Structure absorption spectra correlation in a series of 2,6-dimethyl-4-arylpyrylium salts

A combined experimental and theoretical study of the absorption spectra of a group of closely related pyrylium perchlorates 1-11 are presented. Minor changes in the position of the substituents lead to drastic changes in the absorption spectra in this series of compounds. We have attempted to explain the observed changes using the x,y-band notation developed by Balaban and co-workers. Absorption spectra of all compounds are compared with results from time-dependent density functional theory (TDDFT) and Zerner's intermediate neglect of differential overlap (ZINDO/S) level calculations. Results of the calculations are in good agreement with experimental observations and an interesting correlation between Balaban's notations and the MO transitions are obtained for simple derivatives. It is suggested that for more complex systems such as alpha- and beta-naphthyl substituted systems, the empirical method is not appropriate.     

Synthesis and binding studies of novel thiacalixpodands and bisthiacalixarenes having O,O″-dialkylated thiacalix[4]arene unit(s) of 1,3-alternate conformation

A series of thiacalixpodands and bisthiacalixarenes with imine units have been prepared by condensation of O,O″-bis(2-aminoethyl)-O′,O?-dipropyl-p-tert-butylthiacalix[4]arene of 1,3-alternate conformation with different aromatic (di)aldehydes. The molecules derived from pyridine-2-carbaldehyde and -2,6-dicarbaldehyde quantitatively extract silver ion from aqueous into organic phase with complete selectivity over other metal ions (Na⁺, K⁺ and Cs⁺) under neutral conditions. The former compound forms a 1:2 (L:M) complex with silver ion as proved by NMR spectroscopy, Job’s plot and X-ray crystallography.     

Can an α-anomer of the trinitro form of D-glucopyranose be more easily hydrolyzed in alkaline environment than the β-anomer? A detailed theoretical analysis

Comprehensive computational investigations of detailed alkaline hydrolysis reaction pathways of the α-anomeric form of nitrocellulose monomer (2,3,6-trinitro-α-D-glucopyranose) in the (4)C(1) chair conformation within the S(N)2 framework in the gas phase and in bulk water solution are reported. Geometries of reactant complexes, transition states, intermediates, and completely denitrated product were optimized at the density functional theory (DFT) level using the B3LYP functional and the 6-311G(d,p) basis set both in the gas phase and in the bulk water solution. The effect of bulk water was modeled using the polarizable continuum model (PCM) approach. The nature of the potential energy surface of the local minima and transition states was ascertained through vibrational frequency analysis. Intrinsic reaction coordinate (IRC) calculations were also performed to validate the computed transition state structures. Effect of electron correlation on computed energies was considered through a single point energy calculation at the MP2 level using the cc-pVTZ basis set. It was revealed that the presence of hydrogen bonds between the attacking OH(-) ion and various hydrogen bond donating sites (including CH sites) of monomer was necessary for stabilization of the transition state. It was revealed that the α-anomer will be more reactive than the β-anomer with regard to the denitration reaction. The role of entropy and the denitration ability of various sites are also discussed.     

Orthogonal grid generation for Navier–Stokes computations

Body conforming orthogonal grids were generated using a fast hyperbolic method for aerofoils, and were used to solve the Navier–Stokes equation in the generalized orthogonal system for the first time for time accurate simulation of incompressible flow. For grid generation, the Beltrami equation and the definition equation for the orthogonality are solved using a finite difference method. The grids generated around aerofoils by this method have better orthogonality than the results published by earlier investigators. The Navier–Stokes equation at Reynolds numbers of 3000 and 35 000 for NACA 0012 and NACA 0015 respectively, have been solved as an application. The obtained results match quite well with the corresponding experimental results. © 1998 John Wiley & Sons, Ltd.     

Determination of the 15N chemical shift anisotropy in natural abundance samples by proton-detected 3D solid-state NMR under ultrafast MAS of 70 kHz

Chemical shift anisotropy (CSA) is a sensitive probe of electronic environment at a nucleus, and thus, it offers deeper insights into detailed structural and dynamic properties of different systems, for example, chemical, biological, and materials. Over the years, massive efforts have been made to develop recoupling methods that reintroduce CSA interaction under magic angle spinning (MAS) conditions. Most of them require slow or moderate MAS (≤20 kHz) and isotopically enriched samples. On the other hand, to the best of the authors' knowledge, no ¹³C or ¹⁵N CSA recoupling schemes at ultrafast MAS (≥60 kHz) suitable for cost-effective natural abundant samples have been developed. We present here a proton-detected 3D ¹⁵N CS/¹⁵N CSA/¹H CS correlation experiment which employs ¹H indirect detection for sensitivity enhancement and a γ-encoded -symmetry-based CSA recoupling scheme. In particular, two different symmetries, that is, R8³₇ and R10⁴₉, are first tested, in a 2D ¹⁵N CSA/¹H CS version, on [U-¹⁵N]-L-histidine·HCl·H₂O as a model sample under 70 kHz MAS. Then the 3D experiment is applied on glycyl-L-alanine at natural abundance, resulting in site-resolved ¹⁵N CSA lineshapes from which CSA parameters are retrieved by SIMPSON numerical fittings. We demonstrate that this 3D R-symmetry-based pulse sequence is highly robust with respect to wide-range offset mismatches and weakly dependent to rf inhomogeneity within mis-sets of ±10% from the theoretical value.