Synthesis and Molecular Structure Investigation by DFT and X-Ray Diffraction of ARNO

Abstract  

We report here the synthesis of (Z)-5-(4-nitrobenzyliden)-3-N(2-ethoxyphenyl)-2-thioxo-thiazolidin-4-one (ARNO) compound. The crystal structure has been determined by X-ray diffraction. The compound crystallizes in the triclinic system with space group P[`1] P\bar{1} and cell parameters: a = 9.1289(19), b = 9.3717(7), c = 12.136(3) ?, α = 102.133(11)°, β = 90.99(2)°, γ = 117.165(9)°, V = 895.4(3) ?³ and Z = 2. The structure has been refined to a final R = 0.05 for 2591 observed reflections. The refined structure was found to be significantly non planar. The molecule exhibits intermolecular hydrogen bond of type C–H⋯O and C–H⋯S. ab initio calculations were also were performed at Hartree–Fock and density functional theory levels. The full HF and DFT geometry optimization was carried out using LANL2DZ, 6-31G* and B3LYP/6-31+G** basis sets. The optimized geometry of the title compound was found to be consistent structure determined by X-ray diffraction. The minimum energy of geometrical structure is obtained by using level HF/LANL2DZ basis sets.     

Qualitative possibilistic influence diagrams based on qualitative possibilistic utilities

This paper proposes a new approach for decision making under uncertainty based on influence diagrams and possibility theory. The so-called qualitative possibilistic influence diagrams extend standard influence diagrams in order to avoid difficulties attached to the specification of both probability distributions relative to chance nodes and utilities relative to value nodes. In fact, generally, it is easier for experts to quantify dependencies between chance nodes qualitatively via possibility distributions and to provide a preferential relation between different consequences. In such a case, the possibility theory offers a suitable modeling framework. Different combinations of the quantification between chance and utility nodes offer several kinds of possibilistic influence diagrams. This paper focuses on qualitative ones and proposes an indirect evaluation method based on their transformation into possibilistic networks. The proposed approach is implemented via a possibilistic influence diagram toolbox (PIDT).     

Ultraviolet-B radiation effects on the structure and function of lower trophic levels of the marine planktonic food web

The impact of UV-B radiation (UVBR; 280-320 nm) on lower levels of a natural plankton assemblage (bacteria, phytoplankton and microzooplankton) from the St. Lawrence Estuary was studied during 9 days using several immersed outdoor mesocosms. Two exposure treatments were used in triplicate mesocosms: natural UVBR (N treatment, considered as the control treatment) and lamp-enhanced UVBR (H treatment, simulating 60% depletion of the ozone layer). A phytoplankton bloom developed after day 3, but no significant differences were found between treatments during the entire experiment for phytoplankton biomass (chlorophyll a and cell carbon) nor for phytoplankton cell abundances from flow cytometry and optical microscopy of three phytoplankton size classes (picoplankton, nanoplankton and microplankton). In contrast, bacterial abundances showed significantly higher values in the H treatment, attributed to a decrease in predation pressure due to a dramatic reduction in ciliate biomass (approximately 70-80%) in the H treatment relative to the N treatment. The most abundant ciliate species were Strombidinium sp., Prorodon ovum and Tintinnopsis sp.; all showed significantly lower abundances under the H treatment. P. ovum was the less-affected species (50% reduction in the H treatment compared with that of the N control), contrasting with approximately 90% for the other ones. Total specific phytoplanktonic and bacterial production were not affected by enhanced UVBR. However, both the ratio of primary to bacterial biomass and production decreased markedly under the H treatment. In contrast, the ratio of phytoplankton to bacterial plus ciliate carbon biomass showed an opposite trend than the previous results, with higher values in the H treatment at the end of the experiment. These results are explained by the changes in the ciliate biomass and suggest that UVBR can alter the structure of the lower levels of the planktonic community by selectively affecting key species. On the other hand, linearity between particulate organic carbon (POC) and estimated planktonic carbon was lost during the postbloom period in both treatments. On the basis of previous studies, our results can be attributed to the aggregation of carbon released by cells to the water column in the form of transparent exopolymer particles (TEPs) under nutrient limiting conditions. Unexpectedly, POC during such a period was higher in the H treatment than in controls. We hypothesize a decrease in the ingestion of TEPs by ciliates, in coincidence with increased DOC release by phytoplankton cells under enhanced UVBR. The consequences of such results for the carbon cycle in the ocean are discussed.     

Modeling high-pressure adsorption of gas mixtures on activated carbon and coal using a simplified local-density model

The simplified local-density (SLD) theory was investigated regarding its ability to provide accurate representations and predictions of high-pressure supercritical adsorption isotherms encountered in coalbed methane (CBM) recovery and CO2 sequestration. Attention was focused on the ability of the SLD theory to predict mixed-gas adsorption solely on the basis of information from pure gas isotherms using a modified Peng-Robinson (PR) equation of state (EOS). An extensive set of high-pressure adsorption measurements was used in this evaluation. These measurements included pure and binary mixture adsorption measurements for several gas compositions up to 14 MPa for Calgon F-400 activated carbon and three water-moistened coals. Also included were ternary measurements for the activated carbon and one coal. For the adsorption of methane, nitrogen, and CO2 on dry activated carbon, the SLD-PR can predict the component mixture adsorption within about 2.2 times the experimental uncertainty on average solely on the basis of pure-component adsorption isotherms. For the adsorption of methane, nitrogen, and CO2 on two of the three wet coals, the SLD-PR model can predict the component adsorption within the experimental uncertainties on average for all feed fractions (nominally molar compositions of 20/80, 40/60, 60/40, and 80/20) of the three binary gas mixture combinations, although predictions for some specific feed fractions are outside of their experimental uncertainties.     

