Static and Kinetic Studies on the Adsorption Behavior of Sulfadiazene

To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10^–3 mol cm^–3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl^–, SO^2– ₄ and PO^3– ₄ (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.     

Theoretical insight of nitric oxide adsorption on neutral and charged Pdn (n = 1–5) clusters

Density functional theory (DFT) calculations within the framework of generalized gradient approximation have been used to systematically investigate the adsorption of nitric oxide (NO) molecule on neutral, cationic, and anionic Pd_n (n = 1–5) clusters. NO coordinate to one Pd atom of the cluster by the end‐on mode, where the tilted end‐on structure is more favorable due to the additional electron in the π* orbital. On the contrary, in the neutral and cationic Pd₂ system, NO coordinates to the bridge site of cluster preferably by the side‐on mode. Charge transfer between Pd clusters and NO molecule and the corresponding weakening of N? O bond is an essential factor for the adsorption. The N? O stretching frequency follow the order of cationic > neutral > anionic. Binding energy of NO on anionic clusters is found to be greater than those of neutral and cationic clusters. © 2015 Wiley Periodicals, Inc.     

Sensing of Phosphates by Using Luminescent EuIII and TbIII Complexes: Application to the Microalgal Cell Chlorella vulgaris

Phenanthroline‐based chiral ligands L¹ and L² as well as the corresponding Eu^III and Tb^III complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F^?, Cl^?, Br^?, I^?, NO₃^?, NO₂^?, HPO₄^2?, HSO₄^?, CH₃COO^?, and HCO₃^?. Among the anions, HPO₄^2? exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties.     

Photopolymerization initiated by charge-transfer complex. I. Photopolymerization of methylmethacrylate with the use of quinaldine-bromine and lutidine–bromine charge-transfer complexes as photoinitiator

Photopolymerization of MMA was carried out with quinaldine–bromine (QN–Br₂) and lutidine–bromine (LU–Br₂) charge-transfer complexes as initiators. The rate of polymerization R_p increased with rising monomer concentration and the monomer exponent was computed as unity. At first the rate of polymerization accelerated and then reduced as the initiator concentration was increased. The initiator exponent was 0.5. The reaction was carried out at three different temperatures and overall activation energy was calculated at 4.0 kcal/mol. The kinetic data and other evidence indicate that the overall polymerization takes place in a radical mechanism. A suitable mechanism is suggested.     

Molecular structural investigations of quinoxaline derivatives through 3D-QSAR,molecular docking,ADME prediction and pharmacophore modeling studies for the search of novel antimalarial agent

In the present article, a dataset of 63 quinoxaline derivatives were taken for antimalarial activity and pharmacophore were developed. Atom based method was used to develop a three dimensional quantitative structure activity relationship (3D-QSAR) model. On comparison of all statistical parameters, model AHRRR23 was found to be the most effective and predictive QSAR model as it satisfied all statistical parameters of a good model. The model AHRRR23 showed an adequate R² value for the training set 0.9446, good predictive power with Q² of 0.6409, good F- value, low SD 0.1218 value and outstanding Pearson-R values and low RMSE 0.2779 values of the model. The docking studies also gives very good results with good RMSD values. 3D QSAR, docking and ADME studies exhibits that the developed model could be employed as a potential lead for further study as antimalarial drug.     

An ab initio study of water clusters in gas phase and bulk aqueous media: (H2O)n,n=1–12

Geometries of several clusters of water molecules including single minimum energy structures of n‐mers (n=1–5), several hexamers and two structures of each of heptamer to decamer derived from hexamer cage and hexamer prism were optimized. One structural form of each of 11‐mer and 12‐mer were also studied. The geometry optimization calculations were performed at the RHF/6‐311G* level for all the cases and at the MP2/6‐311++G** level for some selected cases. The optimized cluster geometries were used to calculate total energies of the clusters in gas phase employing the B3LYP density functional method and the 6‐311G* basis set. Frequency analysis was carried out in all the cases to ensure that the optimized geometries corresponded to total energy minima. Zero‐point and thermal free energy corrections were applied for comparison of energies of certain hexamers. The optimized cluster geometries were used to solvate the clusters in bulk water using the polarized continuum model (PCM) of the self‐consistent reaction field (SCRF) theory, the 6‐311G* basis set, and the B3LYP density functional method. For the cases for which MP2/6‐311++G** geometry optimization was performed, solvation calculations in water were also carried out using the B3LYP density functional method, the 6‐311++G** basis set, and the PCM model of SCRF theory, besides the corresponding gas‐phase calculations. It is found that the cage form of water hexamer cluster is most stable in gas phase among the different hexamers, which is in agreement with the earlier theoretical and experimental results. Further, use of a newly defined relative population index (RPI) in terms of successive total energy differences per water molecule for different cluster sizes suggests that stabilities of trimers, hexamers, and nonamers in gas phase and those of hexamers and nonamers in bulk water would be favored while those of pentamer and decamer in both the phases would be relatively disfavored. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 81: 90–104, 2001     

Further study of alternating iterations for rectangular matrices

Theory of matrix splittings is a useful tool in the analysis of iterative methods for solving systems of linear equations. When two splittings are given, it is of interest to compare the spectral radii of the corresponding iteration matrices. This helps to arrive at the conclusion that which splitting should one choose so that one can reach the desired solution of accuracy or the exact solution in a faster way. In the case of many splittings are provided, the comparison of the spectral radii is time-consuming. Such a situation can be overcome by introducing another iteration scheme which converges to the same solution of interest in a much faster way. In this direction, the theory of alternating iterations for real rectangular matrices is recently proposed. In this note, some more results to the theory of alternating iterations are added. A comparison result of two different alternating iteration schemes is then presented which will help us to choose the iteration scheme that will guarantee the faster convergence of the alternating iteration scheme. In addition to these results, a comparison result for proper weak regular splittings is also obtained.     

On‐Surface Synthesis of Cumulene‐Containing Polymers via Two‐Step Dehalogenative Homocoupling of Dibromomethylene‐Functionalized Tribenzoazulene

Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. Here we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C?C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on‐surface synthesis of cumulene‐containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces.