The effect of dipole-dipole interaction on zero-THz frequency polarisation

The effect of intramolecular dipole-dipole interaction on polarisation at frequencies from 0 – 10¹² Hz in dipolar media is investigated using a numerical solution of the Sturm-Liouville eigenvalue problem to which the governing Smoluchowski equation reduces. The results of Budó for the long-wavelength limit are extended to all frequencies up to the far infrared, where the predominant inertial effects are treated using a preliminary first-order correction. The numerical method of Pryce may be used to investigate much more realistic interaction potentials than the simple harmonic and cosine form considered by Budó. These simple forms are, however, sufficient to indicate that the integrated absorption intensity per molecule in the far infrared is very sensitive to dipole-dipole interaction and relative hydrodynamic drag on both interacting groups. Applications of the theory to the disordered solid and nematic phases are considered.     

A study of the oxidation of vegetable oils by inverse gas chromatography

Summary Inverse gas chromatography is shown to be suitable for the study of the oxidation of vegetable oils. With air as carrier gas characteristic plots of retention index versus time are obtained for hydroxylic test solutes that are consistent with the oxidation behaviour of vegetable oils. Shifts of retention are found to be accompanied by changes of column efficiency due to the oxidative crosslinking of polyunsaturated vegetable oils. The technique also leads to useful information concerning the oxidation of antioxidant inhibited systems. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Substituted γ-lactones. Some observations on the synthesis and reactivity of 4-aroyl-3-hydroxy-2(5H)-furanones

The reaction pathway towards formation of 4-aroyl-3-hydroxy-2(5H)-furanones 1 from the base catalyzed reaction between an acetophenone, diethyl oxalate and formaldehyde was investigated. If methoxide was used as base, a transesterification was found to occur in the first step, while a side reaction, namely the retro Claisen reaction, was in competition with the desired lactone formation in the second step. The nature of the solvent and the acidic character of 1 as well as the basicity of the aminoarylene were found to have a profound influence on the course of the reaction of 1 with aminoarylenes.     

A hexacyclic ent-trachylobane diterpenoid possessing an oxetane ring from Mitrephora glabra

[chemical reaction: see text]. Three new ent-trachylobane diterpenoids (1-3) were isolated and structures elucidated from Mitrephora glabra Scheff. (Annonaceae). Mitrephorone A (1) possesses a hexacyclic ring system with adjacent ketone moieties and an oxetane ring, both of which are unprecedented among trachylobanes. All compounds were evaluated for cytotoxicity against a panel of cancer cells, where 1 displayed the most potent and broadest activity, and against a battery of antimicrobial assays, where all compounds were approximately equipotent.     

PHOTOLYTIC REARRANGEMENT OF METRONIDAZOLE TO 1-HYDROXYETHYL-2-METHYL-4-HYDROXYIMINO-5-OXO-IMIDAZOLE AND THE FORMATION OF COPPER COMPLEXES OF THESE COMPOUNDS

Abstract— A labile intermediate in the photolytic rearrangement of the antibacterial drug, metronidazole, was identified by isolating the product of photolysis of metronidazole benzoate in methanol. The intermediate, 1-hydroxyethyl-2-methyl-4-hydroxyimino-5-oxo-imidazole, was shown to act as a bidentate chelating agent for copper(II) ions, whereas metronidazole forms a weak monodentate complex. The intermediate may be relevant to the bioactivation mechanism of metronidazole.     

The preparation of 4-oxo-N-aryl-4H-1-benzopyran-2-acetamides by the condensation/cyclization of trilithiated acetoacetanilides with lithiated methyl salicylates

Several acetoacetanilides were trilithiated in excess lithium diisopropylamide, and the resulting polylithiated intermediates were regioselectively condensed with lithiated methyl salicylates followed by acid cyclization to substituted 4-oxo-N-aryl-4H-1-benzopyran-2-acetamides (benzopyranone-2-acetamides).     

Regressions and monotone chains II: The poset of integer intervals

A regressive function (also called a regression or contractive mapping) on a partial order P is a function mapping P to itself such that (x)x. A monotone k-chain for is a k-chain on which is order-preserving; i.e., a chain x ₁<...ksuch that (x ₁)...(x_k). Let P _nbe the poset of integer intervals {i, i+1, ..., m} contained in {1, 2, ..., n}, ordered by inclusion. Let f(k) be the least value of n such that every regression on P _nhas a monotone k+1-chain, let t(x,j) be defined by t(x, 0)=1 and t(x,j)=x ^t(x,j–1). Then f(k) exists for all k (originally proved by D. White), and t(2,k) < f(K) <t( + _k, k) , where _k 0 as k. Alternatively, the largest k such that every regression on P _nis guaranteed to have a monotone k-chain lies between lg^*(n) and lg^*(n)–2, inclusive, where lg^*(n) is the number of appliations of logarithm base 2 required to reduce n to a negative number. Analogous results hold for choice functions, which are regressions in which every element is mapped to a minimal element.