Thermal expansion of zirconium—II

The generalised Gruneisen parameters γ′ = ?? log ω/??′ and γ″ = ?? log ω/??″ have been calculated for various normal mode frequencies using the force model for Zirconium obtained on Keating's approach. There is a general agreement between the normalised frequency distribution curve of Zirconium obtained on the present model and that of Bezdek et al. The temperature dependence of the effective Gruneisen functions $\text{γ}\text{?}{}_{\mathrm{\perp }}\text{(T)}$ and $\text{γ}\text{?}{}_{\mathrm{|}}\text{(T)}$ has been calculated using the procedure of Blackman. The high temperature limits of $\text{γ}\text{?}{}_{\mathrm{\perp }}\text{(T)}$, $\text{γ}\text{?}{}_{\mathrm{|}}\text{(T)}$ and $\text{γ}\text{?}{}_{\mathrm{v}}$ are in good agreement with those obtained by Goldak et al. from an analysis of the thermal expansion data of Zirconium.     

Isotopic sum rules and compliance scheme

It is known that compliance scheme does not provide simple linear isotopic sum rules in λ^?1 similar to the ones in λ in the force constant scheme. The advantage of not having such sum rules in the compliance scheme is discussed in relation to the uniqueness problem of the molecular force field.Incidentally, for the molecules H₂O, D₂O, and HDO, two quadratic relations in terms of the inverse frequency parameters λ^?1 are obtained. These supplement the three obvious product rule relations.     

Solvent influences in the alkaline hydrolysis of esters in aqueous ethanol

The rate data for the alkaline hydrolysis of a number of monoesters, diesters and lactones have been obtained in varying compositions of aqueous ethanol. The application of the Amis and Laidler-Landskroener equations to the data yields reasonable values for the parameters representing the radius of the transition state for the hydrolysis confirming the ion-dipole nature of the reaction. An attempt to explain the rate data on the basis of the solvation requirements of the transition state has been made.     

Solvent extraction of chromium: A review

The separation of chromium by solvent extraction is reviewed.     

Separation theorems for singular values of matrices and their applications in multivariate analysis

Separation theorems for singular values of a matrix, similar to the Poincaré separation theorem for the eigenvalues of a Hermitian matrix, are proved. The results are applied to problems in approximating a given r.v. by an r.v. in a specified class. In particular, problems of canonical correlations, reduced rank regression, fitting an orthogonal random variable (r.v.) to a given r.v., and estimation of residuals in the Gauss-Markoff model are discussed. In each case, a solution is obtained by minimizing a suitable norm. In some cases a common solution is shown to minimize a wide class of norms known as unitarily invariant norms introduced by von Neumann.     

A carbohydrate-based approach for the total synthesis of 1,3-polyol/alpha-pyrone antifungal natural products

[Chemical reaction: see text] An elimination and stereoselective hydrogenation of alpha-D-glucoheptonic-gamma-lactone derivative has been applied to prepare a differentially protected anti,anti-1,3,5-triol system, the utility of which has been extended for the total synthesis of anti-fungal 1,3-polyol/alpha-pyrone natural products.     

Ultrasound-assisted analyte extraction for the determination of sulfate and elemental sulfur in zinc sulfide by different liquid chromatography techniques

The speciation and determination of sulfate (SO4(2-)) and elemental sulfur (S degree) in zinc sulfide (ZnS) using ion-chromatography (IC) and reversed-phase liquid chromatography (RPLC) respectively is described. Three sample pretreatment approaches were employed with the aim of determining sulfate: (i) conventional water extraction of the analyte; (ii) solid-liquid aqueous extraction with an ultrasonic probe; and (iii) elimination of the zinc sulfide matrix via ion-exchange dissolution (IED). The separation of sulfate was carried out by an anion-exchange column (IonPac AS17), followed by suppressed conductivity detection. Elemental sulfur was extracted ultrasonically from the acid treated sample solution into chloroform and separated on a reversed phase HPLC column equipped with a diode array detector (DAD) at 264 nm. The achievable solid detection limits for sulfate and sulfur were 35 and 10 microg g(-1) respectively.     

Near-infrared absorption in symmetric squarylium and croconate dyes: a comparative study using symmetry-adapted cluster-configuration interaction methods

Symmetric croconate (CR) and squarylium dyes (SQ) are well-known near-infrared (NIR) dyes and, in general, are considered to be donor-acceptor-donor type molecules. It is established in the literature that CR dyes absorb in a longer wavelength region than the corresponding SQ dyes. This has been attributed to the CR ring being a better acceptor than the SQ ring. Thus increasing the donor capacity should lead to a bathochromic shift in both SQ and CR. On the other hand, some experiments reported in the literature have revealed that increasing the conjugation in the donor part of the SQ molecule leads first to red shift, which upon a further increase of the conjugation changes to a blue shift. Hence, to understand the role of the central ring and the substitutions in the absorption of these dyes, we carried out high-level symmetry-adapted cluster-configuration interaction (SAC-CI) calculations of some substituted SQ and CR dyes and compare the absorption energy with the existing experimental data. We found that there is very good agreement. We also carried out SAC-CI calculations of some smaller model molecules, which contain the main oxyallyl substructure. We varied the geometry (angle) of the oxyallyl subgroup and the substitution in these model molecules to establish a correlation with the bathochromic shift. We found that the charge transfer is very small and does not play the key role in the red shift, but on the other hand, the perturbation of the HOMO-LUMO gap (HLG) from both the geometry and substitution seems to be responsible for this shift. We suggest as a design principle that increasing the donor capacity of the groups may not help in the red shift, but introducing groups which perturb the HLG and decrease it without changing the MO character should lead to a larger bathochromic shift.