1H relaxation study in (NH4)2SbF5

¹H spin-lattice relaxation rate (T ₁ ⁻¹ ) has been measured using inversion recovery technique in polycrystalline (NH₄)₂SbF₅ system in the temperature range 140–400 K. From the plot of log (M ₀−M) againstτ, we have estimated two differentT ₁ corresponding to two inequivalent ammonium ions in the unit cell. Temperature-dependence ofT ₁ in each case exhibits features of double minima indicating the influence of different correlation times corresponding to different types of motion. Activation energies at different temperature regions have been estimated. Some features of dynamics of motion of the different groups of ions across the phase transitions have been discussed.     

Four constant potential function of amorphous selenium and evaluation of its thermodynamic and acoustic properties

Litov and Anderson after various considerations suggested a four constant potential function for a-Se as well as a-As₂S₃. Hence we also used a four constant potential function with the sole purpose of applying this potential function to obtain several acoustic, thermodynamic and other properties. We calculated several acoustic properties of a-Se like second order elastic constants (SOECs), their pressure derivatives, the longitudinal and transverse Grüneisen constant by two different methods, phonon frequencies, absorption band position through the use of Nath-Smith-Delaunay’s equation, and the thermodynamic properties like heat capacity, bulk modulus, thermal Grüneisen constant, the pressure derivative of the bulk modulus (dK _T/dP=C ₁), the pressure derivative ofC ₁ which is related to Anderson-Grüneisen parameter, pressure derivative of Grüneisen constant namelyγ′ _g which is related to second Grüneisen constant, characteristics of phonon frequencies, potential energy function through the use of fitted parameters and third order elastic constants. Finally we calculatedK _T at the reduced density ofρ/ρ ₀=1.1.K _T is obtained from the potential function with the fitted parameters. In all the above cases the calculated values are found to be in good agreement with experiment wherever available. In this connection it is important to point out that we eliminated ‘C’ a constant in the potential function using the equilibrium condition as was done by Litovet al in a-Se and Gerlichet al in the case of a-As₂S₃ as all amorphous substances are isotropic as mentioned by several authors. We contemplate to calculate several other properties for a-Se and a-As₂S₃ and present them at a later stage.     

A finite volume method for viscous incompressible flows using a consistent flux reconstruction scheme

An incompressible Navier–Stokes solver using curvilinear body‐fitted collocated grid has been developed to solve unconfined flow past arbitrary two‐dimensional body geometries. In this solver, the full Navier–Stokes equations have been solved numerically in the physical plane itself without using any transformation to the computational plane. For the proper coupling of pressure and velocity field on collocated grid, a new scheme, designated ‘consistent flux reconstruction’ (CFR) scheme, has been developed. In this scheme, the cell face centre velocities are obtained explicitly by solving the momentum equations at the centre of the cell faces. The velocities at the cell centres are also updated explicitly by solving the momentum equations at the cell centres. By resorting to such a fully explicit treatment considerable simplification has been achieved compared to earlier approaches. In the present investigation the solver has been applied to unconfined flow past a square cylinder at zero and non‐zero incidence at low and moderate Reynolds numbers and reasonably good agreement has been obtained with results available from literature. Copyright © 2006 John Wiley & Sons, Ltd.     

Supramolecular Gels Derived from the Salts of Variously Substituted Phenylacetic Acid and Dicyclohexylamine: Design,Synthesis, Structures,and Dye Adsorption

A well‐studied supramolecular synthon, namely, secondary ammonium monocarboxylate (SAM), was exploited to generate a new series of organic salts derived from variously substituted phenylacetic acid and dicyclohexylamine as potential low‐molecular‐weight gelators. As much as 25 % of the SAM salts under study were gelators. The gels were characterized by rheology, and the morphology of the gel networks was studied by high‐resolution electron microscopy. Single‐crystal and powder XRD data were employed to study structure–property (gelation) correlations. One of the gels could adsorb a hydrophobic dye (Nile Red) more efficiently than that of a hydrophilic dye (Calcein) from dimethyl sulfoxide; this might provide useful clues towards the development of stain‐removing gels.     

Reaktionen von 3-Dimethylamino-2,2-dimethyl-2H-azirin mit Phenolen und Halogenaromaten