Spectrophotometric determination of acyclovir and ribavirin in their dosage forms

Two simple, accurate, and reliable spectrophotometric methods have been developed for the determination of 2 antiviral drugs, acyclovir (ACV) and ribavirin (RBV), in their pharmaceutical formulations. These methods are based on oxidation of the 2 drugs with either cerium (IV) ammonium sulfate (Method A) or potassium persulfate (Method B). The products of oxidation in both methods are coupled with 3-methylbenzothiazolin 2-one hydrazone, producing a deep blue color with a maximum absorption wavelength at 630 nm. In Method A, the absorbance-concentration plots were linear over the ranges of 5-50 and 10-60 microg/mL with detection limits of 0.18 microg/mL (8 x 10(-7) M) and 0.63 microg/mL (2.58 x 10(-6) M) for ACV and RBV, respectively. In Method B, the ranges were 5-45 and 20-50 microg/mL with detection limits of 0.11 microg/mL (4.88 x 10(-7) M) and 1.40 microg/mL (5.73 x 10(-6) M) for the 2 drugs, respectively. The molar absorptivities were 4.1 x 10(3) and 3.65 x 10(3) L/mol/cm in Method A and 5.03 x 10(3) and 3.97 x 10(3) L/mol/cm in Method B for the 2 drugs, respectively. The proposed methods were applied successfully for the determination of the 2 drugs in their pharmaceutical formulations. The percentage recoveries +/- standard deviation were 99.57 +/- 0.86 and 100.82 +/- 0.46 for ACV; 99.41 +/- 1.08 and 100.35 +/- 1.03 for RBV. The results obtained were compared statistically with those given by official methods and showed no significant differences regarding accuracy and precision.     

An efficient quantitative ultrasonic elastography based on variational h-refinement

Quantitative elastography is a method to visualise a stiffness distribution. It is motivated by the observation that changes in mechanical properties of soft tissue mostly include important diagnostic information. With an ultrasound–elastography system, the displacement field can be calculated from the pre– and post–deformation image. Using the assumption that the material is elastic, isotropic and nearly incompressible, the distribution of shear modulus is determined by solving an inverse problem. While common approaches use a constant mesh, a variational h–refinement is in the focus of this work. In doing so, the efficiency and accuracy of the determination can be increased. The presented results are generated by using numerical simulations. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A self-tuning guidance and control system for marine surface vessels

An integrated guidance and control system has been developed to enable underactuated marine surface vessels to operate autonomously and yield robust tracking performance in spite of significant external disturbances and modeling imprecision. A nonlinear ship model, accounting for all six degrees-of-freedom of the ship, has been used as a test bed to assess the performance of the proposed scheme. The controller combines the advantages of the variable structure systems (VSS) theory with the self-tuning fuzzy logic scheme. It does not require an accurate dynamic model of the ship or the construction of a rule-based expert system. Its asymptotic stability is ensured by knowing the upper bounds on modeling imprecision and external disturbances and by forcing the tuning parameters to satisfy the sliding conditions. The guidance system is based on the concepts of the variable radius line-of-sight (LOS) and the acceptance circle around the waypoints. The current system varies the LOS radius exponentially with the cross track error in order to achieve a fast convergence rate of the ship to its desired trajectory. The simulation results demonstrate the robust tracking characteristic of the integrated guidance and control system in spite of significant modeling uncertainties and environmental disturbances.     

Modelling of inflow-conditions for vortex particle methods to simulate atmospheric turbulence and its induced aerodynamic admittance on line-like bluff bodies

ABSTRACT

This paper presents a novel method for the simulation of aerodynamic admittance of turbulent wind on bluff line-like structures using a pseudo 3D model of Vortex Particle Method (VPM). The method is a computationally efficient extension of the 2D VPM, where a coupled set of simulation slices accounts for the 3D nature of the oncoming wind flow. Pre-computed vortex particles are seeded in each of the parallel 2D simulation slices in order to model the turbulent velocity perturbations. Here, the modelling of the inflow seeding particles is enhanced, reducing the computational cost and allowing extendibility into quasi 3D domain. This a priori computation of the seeding vortex particles is based on modelling the atmospheric turbulence characteristics. The method is applied to simulate turbulent flow around an infinitesimally thin flat-plate, to asses its validity at the viscous-rotational boundary layer, which is important for accurate fluid-structure Interaction simulations. Furthermore, sensitivity analysis to different attributes is assessed     

3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction

Three-dimensional (3D) N-doped graphene aerogel (N-GA)-supported Fe(3)O(4) nanoparticles (Fe(3)O(4)/N-GAs) as efficient cathode catalysts for the oxygen reduction reaction (ORR) are reported. The graphene hybrids exhibit an interconnected macroporous framework of graphene sheets with uniform dispersion of Fe(3)O(4) nanoparticles (NPs). In studying the effects of the carbon support on the Fe(3)O(4) NPs for the ORR, we found that Fe(3)O(4)/N-GAs show a more positive onset potential, higher cathodic density, lower H(2)O(2) yield, and higher electron transfer number for the ORR in alkaline media than Fe(3)O(4) NPs supported on N-doped carbon black or N-doped graphene sheets, highlighting the importance of the 3D macropores and high specific surface area of the GA support for improving the ORR performance. Furthermore, Fe(3)O(4)/N-GAs show better durability than the commercial Pt/C catalyst.