Density Functional Calculations On First-Row Transition Metals

The excitation energies and ionization potentials of the atoms in the first transition series are notoriously difficult to compute accurately. Errors in calculated excitation energies can range from 1--4 eV at the Hartree-Fock level, and errors as high as 1.5eV are encountered for ionization energies. In the current work we present and discuss the results of a systematic study of the first transition series using a spin-restricted Kohn-Sham density-functional method with the gradient-corrected functionals of Becke and Lee, Yang and Parr. Ionization energies are observed to be in good agreement with experiment, with a mean absolute error of approximately 0.15eV; these results are comparable to the most accurate calculations to date, the Quadratic Configuration Interaction (QCISD(T)) calculations of Raghavachari and Trucks. Excitation energies are calculated with a mean error of approximately 0.5eV, compared with \sim 1\mbox{eV} for the local density approximation and 0.1eV for QCISD(T). These gradient-corrected functionals appear to offer an attractive compromise between accuracy and computational effort.Comment: Journal of Chemical Physics, 29, LA-UR-93-425

Cancer-Associated Thrombosis in Cirrhotic Patients with Hepatocellular Carcinoma.

It is common knowledge that cancer patients are more prone to develop venous thromboembolic complications (VTE). It is therefore not surprising that patients with hepatocellular carcinoma (HCC) present with a significant risk of VTE, with the portal vein being the most frequent site (PVT). However, patients with HCC are peculiar as both cancer and liver cirrhosis are conditions that can perturb the hemostatic balance towards a prothrombotic state. Because HCC-related hypercoagulability is not clarified at all, the aim of the present review is to summarize the currently available knowledge on epidemiology and pathogenesis of non-malignant thrombotic complications in patients with liver cirrhosis and HCC. They are at increased risk to develop both PVT and non-splanchnic VTE, indicating that both local and systemic factors can foster the development of site-specific thrombosis. Recent studies have suggested multiple and often interrelated mechanisms through which HCC can tip the hemostatic balance of liver cirrhosis towards hypercoagulability. Described mechanisms include increased fibrinogen concentration/polymerization, thrombocytosis, and release of tissue factor-expressing extracellular vesicles. Currently, there are no specific guidelines on the use of thromboprophylaxis in this unique population. There is the urgent need of prospective studies assessing which patients have the highest prothrombotic profile and would therefore benefit from early thromboprophylaxis

Drying kinetics and physico-chemical quality of mango slices

Mango (Mangifera indica L.) is an important tropical fruit consumed worldwide and grown in Italy only in Sicily, where the areas of the Tyrrhenian coast have proved to be suitable to produce valuable fruits. Mango fruit has a pleasant aroma and taste, which are important qualities for consumer’s sensorial acceptance. However, they are highly perishable, prone to progressive undesired changes if stored untreated, resulting in around 25% postharvest losses, which is further increased during storage and transportation. An alternative for reducing the above-mentioned undesired changes is the dehydration of the cut fruit, which reduce the fruit water activity, thereby avoiding the deteriorative process and extending the shelf-life. This study investigates the effect of dehydration at different temperatures (50, 60 and 70°C) on drying kinetics and volatile compounds of two cultivars (Keitt and Osteen) of mango fruits cultivated in Sicily. Significant losses of volatile constituents of fresh mango occurred at higher temperature, especially for the Osteen cultivar. A diffusion model including the effect of shrinkage is also proposed, which may be used to describe drying behaviour of fruits and to define the optimal drying conditions.. Experimental data of the moisture ratio during drying were well predicted by the model

Thermo-treatment affects Quercus cerris L. wood properties and the antioxidant activity and chemical composition of its by-product extracts