Reactions of 3-dimethylamino-2,2-dimethyl-2H-azirine with phenols and aryl halides The reactions of 3-dimethylamino-2,2-dimethyl-2H-azirine ( 1 ) with phenols are described in chap. 1. The azirine 1 reacts with the 2-formyl- and 2-acetylphenols 5 – 8 to yield the N′-methylidene derivatives of 2-amino-N,N-dimethyl-isobutyramide 9 - 12 (Scheme 2, tautomeric form b ). These products are in equilibrium with the tautomeric quinoide forms 9a-12a . Under similar conditions 4-hydroxybenzaldehyde did not react with 1 . Reaction of 1 with 4-hydroxycoumarine ( 13 ) gives the 4-amino-coumarine 14 (Scheme 2). The mechanism of these reactions is analogous to the previously reported one for the reaction of 1 with cyclic enolisable 1,3-diketones [2] [3]. Activated phenols with pK_a-values < 8, e.g. 2- and 4-nitrophenol, 2,4-dinitrophenol and pentachlorophenol, undergo addition reactions with 1 in boiling benzene solution to give the aniline derivatives 15 - 18 (Scheme 3). A reaction mechanism is given in Scheme 3: after protonation of the azirine 1 followed by attack of the phenolate ion at the amidinium-C-atom, the intermediate of type e undergoes a rearrangement to the spiro-Meisenheimer complexes of type f . Ring opening leads to 15 – 18 . A similar reaction is observed for 2,4-dinitro-thiophenol and 1 , giving 2-(N′-(2,4-dinitrophenyl)amino)-N,N-dimethyl-isobutyrothioamide ( 19 ). The azirine 1 reacts with the more acidic 2,4,6-trinitrophenol (picric acid) to yield 3,3,6,6-tetramethylpiperazine-2,5-bis(N,N-dimethyliminium) dipicrate ( 21 , Scheme 4). The methacrylamidinium salt 22 is the only product (97% yield) in the reaction of 8-hydroxy-5,7-dinitroquinoline and 1 in acetonitrile solution. The reaction of 1 with picric acid can be explained in a similar way as the previously reported one with strong acids (cf. Scheme 1, [1] [3] [5]). An alternative mechanism without formation of the 1-aza-allylcation c is postulated in Scheme 5, together with a mechanism which could explain the exclusive formation of 22 in the reaction of 1 with 8-hydroxy-5,7-dinitroquinoline. In chap. 2 a few reactions of the azirine 1 with aryl halides are reported. In the reaction with 2,4-dinitrofluorobenzene it is shown by UV. and NMR., that m , n and o are intermediates (Scheme 6). Working up the reaction mixture with water, hydrogen sulfide or benzylamine leads to the aniline derivatives 17 , 19 and 26 , respectively. With picryl chloride and 8-hydroxy-5,7-dinitroquinoline the azirine 1 undergoes a nucleophilic aromatic substitution to afford the intermediates p and q , which via deprotonation and ring opening give acrylamidine derivatives ( 27 and 29 , Scheme 7 and 8). The steric hindrance in p and q between the aziridine ring and the two groups in o-position could be the reason for the different behaviour of the intermediates n and p or q (cf. Schemes 6 and 8).     

Boronic acid based dynamic click chemistry: recent advances and emergent applications

Recently, reversible click reactions have found numerous applications in chemical biology, supramolecular chemistry, and biomedical applications. Boronic acid (BA)-mediated cis-diol conjugation is one of the best-studied reactions among them. An excellent understanding of the chemical properties and biocompatibility of BA-based compounds has inspired the exploration of novel chemistries using boron to fuel emergent sciences. This topical review focuses on the recent progress of iminoboronate and salicylhydroxamic–boronate constituted reversible click chemistries in the past decade. We highlight the mechanism of reversible kinetics and its applications in chemical biology, medicinal chemistry, biomedical devices, and material chemistry. This article also emphasizes the fundamental reactivity of these two conjugate chemistries with assorted nucleophiles at variable pHs, which is of utmost importance to any stimuli-responsive biological and material chemistry explorations.

Fundamental progress, current developments, and rapidly growing applications of iminoboronate and salicylhydroxamic–boronate conjugate esters are deliberated.     

STUDIES ON HUMAN LENSES: II. DISTRIBUTION AND SOLUBILITY OF FLUORESCENT PIGMENTS IN CATARACTOUS AND NON-CATARACTOUS LENSES OF INDIAN ORIGIN

Abstract— Fluorometric studies of cataractous and non-cataractous human lenses were carried out to study the emission characteristics and the distribution and solubility of lenticular pigments. Most of the detected fluorophores were well distributed over the cortical and nuclear portion of the lens. The decrease in solubility of proteins with aging and cataract formation is concomitant with increasing photolysis of tryptophan. However, this is likely a phenomenon independent of the photochemical transformations of the lens proteins. The number of emitting species in the diseased lenses are higher than in the normal mature lenses. A species emitting around 375 or 388 nm is of particular interest (λ_cx, 330 nm) in that the emission characteristics of this fluorophore resemble kynurenic acid which has a high photosensitizing efficiency. The concentration of fluorescent pigments in the lenses of Indian origin is significantly high. The intense pigmentation could be attributed largely to the formation of photoproducts in the absence of normal endogenous antioxidant accumulation that is dependent on nutrition standard. If, indeed, any of these fluorescent pigments, because of their photosensitizing ability, are responsible for lenticular opacity, it is not the abundance of sunlight alone but also malnutrition that could account for the high incidence of cataract in India.     

SL(2,C)-gauge theory andN=1 supergravity

It is shown that as Riemannian space may be taken to give rise to a Poincaré gauge theory of gravitation, the superspace where the coordinates are given by (X, ), being a spinorial variable gives rise to anSL(2, C)-gauge theory and corresponds toN= 1 supergravity. It leads to a conserved current and the conserved quantity here corresponds to isospin, where the latter is taken to be generated from conformal reflection. Thus, supergravity plays a predominant role in the microlocal space-time.