Rhodium(I) derivatives of diethylbispyrazolylborate

Bis-substituted rhodium(I) polypyrazolylborates of the type L₂RhBPz₂Et₂ (L = CO or RNC where R = p-CH₃C₆H₄, t-C₄H₉ or p-CH₃C₆H₄SO₂CH₂) have been prepared and characterized and hence the analogous rhodium(III) derivatives by oxidative addition reactions with iodine, iodomethane, or mercury(II) chloride.     

Attractions, water structure, and thermodynamics of hydrophobic polymer collapse

We explore the prospects of a perturbation approach for predicting how weak attractive interactions affect collapse thermodynamics of hydrophobic polymers in water. Specifically, using molecular dynamics simulations of model polymers in explicit water, we show that the hydration structure is sensitive to the strength of the van der Waals attractions but that the hydration contribution to the potential of mean force for collapse is not. We discuss how perturbation theory ideas developed for small spherical apolar solutes need to be modified in order to account for the effect of attractions on the conformational equilibria of polymers.     

Lattice dynamics of ND4I and NH4I crystals

The phonon dispersion curves and one phonon density of states for ND₄I and NH₄I crystals in the sodium chloride structure have been calculated by making use of the deformation dipole model of Hardy incorporating general short range forces out to second neighbours. Since the electronic configuration of both the compounds is identical, we have used the input data of NH₄I to calculate the model parameters for both the crystals. The results have been compared in the three principal symmetry directions with the neutron scattering measurements available only in case of ND₄I. The theoretical results show a reasonably good agreement with the experimental data.     

A 10000 particle molecular dynamics model with long range forces

A technique is described for the computer simulation of the motion of 10000 simulated molecules. The number of computer operations per time-step is proportional to the number of simulated particles even though the force of interaction may be long range and no force cut-off is employed.     

Retailer’s optimal replenishment decisions with credit-linked demand under permissible delay in payments

Usually it is assumed that the supplier would offer a fixed credit period to the retailer but the retailer in turn would not offer any credit period to its customers, which is unrealistic, because in real practice retailer might offer a credit period to its customers in order to stimulate his own demand. Moreover, it is observed that credit period offered by the retailer to its customers has a positive impact on demand of an item but the impact of credit period on demand has received a very little attention by the researchers. To incorporate this phenomenon, we assume that demand is linked to credit period offered by the retailer to the customers.     

Mechanistic study of the oxidation of <Emphasis Type="SmallCaps">l</Emphasis>-phenylalanine by hexacyanoferrate(III) catalyzed by iridium(III) in aqueous alkaline medium

The oxidation of l-phenylalanine by hexacyanoferrate(III) (abbreviated as HCF) catalyzed by Ir(III) has been studied spectrophotometrically at 35 °C and at a constant ionic strength of 0.50 mol dm⁻³. The main oxidation product was identified as phenylpyruvic acid by physico-chemical and spectroscopic methods. The stoichiometry was found to be 2:1, i.e. 2 mol of hexacyanoferrate(III) reacted with 1 mol of phenylalanine. The reaction was first order with respect to both HCF and alkali concentration. The order with respect to [Phe] changed from first to zero as the concentration was increased. The effect of ionic strength was also investigated. Thermodynamic parameters were evaluated by studying the reaction at four different temperatures between 35 and 50 °C. Based on the experimental results, a suitable mechanism involving complex formation has been proposed.     

Density functional studies of LiN and LiN+ (N = 2–30) clusters: Structure,binding and charge distribution

Density functional calculations using B3LYP/6‐311G method have been carried out for small to medium‐sized lithium clusters (Li_N, N = 2–30). The optimized geometries of neutral and singly charged clusters, their binding energies, ionization potential, electron affinity, chemical potential, softness, hardness, highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO–LUMO) gap, and static dipole polarizability have been investigated systematically. In addition, we study the distribution of partial charges in detail using natural population analysis (NPA) in small‐sized clusters (Li_N, N = 2–10), both neutral and cationic, and demonstrate the correlation between symmetry and charge. Uniform distribution of charges in cationic clusters confirms them to be energetically more favorable than the neutral counterparts. Whenever possible, results have been compared with available data. An excellent agreement in every case supports new results as reliable predictions. A careful study of optimized geometries shows that Li₉ is derivable from bulk Li structure, i.e., body centered cubic cell, and higher clusters have optimized shapes derived from this. Further, the turnover form two to three dimensional structure occurs at cluster size N = 6. The quantity α^1/3 (α = polarizability) per atom is found to be broadly proportional to softness (per atom) as well as inverse ionization potential (per atom). The present work forms a sound basis for further study of large‐sized clusters as well as other atomic clusters. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Synthesis and characterization of poly (indene‐co‐pyrrole) nanofibers

