Temperature and magnetic field induced structural transformation in Si-doped CeFe2: An in-field X-ray diffraction study

Using the X-ray powder diffraction technique at various temperatures and applied magnetic fields, we have studied the magnetostructural properties of Ce(Fe_0.95Si_0.05)₂. The X-ray diffraction data establish quantitative relationships between bulk magnetization and the evolution of structurally distinct phases with magnetic field and temperature, and confirm the distinct features of a first-order phase transition such as supercooling and superheating, metastability, and phase co-existence of different structural polymorphs. We observe the lattice volume mismatch across the structural phase transition, which appears to be the cause for the step behavior of the magnetization isotherms at low temperatures. The present study shows that the lattice distortion has to be treated explicitly, like spin, along with the effects of lattice–spin coupling to account for the magnetization behavior of this system. This structure template can resolve the issue of kinetics in this material as observed in different time scale measurements and with different experimental protocols.     

Structural,electrical, magnetic,elastic and anelastic behaviour of Nd0.6Ca0.4MnO3

With a view to understanding the structural, electrical and magnetic, elastic and anelastic behaviour of charge ordered Nd_0.6Ca_0.4MnO₃, systematic investigations were undertaken. The sample was synthesized by a sol–gel route. The sample was characterized by X-ray diffraction (XRD) using a Rietveld refinement technique and was found to have orthorhombic structure with space group Pnma. A study on the variation of electrical resistivity with temperature has been carried out in the range 100–300 K and it was found to exhibit a field induced transition. The ac susceptibility studies show two transition temperatures, which are attributed to charge ordering and a Néel transition. Internal friction and longitudinal modulus studies were carried out using the composite oscillator technique. An effort has been made to explain the observed anomalous behaviour by a qualitative model.     

Preferential mode of cyclization of tetrahydrofuran amino acids containing peptides: some theoretical insights

Theoretical insights have been provided for the observed preference of cyclodimerization over intramolecular cyclization reactions in linear tripeptides containing “2,5‐cis” (2S,5R)‐tetrahydrofuran amino acid as well as in those containing “2,5‐trans” (2S,5S)‐tetrahydrofuran amino acid, using quantum chemical methods. The geometries of species involved as well as the feasibility of cyclization reactions are studied at the B3LYP/6‐31G(d,p) level of theory in gas phase as well as in solvent phase. Thermodynamic data from Hessian calculations favor the intermolecular cyclization. Analysis of optimized geometries reveals the existence of additional stabilizing hydrogen bonding interactions in intermolecularly cyclized products. The existence of these second‐order interactions is substantiated by topological (atoms in molecules (AIM)) and natural bond orbital (NBO) analyses. Such interactions are absent in the intramolecular cyclization products. Further justification for the presence of stabilizing interactions in intermolecularly cyclized products comes from the molecular electrostatic potentials and electron density surfaces. Kinetic control favoring the intermolecularly cyclized products due to additional entropy of activation in the intramolecular case is surmised. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies on the adsorption of arsenic on calix[6]arene

p‐tert‐butyl calix[6]arene (PTC6) was synthesized and characterized by solid‐ and liquid‐state NMR and LC‐MS techniques. The adsorption of arsenite and arsenate on calix[6]arene under different pH conditions and adsorbate doses was studied. The maximum adsorption of arsenic species on calix[6]arene was observed around neutral pH and the adsorption density of As (III) was higher than that of As (V). The adsorption of neutral H₃AsO₃ and negatively charged H₂AsO molecules on calix[6]arene was attributed to the condensation reaction between hydroxyl groups of PTC6 and arsenic species. The complexation of arsenite with phenolic oxygen was confirmed by solid‐state ¹³C NMR CP‐MAS. Exo attack mechanism was proposed to describe the interaction of arsenous and arsenic acid molecules with PTC6. The specific interaction between calix[6]arene and arsenic species was further substantiated by zeta‐potential (ζ‐potential) measurements and free energy of adsorption. The free energy of adsorption ( ) estimated from Stern–Grahame equation was found to be 25 kJ/mole for As (III) and 19 kJ/mole for As (V). Copyright © 2010 John Wiley & Sons, Ltd.     

