The correlation of proton affinities with atomic charges and electronegativities for the group 14 to 17 hydrides

Proton affinities for hydrides of formula $\mathrm{AH}^{-}_{n-1}$ containing the elements A from the second to the fifth period of the periodic table and groups 14 to 17 are predicted at the Hartree–Fock, MP2 and B3LYP levels of theory employing both core potential basis sets and the 3‐21G basis set. The core potential methods perform well when compared with all electron calculations using the 3‐21++G** basis set. The proton affinities of the hydrides containing elements from groups 15 and 16 of the periodic table are more accurate than those with elements from groups 14 and 17. A cancellation of errors appears to occur more completely if the protonated and nonprotonated molecules contain both bond and lone pairs before and after the protonation reaction. Proton affinities correlate nearly linearly with the atomic charges on the hydrogen atoms when these charges are determined by the generalized atomic polar tensor (GAPT) method. This tendency can be associated, in principle, with the group electronegativities as introduced by Iczkowski and Margrave. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1119–1131, 2000     

Structure and protonation of the bis-ethylene adduct [Pt(micro-PBut2)(eta2-CH2=CH2)]2. Pt-H-P agostic interaction and proton scrambling

The bis-ethylene derivative [Pt(micro-PBu(t)(2))(eta(2)-CH(2)=CH(2))](2) was prepared and characterized by X-ray diffraction; its protonation affords [Pt(2)(micro-PBu(t)(2))(micro-PBu(t)(2)H)(eta(2)-CH(2)=CH(2))(2)](CF(3)SO(3)), with a rarely observed P-H-M agostic proton in rapid exchange with those of the adjacent ethylene molecule.     

Antioxidant bibenzyl derivatives from Notholaena nivea Desv

Four new bibenzyl derivatives were isolated, together with other known bibenzyls, by bioassay-guided fractionation of a CHCl?-MeOH extract of Notholaena nivea Desv. (Pteridaceae) aerial parts. The structures were elucidated by NMR, ESIMS and other spectral analyses. Their antioxidative effects towards superoxide, lipidic peroxidation and the 2,2'-azino-bis-3-ethilbenzothiazoline-6-sulfonic acid (ABTS) radical were assayed. Results showed that the compound 3,12-dihydroxy-5-methoxybibenzyl (6) is the most active compound in the ABTS free-radical scavenging test, while in the coupled oxidation of β-carotene and linoleic acid assay the compound 5,12-dihydroxy-3-methoxydibenzyl-6-carboxylic acid (1) exerted the highest activity after 1h. A superoxide anion enzymatic test was also carried out and the results were confirmed by an inhibition of xanthine oxidase activity assay. The putative protective role played by compounds 1 and 6 on the injurious effects of reactive oxygen metabolites on the intestinal epithelium, using a Caco-2 human cell line, was investigated. H?O?-induced alterations were prevented by preincubating the cells with compounds 1 and 6.     

Electrocatalytic Performances of Pure and Mixed Hexacyanoferrates of Cu and Pd for the Reduction of Hydrogen Peroxide

A study on the performances of mixed hexacyanoferrates of Cu and Pd (CuPdHCFs), potentiodynamically grown on glassy carbon surfaces, was carried out. Morphological (SEM‐EDX analysis) and electrochemical characterizations were performed, and the electrocatalytic ability of films with various compositions was tested by chronoamperometry. CuPdHCFs were found to display good electrocatalytic performances, with a maximum sensitivity of 45.3 mA M^?1 cm^?2 at 0.0 V vs. SCE (depending on the Cu and Pd ratio), against the value of 9.1 mA M^?1 cm^?2 obtained with pure copper hexacyanoferrate (CuHCF). Additionally, mixed hexacyanoferrates showed a higher pH and operational stability. The key role of Cu in Cu‐based hexacyanoferrates was investigated and highlighted.     

SU (3) Chern-Simons field theory in three-manifolds

We present the solution of the non-Abelian SU (3) Chern-Simons field theory defined in a generic three-manifold which is closed, connected and orientable. The surgery rules, which permit us to solve the theory, are derived and several examples of vacuum expectation values of Wilson line operators are computed. The three-manifold invariant associated with the non-Abelian SU (3) Chern-Simons model is defined and its values are computed for various three-manifolds.     

