Mechanical stresses in vapour quenched films of Al and Al rich compounds

The measurement of mechanical stresses in vapour quenched metal films can give additional structural information. Especially the near absence of stresses yields a sufficient condition for the formation of amorphous structures, since stress contributions due to the crystallite boundary mismatch are present in every micro crystalline film. From this point of view we find that Al films containing more than 25 at.% Ag grow in an amorphous phase whereas films with less than 25 at.% Ag are micro crystalline. The influence of other impurities, especially oxygen, is also investigated. Further evidence is presented for the high superconducting transition temperatures of Al films evaporated from Al₂O₃ crucibles, which films are micro crystalline, to be due to the presence of Al₂O impurities in these films.     

The inhibition of factor inhibiting hypoxia-inducible factor (FIH) by beta-oxocarboxylic acids

Cyclic beta-oxocarboxylic acids inhibit factor inhibiting hypoxia-inducible factor via ligation to the active site iron.     

A rutherford scattering study of the diffusion of heavy metal impurities in silicon to ion-damaged surface layers

Rutherford backscattering of 1.75 and 2 MeV ⁴He⁺ ions has been utilized to study the high temperature gettering of Fe, Co, Ni, Cu and Au from silicon by ion-damaged surface layers. In a typical experiment a metal film was evaporated onto one side of a silicon wafer (125 microm thick) which had received ion implantation damage (10¹⁶/cm² Si⁺ ions at 100 keV) on the opposite side; the wafer was then annealed at 900°C, usually for 30 min. The results of such experiments show that the metals studied may be divided into two classes, those which are gettered slowly - Fe, Co, and Au, and those gettered rapidly - Cu and Ni. Fe, Co, and Au were found at levels of 1×10¹³?1×10¹⁴/cm² in the damaged layer, whereas Cu and Ni appeared at levels of 6×10¹⁴ to 5 ×10¹⁶cm². The gettered level of Au, one of the “slow” group, was increased ten-fold by an equal increase in the anneal time to 300 min. The gettered Cu and Au exhibited double peaks in the scattered ion spectra, corresponding to metal concentrated at the most heavily damaged region (end of range for Si implant) and also at the outer surface, with a separation of ~ 1300 Å. A simple model is proposed to explain the slow and fast gettering, based on published interstitial diffusivities and solubilities of the five elements studied.Rutherford scattering has proven to be well suited for the quantitative identification of low levels of impurities on Si surfaces and for impurities gettered at damaged layers close to the surface.     

Dilute solution studies of nitrogen-substituted polyurethanes

A high molecular weight linear polyurethane was prepared by the polyaddition of equimolar amounts of ethylene glycol and methylene bis(4-phenyl isocyanate). Varying amounts of the labile carbamate protons of the polyurethane backbone were substituted by a number of groups of varying length and composition. The resultant grafted or nitrogen-substituted polyurethanes were then studied viscometrically in both polymer solvent and in a polymer solvent—nonsolvent mixture. The configuration of the nitrogen-substituted polyurethane was found to be dependent upon the number and length of pendent branches.     

Linear electric field (LEF) effects in 13C NMR. Some model calculations on 5-chloro-1-pentene

The usefulness and some of the limitations of the linear electric field (LEF) effect in ¹³C NMR are illustrated by means of model calculations on the ¹³C NMR chemical shifts of C-1 and C-2 in 5-chloro-1-pentene in nine different conformations. Two different concepts are used in order to calculate the electric fields near C-1 and C-2 caused by the C-5? Cl dipole. It is also demonstrated that, when using charges calculated by CNDO/2, the influences of the hydrogen atoms at C-5 cannot be neglected. The use of the dipole–dipole interaction formula is advocated. The consequences of taking into account the additional contributions of the vinylic bonds to the accumulated charges at C-1 and C-2 are described. The results with the dipole–dipole formula show that the same signs and similar magnitudes of the LEF effects are calculated in seven out of nine conformations of 5-chloro-1-pentene. This reduces the LEF to a means of confirming, rather than deducing, conformational equilibria in acylic flexible compounds. The usefulness of some recently published applications of the LEF concept to explain some short range substituent effects is critically discussed, mainly in view of the inhomogeneities of the calculated electric fields.     

Cucurbituril binding of trans-[{PtCl(NH3)2}2(micro-NH2(CH2)8NH2)]2+ and the effect on the reaction with cysteine

The effect of encapsulation by cucurbiturils Q[7] and Q[8] on the rate of reaction of the anti-cancer dinuclear platinum complex trans-[{PtCl(NH3)2}2(micro-NH2(CH2)8NH2)]2+ with the model biological nucleophiles glutathione and cysteine has been examined by NMR spectroscopy. It was expected that the octamethylene linking chain would fold inside the cucurbituril host and hence position the reactive platinum centres close to the cucurbituril portals, and thereby, confer resistance to degradation by biological nucleophiles. The upfield shifts of the resonances from the methylene protons in the linking ligand observed in 1H NMR spectra of the platinum complex upon addition of either Q[7] or Q[8] indicate that the cucurbituril is positioned over the linking ligand, with the Pt(II) centres projecting out of the portal. Furthermore, the relative changes in chemical shift of the methylene resonances suggest that the octamethylene linking chain folds within the cucurbituril cavity, particularly in Q[8]. Simple molecular models, based on the observed relative changes in chemical shift, could be constructed that were consistent with the proposed folding of the linking ligand within the cucurbituril cavity. Encapsulation by Q[7] was found to reduce the rate of reaction of the platinum complex with glutathione. Encapsulation by Q[7] and Q[8] was also found to reduce the rate of reaction of the platinum complex with cysteine, with Q[8] slowing the reaction to a greater extent than Q[7], consistent with the inferred encapsulation geometries. Encapsulation of dinuclear platinum complexes within the cucurbituril cavity may provide a novel way of reducing the reactivity and degradation of these promising chemotherapeutic agents with blood plasma proteins.     

Configurational analysis of cyclopropyl fatty acids isolated from Escherichia coli

[reaction: see text] The absolute configuration of methyl lactobacillate and its 9,10 homologue, both isolated from Escherichia coli B-ATCC 11303, was found to be 11R,12S and 9R,10S, respectively.     

A Theorem on Homogeneous Differential Polynomials

We substantially strengthen an unpublished result of Whitehead from his PhD thesis (Whitehead, A.: Differential equations and differential polynomials in the complex. PhD thesis, University of Nottingham, 2002) using a refinement of his techniques.