Facile approach to diverse range of 1,3-diaza-heterocycles: angular/linear selectivity paradigm and a remarkable intramolecular methyl migration

Starting from cyclic anhydrides and tert-butyl 2-aminobenzylcarbamate, simple and efficient synthesis of diverse range of kinetically controlled angular and thermodynamically controlled linear tricyclic and tetracyclic 1,3-diaza-heterocycles have been described via the intramolecular cyclizations of the corresponding imides/anilic acid esters. The effect of imide stability on the angular/linear product selectivity has also been described. The kinetically controlled angular products were successfully transformed to the corresponding thermodynamically controlled linear products by refluxing in methanol or methanol and acetic acid mixture. An interesting in situ 1,2-intramolecular methyl group migration has also been described.     

Bonding in the metallic molecular solid α-Gallium

ABSTRACT

Solid, liquid and alloyed phases of gallium play a role in a variety of important technological applications. While many of the gallium phases involved in these applications are metallic, some have been proposed or are known to contain covalently bound Ga dimers. Thus, understanding the nature of bonding in Ga is crucial to the development of Ga-based materials. The solid phase of gallium at ambient conditions, α-Ga, is metallic and composed of molecular dimers, and can serve as a testing ground for studying gallium bonding with electronic structure calculations. We use density functional theory-based molecular dynamics simulations in conjunction with maximally localised Wannier functions to examine the nature of chemical bonding in α-Ga. We propose a geometric criterion for defining various bonding environments, which enables the quantification of covalent and weak bonds in solid gallium. We additionally connect the bonding structure of α-Ga to its phonon density of states and discuss similarities and differences with diatomic halogen crystals.     

First order transition to oscillation death through an environment

The emergence of dynamical abrupt transitions for the first time in an ensemble of identical limit-cycle and chaotic oscillators coupled via a common environment is reported. The transition from the oscillatory state to the death state and vice versa, in these networks of oscillators are found not only discontinuous as well as irreversible in the parameter space. This first order phase transition in these systems is termed as Explosive Death. The occurrence of such transition is studied in details by using an appropriate order parameter for both limit-cycle and chaotic oscillators, in particular, Stuart–Landau and Rössler oscillators. The backward transition point for this phenomenon is obtained analytically using linear stability analysis and is found to be consistent with the numerical results.     

Single-Phase Convective Heat Transfer of Water and Aqua Ethylene Glycol Mixture in a Small-Diameter Tube

A tailor-made convective heat transfer test facility is constructed to study the single-phase convective heat transfer of deionized water and 30 vol% and 60 vol% aqua–ethylene glycol in a stainless steel tube of 4 mm in inner diameter and 1 m in length. The heat flux is varied between 1 and 4 kW·m^?2 and for mass flux ranging from 160 to 475 kg·m^?2 s^?1. The experiments were predominantly conducted only for laminar flow regime. Finally, the heat transfer coefficient is recorded and compared with the conventional theories. It is observed that the presence of ethylene glycol in water decreases the heat transfer coefficient by more than 50%, due to the decreased Reynolds number and thermal conductivity of the mixture.     

Multiple pure tone noise prediction

This paper presents a fully numerical method for predicting multiple pure tones, also known as “Buzzsaw” noise. It consists of three steps that account for noise source generation, nonlinear acoustic propagation with hard as well as lined walls inside the nacelle, and linear acoustic propagation outside the engine. Noise generation is modeled by steady, part-annulus computational fluid dynamics (CFD) simulations. A linear superposition algorithm is used to construct full-annulus shock/pressure pattern just upstream of the fan from part-annulus CFD results. Nonlinear wave propagation is carried out inside the duct using a pseudo-two-dimensional solution of Burgers? equation. Scattering from nacelle lip as well as radiation to farfield is performed using the commercial solver ACTRAN/TM. The proposed prediction process is verified by comparing against full-annulus CFD simulations as well as against static engine test data for a typical high bypass ratio aircraft engine with hardwall as well as lined inlets. Comparisons are drawn against nacelle unsteady pressure transducer measurements at two axial locations as well as against near- and far-field microphone array measurements outside the duct.     