Sensitivity Analysis and Quantification of the Role of Governing Transport Mechanisms and Parameters in a Gas Flow Model for Low-Permeability Porous Media

Recent models represent gas (methane) migration in low-permeability media as a weighted sum of various contributions, each associated with a given flow regime. These models typically embed numerous chemical/physical parameters that cannot be easily and unambiguously evaluated via experimental investigations. In this context, modern sensitivity analysis techniques enable us to diagnose the behavior of a given model through the quantification of the importance and role of model input uncertainties with respect to a target model output. Here, we rely on two global sensitivity analysis approaches and metrics (i.e., variance-based Sobol’ indices and moment-based AMA indices) to assess the behavior of a recent interpretive model that conceptualizes gas migration as the sum of a surface diffusion mechanism and two weighted bulk flow components. We quantitatively investigate the impact of (i) each uncertain model parameter and (ii) the type of their associated probability distribution on the evaluation of methane flow. We then derive the structure of an effective diffusion coefficient embedding all complex mechanisms of the model considered and allowing quantification of the relative contribution of each flow mechanism to the overall gas flow.

     

Strengthening of RC beams with an innovative timber-FRP composite system

The results of a theoretical and experimental research project on the use of an innovative technique for strengthening concrete beams are presented. A spacer element is inserted between the tension side of a beam and the composite material to increase its lever arm and to enhance the over all stiffness of the strengthened beam. The main aim of this exploratory project was to increase the ultimate failure load of strengthened beam specimens, whilst guaranteeing acceptable over all deflections at the serviceability limit states. This resulted into a significant reduction in the amount of FPR required and in a better utilization of the materials employed. A preliminary theoretical study was carried out to investigate the effect of Young’s modulus, failure strain, and thickness of the element to be used as a spacer in order to determine the best possible candidate material. Three tests on 2.5-m-long beams were carried out, and different anchorage techniques were used to try and prevent the debonding of the strengthening system. The results from this pilot study are very promising, as the strengthening system ensures an adequate initial stiffness along with an improved ultimate flexural capacity. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 44, No. 3, pp. 403–416, May–June, 2008.     

Baryons as solitons and mass formulae

It is shown that the Wess-Zumino term gives the right quantum numbers for the baryons, which appear as solitons in current algebra lagrangians. In these models, the mass formulae for the baryons are derived.     

Interactions between a rectangular cylinder and a free-surface flow

The salient features of the interaction between a free-surface flow and a cylinder of rectangular cross-section are investigated and discussed. Laboratory-scale experiments are performed in a water channel under various flow conditions and elevations of the cylinder above the channel floor. The flow field is characterized on the basis of time-averaged and fluctuating local velocity measurements. Dynamic loadings on the cylinder are measured by two water-insulated dynamometers placed inside the cylinder structure. Starting from frequency and spectral analyses of the force signals, insights on the relationship between force dominant frequencies and the Strouhal number of the vortex shedding phenomenon are provided. Experimental results highlight the strong influence of the asymmetric configuration imposed by the two different boundary conditions (free surface and channel floor) on (i) the mean force coefficients and (ii) the vortex shedding frequencies. We provide an analysis of the nature of the dependence of average force coefficients on relevant dimensionless groups, i.e., the Reynolds number, normalized flow depth and cylinder submersion.     

Retinol modulates site-specific mobility of apo-cellular retinol-binding protein to promote ligand binding

A fundamental question in protein science is how the inherent dynamics of a protein influence its function. If this function involves interactions with a ligand, the protein-ligand encounter has the potential to modulate the protein dynamics. This study reveals how site-specific mobility can be modulated by the ligand to facilitate high affinity binding. We have investigated the mechanism of retinol uptake by the cellular retinol-binding protein type I (CRBP) using line shape analysis of NMR signals. The highly similar structures of apo- and holo-CRBP exhibit closed conformations that seemingly offer no access to ligand, yet the protein binds retinol rapidly and with high affinity. NMR line shape analysis reveals how protein dynamics resolve this apparent paradox. An initial nonspecific encounter with the ligand induces the formation of long-lived conformers in the portal region of CRBP suggesting a mechanism how retinol accesses the cavity.