high as 837.9 micromol N m(sup -2) d(sup -1) in our study area. Our results suggest that N2 fixation occurs at high rates in coastal shelf waters that were previously thought to be unimportant sites of N2 fixation and so were excluded from calculations of pelagic marine N2 fixation. Unicellular N2-fixing group A cyanobacteria were the most abundant diazotrophs in the Atlantic coastal waters and their abundance was comparable to, or higher than, that measured in oceanic regimes where they were discovered. High rates of N2 fixation and the high abundance of diazotrophs along the North American Mid-Atlantic continental shelf highlight the need to revise marine N budgets to include coastal N2 fixation. Integrating areal rates of N2 fixation over the continental shelf area between Cape Hatteras and Nova Scotia, the estimated N2 fixation in this temperate shelf system is about 0.02 Tmol N yr(sup -1), the amount previously calculated for the entire North Atlantic continental shelf. Additional studies should provide spatially, temporally, and seasonally resolved rate estimates from coastal systems to better constrain N inputs via N2 fixation from the neritic zone

Quantum Nondemolition State Measurement via Atomic Scattering in Bragg Regime

We suggest a quantum nondemolition scheme to measure a quantized cavity field state using scattering of atoms in general Bragg regime. Our work extends the QND measurement of a cavity field from Fock state, based on first order Bragg deflection [9], to any quantum state based on Bragg deflection of arbitrary order. In addition a set of experimental parameters is provided to perform the experiment within the frame work of the presently available technology.Comment: 11 pages text, 4 eps figures, to appear in letter section of journal of physical society of Japa

LEED Holography applied to a complex superstructure: a direct view of the adatom cluster on SiC(111)-(3x3)

For the example of the SiC(111)-(3x3) reconstruction we show that a holographic interpretation of discrete Low Energy Electron Diffraction (LEED) spot intensities arising from ordered, large unit cell superstructures can give direct access to the local geometry of a cluster around an elevated atom, provided there is only one such prominent atom per surface unit cell. By comparing the holographic images obtained from experimental and calculated data we illuminate validity, current limits and possible shortcomings of the method. In particular, we show that periodic vacancies such as cornerholes may inhibit the correct detection of the atomic positions. By contrast, the extra diffraction intensity due to slight substrate reconstructions, as for example buckling, seems to have negligible influence on the images. Due to the spatial information depth of the method the stacking of the cluster can be imaged down to the fourth layer. Finally, it is demonstrated how this structural knowledge of the adcluster geometry can be used to guide the dynamical intensity analysis subsequent to the holographic reconstruction and necessary to retrieve the full unit cell structure.Comment: 11 pages RevTex, 6 figures, Phys. Rev. B in pres

Conversions of Tricyclic Antidepressants and Antipsychotics with Selected P450s from Sorangium cellulosum So ce56 s

ABSTRACT Human cytochromes P450 (P450s) play a major role in the biotransformation of drugs. The generated metabolites are important for pharmaceutical, medical, and biotechnological applications and can be used for derivatization or toxicological studies. The availability of human drug metabolites is restricted and alternative ways of production are requested. For this, microbial P450s turned out to be a useful tool for the conversion of drugs and related derivatives. Here, we used 10 P450s from the myxobacterium Sorangium cellulosum So ce56, which have been cloned, expressed, and purified. The P450s were investigated concerning the conversion of the antidepressant drugs amitriptyline, clomipramine, imipramine, and promethazine; the antipsychotic drugs carbamazepine, chlorpromazine, and thioridazine, as well as their precursors, iminodibenzyl and phenothiazine. Amitriptyline, chlorpromazine, clomipramine, imipramine, and thioridazine are efficiently converted during the in vitro reaction and were chosen to upscale the production by an Escherichia coli-based whole-cell bioconversion system. Two different approaches, a whole-cell system using M9CA medium and a system using resting cells in buffer, were used for the production of sufficient amounts of metabolites for NMR analysis. Amitriptyline, clomipramine, and imipramine are converted to the corresponding 10-hydroxylated products, whereas the conversion of chlorpromazine and thioridazine leads to a sulfoxidation in position 5. It is shown for the first time that myxobacterial P450s are efficient to produce known human drug metabolites in a milligram scale, revealing their ability to synthesize pharmaceutically important compounds

Gravity modelling along CROP04 seismic profile

The processing and interpretation of seismic lines, together with the analysis of surficial geological data and hydrocarbon wells data, are powerful tools for the investigation of crust structures. Nevertheless, for depths exceeding that portion of crust usually investigated for commercial purposes, only geophysical data are generally available (among the others: NVR seismic from CROP project, DSS data, magnetic data, gravity data). In this context, the possibility of comparing two independent geophysical data sets, such as data from seismic exploration (CROP Project) and gravimetric analysis (Bouguer anomalies), is of particular interest for investigations into the deeper crust portion. In the present work gravity data modelling was used to study deep crust, constraints being provided by WARR data and by reflection seismic data obtained along the CROP04 profile that crosses the Southern Apennines (Italy) from Agropoli (SW) to Barletta (NE). A preliminary interpretation has been made of the regional gravity anomaly trend in deep crust in Southern Italy; the role of this anomaly trend as an independent constraint for the geological interpretation of the CROP04 seismic line is discussed