Tuning electrochemical potential of LiCoO2 with cation substitution: first-principles predictions and electronic origin

With a goal to improve the performance of LiCoO₂ as a cathode material in Li-ion batteries, we simulate substitution of various elements (X = Be, Mg, Al, Ga, Si and Ti) for Co using first-principles density functional theory and predict changes in its electrochemical potential. While the electrochemical potential of LiCoO₂ is enhanced with substitution of Be, Mg, Al and Ga for Co, an opposite effect is predicted of Si and Ti substitution. We determine the electronic origin of these changes in electrochemical potential using (a) Bader method of topological analysis of charge density, (b) partial density of electronic states to estimate oxidation states of metal and oxygen, and charge re-distribution upon lithiation. We find that the distribution of electronic charge donated by Li is influenced by the nature of the X–O bond. A larger electron transfer to O (in XO₆ octahedron) upon lithiation leads to stronger Li intercalation and thereby higher electrochemical voltage. Our findings provide a platform for a rational design of cathode materials in Li batteries with enhanced voltage.     

Electrochemical Behavior of an Anti-Viral Drug Valacyclovir at Carbon Paste Electrode and Its Analytical Application

Valacyclovir (VCH) is an antiviral drug, used in the management of viral infections such as herpes simplex and varicella-zoster in humans. It is rapidly converted to acyclovir which has antiviral activity against herpes simplex virus types 1 (HSV-1) and 2 (HSV-2) and Varicella-zoster virus (VZV) both in vitro and in vivo. Electrochemical behavior was studied using cyclic voltammetric method, and the analytical application was studied using differential pulse voltammetric technique. The process on the surface of electrode was found to be irreversible and diffusion controlled. The charge transfer coefficient, heterogeneous rate constant, the number of electron transferred and activation parameters were calculated. Possible free radical reaction mechanism taking place on the surface of electrode was proposed. Calibration plot constructed using differential pulse voltammetric technique and applied for quantitative analysis in pharmaceutical and human urine sample. Limit of detection (LOD) and limit of quantification (LOQ) were calculated and found to be 0.028 and 0.09 μM, respectively. The present work describes the electrochemical behavior of an antiviral drug, VCH and its determination in pharmaceutical samples. The method shows the development of a sensor for selective and sensitive determination of VCH.     

Bimetallic complexes of a potentially pentadentate,acyclic, symmetrical compartmental Schiff base ligand that provides suitable topology for an exogenous bridge

The binucleating ligand LH₃, 2,6-diformyl-p-cresol-bis(phenylthioacetyldrazone), a Schiff base condensation product of 2,6-diformyl-p-cresol and phenylthioacetyldrazide forms complexes of the [M₂ClL] type with Co^II, Ni^II and Cu^II ions, which were characterized by elemental analysis, magnetic susceptibility, electronic spectra, molar conductance, i.r., n.m.r., e.p.r., t.g. and FAB mass spectral measurements. Sub-normal magnetic moments indicate the operation of antiferromagnetic coupling between the metal centres. The ligand and its copper complex show a pronounced fungistatic activity.     

Kinetics and mechanism of certain benzoylation reactions under Vilsmeier–Haack conditions using benzamide and oxychloride in acetonitrile medium

Vilsmeier–Haack (VH) benzoylation reactions with benzaldehydes and acetophenones in acetonitrile medium obeyed second‐order reaction kinetics. Under kinetic conditions, the reactions afforded benzoyl derivatives irrespective of the nature of oxychloride (POCl₃ or SOCl₂) used for the preparation of VH reagent along with benzamide. The present finding is advantageous to understand the nature of reactive species as well as the mechanism of benzoylation. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: 69–80, 2013     

Rapid and efficient microwave-assisted synthesis of highly sulfated organic scaffolds

Sulfation of multiple hydroxylated small organic molecules is fraught with problems of poor yield, multitude of products, and long reaction times. We have developed a rapid microwave-based method for synthesis of highly sulfated small organic molecules, which affords the per-sulfated product in moderate to excellent yields and high purity. The method is expected to be of value in the discovery of per-sulfated organic molecules as mimics of glycosaminoglycans, which are being increasingly recognized as modulators of key physiological functions.