Investigation of Ethacrynic Acid and Random-methyl-β-cyclodextrin Binary Complexes

Cyclodextrin complexation was applied to achieve better aqueous solubility of the drug and to formulate suppositories. Binary products were prepared in several mole ratios by two different methods. The dissolution profiles and in vitro membrane diffusion behaviour of the compositions were investigated. Thermoanalytical studies were performed in order to confirm inclusion complex formation. Compositions were selected for further detailed investigations and for incorporation into suppository dosage form.     

Single item lot-sizing problem for a warm/cold process with immediate lost sales

We consider the dynamic lot-sizing problem with finite capacity and possible lost sales for a process that could be kept warm at a unit variable cost for the next period t + 1 only if more than a threshold value Q_t has been produced and would be cold, otherwise. Production with a cold process incurs a fixed positive setup cost, K_t and setup time, S_t, which may be positive. Setup costs and times for a warm process are negligible. We develop a dynamic programming formulation of the problem, establish theoretical results on the structure of the optimal production plan in the presence of zero and positive setup times with Wagner–Whitin-type cost structures. We also show that the solution to the dynamic lot-sizing problem with lost sales are generated from the full commitment production series improved via lost sales decisions in the presence of a warm/cold process.     

The role of vibrations in thermodynamic properties of Cu-Ni alloys

We report results of a systematic study for vibrational thermodynamic functions of Cu-Ni alloys, in the harmonic approximation, using interaction potentials based on the embedded atom method with improved optimization techniques. The vibrational density of states of the systems is calculated using real space Green’s function method. From an investigation of local force fields we found that increasing Ni concentration in the alloy substantially stiffens the force experienced by Cu atoms compared to that of Ni atoms. Our calculations also reveal that vibrational entropy change between ordered and disordered crystals of Cu-Ni is negligible. However, the mixing entropy of the phonons and electronic states is found to be negative and favors un-mixing, and thus contributes to the miscibility gap.     

Hydration thermodynamic properties of amino acid analogues: a systematic comparison of biomolecular force fields and water models

We present an extensive study on hydration thermodynamic properties of analogues of 13 amino acid side chains at 298 K and 1 atm. The hydration free energies DeltaG, entropies DeltaS, enthalpies DeltaH, and heat capacities Deltac(P)() were determined for 10 combinations of force fields and water models. The statistical sampling was extended such that precisions of 0.3, 0.8, 0.8 kJ/mol and 25 J/(mol K) were reached for DeltaG, TDeltaS, DeltaH, and Deltac(P)(), respectively. The three force fields used in this study are AMBER99, GROMOS 53A6, and OPLS-AA; the five water models are SPC, SPC/E, TIP3P, TIP4P, and TIP4P-Ew. We found that the choice of water model strongly influences the accuracy of the calculated hydration entropies, enthalpies, and heat capacities, while differences in accuracy between the force fields are small. On the basis of an analysis of the hydrophobic analogues of the amino acid side chains, we discuss what properties of the water models are responsible for the observed discrepancies between computed and experimental values. The SPC/E water model performs best with all three biomolecular force fields.     

Sol–gel synthesized vanadium doped TiO2 photocatalyst: physicochemical properties and visible light photocatalytic studies

Vanadium doped titanium dioxide (V–TiO₂) photocatalyst was synthesized by the sol–gel method using ammonium vanadate as vanadium source. The prepared samples were characterized by XRD, N₂ adsorption–desorption method, UV–Vis DRS, Fourier transform infrared (FTIR), scanning electron microscope–energy dispersive X-ray and photoluminescence (PL) analysis. The results show that V⁵⁺ ions were successfully incorporated into the crystal lattice of TiO₂ as a consequence, not only an obvious decrease in the band gap and a red shift of the absorption threshold into the visible light region was recorded for the V modified TiO₂, but, also a decrease in photogenerated electrons and holes recombination rate was observed as demonstrated by PL analysis. FTIR study indicated that in undoped TiO₂ sample the acetate group favored a bidentate bridging mode of binding with titanium atoms, whereas a bidentate chelating mode of linkage was observed in V–TiO₂ powders. The crystallite size of the samples calcined at 300 and 500 °C were decreased beyond the molar ratio of 200:1 (V:Ti), this may be due to dopant presence in the grain boundaries hindering the crystal growth. The photocatalytic activities for both pure and vanadium doped TiO₂ powders were tested in the discoloration of a reactive dyestuff, methylene blue, under visible light. The 100:1 (V:Ti) doped photocatalyst, calcined at 300 °C showed enhanced photocatalytic activity under visible light with a rate constant (k_obs) of 5.024 × 10^?3 min^?1 which is nearly five times higher than that of pure TiO₂, as result of low band gap value, high specific surface area and a decrease in recombination rate.     

Competing adsorption between hydrated peptides and water onto metal surfaces: from electronic to conformational properties

Inorganic-(bio)organic interfaces are of central importance in many fields of current research. Theoretical and computational tools face the difficult problem of the different time and length scales that are involved and linked in a nontrivial way. In this work, a recently proposed hierarchical quantum-classical scale-bridging approach is further developed to study large flexible molecules. The approach is then applied to study the adsorption of oligopeptides on a hydrophilic Pt(111) surface under complete wetting conditions. We examine histidine sequences, which are well known for their binding affinity to metal surfaces. Based on a comparison with phenylalanine, which binds as strong as histidine under high vacuum conditions but, as we show, has no surface affinity under wet conditions, we illustrate the mediating effects of near-surface water molecules. These contribute significantly to the mechanism and strength of peptide binding. In addition to providing physical-chemical insights in the mechanism of surface binding, our computational approach provides future opportunities for surface-specific sequence design.     

Working group report: Heavy-ion physics and quark-gluon plasma

This is the report of Heavy Ion Physics and Quark-Gluon Plasma at WHEPP-09 which was part of Working Group-4. Discussion and work on some aspects of quark-gluon plasma believed to have created in heavy-ion collisions and in early Universe are reported.     

Two-Dimensional Geometry Control of Graphene Nanoflakes Produced by Thermal Plasma for Catalyst Applications

The control of nanoparticle synthesis using thermal plasmas is difficult and often leads to problems of chemical and structural purity, and poor process robustness in terms of consistency of product from run to run. Good reactor design allowed to overcome these issues and to develop a new material based on graphene with a flake-like structure (labeled graphene nanoflakes, GNF) supporting nitrogen for catalytic applications, for example as platinum replacement in fuel cells. These structures showed not only to be active, but also stable in polymer electrolyte fuel cell operation. Characterization of these structures, in situ fuel cell studies and modeling analysis all indicate that achievement of stability relates on the crystalline two-dimensional graphene structure. This paper first reviews the basic aspects behind the structural objectives, describes the synthesis process design leading to this crystalline structure, and provides a two-dimensional analysis on the graphitic growth based on fundamental theory and CFD calculations. These calculations indicate that an independent control of the graphene structure thickness (number of atomic planes) and sheet lengths is possible in a thermal plasma reactor.     

The EPR spectrum of triplet excitions in crystalline pyrene

The room temperature EPR spectrum of triplet excitions in crystalline pyrene has been studied. Spin hamiltonian parameters have been obtained and from these the molecular fine structure constants are deduced assuming only monomeric sites. The correspondence between the latter and the directly measured values is taken to imply the absence of an excimeric contribution to the triplet exciton state.