Metal-Organic Frameworks for Hydrogen Energy Applications: Advances and Challenges

Hydrogen is in limelight as an environmental benign alternative to fossil fuels from few decades. To bring the concept of hydrogen economy from academic labs to real world certain challenges need to be addressed in the areas of hydrogen production, storage, and its use in fuel cells. Crystalline metal-organic frameworks (MOFs) with unprecedented surface areas are considered as potential materials for addressing the challenges in each of these three areas. MOFs combine the diverse chemistry of molecular linkers with their ability to coordinate to metal ions and clusters. The unabated flurry of research using MOFs in the context of hydrogen energy related activities in the past decade demonstrates the versatility of this class of materials. In the present review, we discuss major strategical advances that have taken place in the field of “hydrogen economy and MOFs” and point out issues requiring further attention.     

An Eco‐friendly Catalytic System for One‐pot Multicomponent Synthesis of Diverse and Densely Functionalized Pyranopyrazole and Benzochromene Derivatives

An external base‐free, efficient, cost‐effective, and environmentally benign protocol has been developed for the one‐pot multicomponent synthesis of highly functionalized pyranopyrazoles and benzochromenes using water extract of Agave americana (century plant) leaf ash, a waste‐derived catalyst, at room temperature. Mild reaction conditions, high yield, easy isolation of products, eco‐friendly standards, and no chromatographic separation are the salient features of this protocol.     

Synthesis,spectral characterization,and biological evaluation of imidazole‐substituted pyridine‐2‐amine and benzo‐substituted imidazole‐2‐amine

A series of new imidazole‐substituted pyridine‐2‐amine and benzo‐substituted imidazol‐2‐amine 3 – 12 were synthesized by treating various amines 1(a – d) with alkyl/aryl isothiocyanate 2(a‐c) at 60–90°C in isopropyl alcohol without using any catalyst with high yields. The structures of all the newly synthesized compounds were characterized using IR, NMR (¹H, ¹³C), mass, and elemental analyses. All the newly synthesized compounds were screened for their in vitro antioxidant and antimicrobial activities to understand their biological potency. All the title compounds exhibited good antioxidant and antimicrobial activities in vitro when compared to the standard drugs.     

Poly(urethane–urea) based on functionalized polystyrene with HMDI: Synthesis and characterization

The poly(urethane–urea) (PUU) based on α, Ω, hydroxy terminated polystyrene (OH-PSt-OH), 1,6-hexamethylene diisocyanate (HMDI) and three different diamines (1,2-ethylenediamine (EDA), 1,4-butanediamine (BDA), 1,6-hexamethylene diamine (HMDA)) is prepared by a melt polymerization method. The length of the soft segment is varying from 2000 to 8900 g/mol using HMDI as a chain extender. The inherent viscosity of the polymer is found to be in the range of 0.36–2.0 dL/g suggesting that the polymer is of high molecular weight. FT-IR results conclude that the urea groups form both monodendate and bidendate assemblies. Temperature dependent FT-IR and WAXS data confirm that the crystallinity of the copolymer is very high and depends on the spacer length. DSC data show the peaks for Tg of soft and Tm of hard segments. Depending on the concentration and the type of hard segments, melting temperature of the polymers was varied from 142 °C to 266 °C. The solubility of the polymer in chloroform is depending on the concentration of the hard segment. The TGA data reveal that the polymer shows single stage decomposition cantered around 413 °C.     

Modelling the effects of nitrogen doping on the carbon nanofiber growth via catalytic plasma‐enhanced chemical vapour deposition process

An analytical model is developed to describe the effects of nitrogen doping on the growth of the carbon nanofibers (CNFs) and to elucidate the growth mechanism of nitrogen‐contained carbon nanofibers (N‐CNFs) on the catalyst substrate surface through the plasma‐enhanced chemical vapour deposition (PECVD) process. The analytical model accounts for the charging of CNFs, kinetics of all plasma species (electrons, ions, and neutrals) in the reactive plasma, generation of carbon species on the catalyst nanoparticle surface due to dissociation of hydrocarbons, CNF growth due to diffusion and precipitation of carbon species, and various other processes. First‐order differential equations have been solved for glow discharge plasma parameters for undoped CNFs (CNF growth in C₂H₂/H₂ plasma) and nitrogen‐doped CNFs (N‐CNF growth in C₂H₂/NH₃ plasma). Our investigation found that nitrogen‐doped CNFs exhibit lower tip diameters and smaller heights compared to the undoped CNFs. In addition, we have estimated that nitrogen‐doped CNFs have more enhanced field emission characteristics than the undoped CNFs. Moreover, we have also observed that N‐CNFs' growth rate increases and tip diameter decreases as the C₂H₂/NH₃ gas ratio decreases. The theoretical results of the present investigation are consistent with the existing experimental observations.