Nanofibers of poly (indene‐co‐pyrrole) (CInPy) have been synthesized, using a facile chemical oxidative polymerization reaction. The effect of copolymerization was examined in view of the individually synthesized homopolymer nanostructures of polyindene (PIn) and polypyrrole (PPy). Morphological details of CInPy, studied using scanning electron microscopy (SEM) and transmission electron microscopy, (TEM) reveal the appearance of dense cottony mess, comprising of fine fibers with an average diameter of 5–10 nm. Chemical structural analysis of CInPy, conducted using ultraviolet‐visible (UV‐Vis), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR) spectroscopic techniques, reveals that both PIn and PPy are involved in the formation of copolymer organization. Fluorescence properties of nanosized copolymer are observed in the blue region, with emission λ_max placed at 395 nm. Conductivity of copolymer nanofibers (2.4 × 10^?3 S/cm) is consistent with the morphology and thermal stability properties of integral homo‐polymers. Improved thermal stability and processability along with the enhanced optical and electrical properties of copolymer nanostructures outfit it as a better promising material in optoelectronic and light emitting nanodevices, with reference to nanosized PIn and PPy. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and characterization of polypyrrole nanofibers with different dopants

Nanostructures of polypyrrole (PPy) were synthesized in the presence of different dopants including hydrochloric acid (HCl), ferric chloride (FeCl₃), p‐toluene sulfonic acid (p‐TSA), camphor sulfonic acid (CSA), and polystyrene sulfonic acid (PSSA), using a simple interfacial oxidative polymerization method. The method is a reliable non‐template approach with relatively simple instrumentation, ease of synthesis, and economic viability for synthesizing PPy nanostructures. Morphology of synthesized PPy structures was investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which indicate the formation of one‐dimensional (1D) nanofibers with average diameter of 75–180 nm. Energy dispersive spectrum (EDS) of the PPy nanofibers indicates the attachment of the dopants to the PPy backbone; the fact is further confirmed by the Fourier transform infrared (FTIR) spectra of PPy nanostructures. Thermal stabilities of the nanostructures explored using thermal gravimetric analysis (TGA) follow the order PPy‐p‐TSA > CSA > HCl > FeCl₃ > PSSA. It is noticed that the electrical conductivity (EC) of PPy nanostructures depends upon the nature of dopant (PPy‐p‐TSA > CSA > HCl > FeCl₃ > PSSA), PPy‐p‐TSA nanofibers showing the highest EC of 6 × 10^?2 Scm^?1. Copyright © 2009 John Wiley & Sons, Ltd.     

An analytic framework to develop policies for testing, prevention, and treatment of two-stage contagious diseases

In this paper we consider healthcare policy issues for trading off resources in testing, prevention, and cure of two-stage contagious diseases. An individual that has contracted the two-stage contagious disease will initially show no symptoms of the disease but is capable of spreading it. If the initial stages are not detected which could lead to complications eventually, then symptoms start appearing in the latter stage when it would be necessary to perform expensive treatment. Under a constrained budget situation, policymakers are faced with the decision of how to allocate budget for prevention (via vaccinations), subsidizing treatment, and examination to detect the presence of initial stages of the contagious disease. These decisions need to be performed in each period of a given time horizon. To aid this decision-making exercise, we formulate a stochastic dynamic optimal control problem with feedback which can be modeled as a Markov decision process (MDP). However, solving the MDP is computationally intractable due to the large state space as the embedded stochastic network cannot be decomposed. Hence we propose an asymptotically optimal solution based on a fluid model of the dynamics in the stochastic network. We heuristically fine-tune the asymptotically optimal solution for the non-asymptotic case, and test it extensively for several numerical cases. In particular we investigate the effect of budget, length of planning horizon, type of disease, population size, and ratio of costs on the policy for budget allocation.