Nowadays, there is an increasing interest on thermo-treatment and its effects on wood structure and extraction processes, connected to the wood use for industrial application and for its use as biorefinery. The present investigation aimed to provide the main changes on wood properties (mass loss, color variation and modulus of elasticity) and a comparative analysis of the antioxidant properties and GC–MS profile of the extracts from Turkey oak (Quercus cerris L.) wood. Untreated and thermo-treated wood (170 °C x 3 h) samples were compared. Thermo-treatment induced a mass loss (5.1%) in wood, a darkening of color surface (ΔE = 7.6) and a decrease of MOE (4.1%). Moreover samples were extracted using different techniques: maceration (ME), ultrasound assisted extraction (UAE) and accelerated solvent extraction (ASE). Extracts were tested to evaluate the content of polyphenols and flavonoids along with the in vitro antioxidant activity. Results showed that extracts obtained from thermo-treated wood reported the highest Relative Antioxidant Capacity Index and extraction techniques affected the value in the following rating: UAE > ME > ASE. Qualitative and quantitative measurements of chemical compounds were carried out by GC–MS system. Taking into account the thermo-treatment and extraction techniques, principal component analysis (PCA) was performed also in order to evaluate the relationships among principal chemical compounds. According to results obtained, thermo-treatment and extraction technique had a determinant role in the antioxidant efficiency and, consequently, on the potential application of extracts

Relationship between blood remifentanil concentration and stress hormone levels during pneumoperitoneum in patients undergoing laparoscopic cholecystectomy

The effect of remifentanil on stress response to surgery is unclear. However, there are not clinical studies investigating the relationship between blood remifentanil concentrations and stress hormones. Therefore, the aim of the present study was to assess the association between blood remifentanil concentrations measured after pneumoperitoneum and cortisol (CORT) or prolactin (PRL) ratio (intraoperative/preoperative value), in patients undergoing laparoscopic cholecystectom

On special quadratic birational transformations of a projective space into a hypersurface

We study transformations as in the title with emphasis on those having smooth connected base locus, called "special". In particular, we classify all special quadratic birational maps into a quadric hypersurface whose inverse is given by quadratic forms by showing that there are only four examples having general hyperplane sections of Severi varieties as base loci.Comment: Accepted for publication in Rendiconti del Circolo Matematico di Palerm

Supersymmetry and Positive Energy in Classical and Quantum Two-Dimensional Dilaton Gravity

An $N = 1$ supersymmetric version of two dimensional dilaton gravity coupled to matter is considered. It is shown that the linear dilaton vacuum spontaneously breaks half the supersymmetries, leaving broken a linear combination of left and right supersymmetries which squares to time translations. Supersymmetry suggests a spinorial expression for the ADM energy $M$, as found by Witten in four-dimensional general relativity. Using this expression it is proven that ${M}$ is non-negative for smooth initial data asymptotic (in both directions) to the linear dilaton vacuum, provided that the (not necessarily supersymmetric) matter stress tensor obeys the dominant energy condition. A {\it quantum} positive energy theorem is also proven for the semiclassical large-$N$ equations, despite the indefiniteness of the quantum stress tensor. For black hole spacetimes, it is shown that $M$ is bounded from below by $e^{- 2 \phi_H}$, where $\phi_H$ is the value of the dilaton at the apparent horizon, provided only that the stress tensor is positive outside the apparent horizon. This is the two-dimensional analogue of an unproven conjecture due to Penrose. Finally, supersymmetry is used to prove positive energy theorems for a large class of generalizations of dilaton gravity which arise in consideration of the quantum theory.Comment: 21 page

Nanoflows through disordered media: a joint Lattice Boltzmann and Molecular Dynamics investigation

We investigate nanoflows through dilute disordered media by means of joint lattice Boltzmann (LB) and molecular dynamics (MD) simulations -- when the size of the obstacles is comparable to the size of the flowing particles -- for randomly located spheres and for a correlated particle-gel. In both cases at sufficiently low solid fraction, $\Phi<0.01$, LB and MD provide similar values of the permeability. However, for $\Phi > 0.01$, MD shows that molecular size effects lead to a decrease of the permeability, as compared to the Navier-Stokes predictions. For gels, the simulations highlights a surplus of permeability, which can be accommodated within a rescaling of the effective radius of the gel monomers.Comment: 4 pages, 4 figure