Hyperfine structure in Ga NQR of Gas and GaSe

Fine structure is reported in the ^69,71Ga NQR spectra of GaS and GaSe. The ⁶⁹Ga (I = ³₂) and ⁷¹Ga (I = ³₂) spectra are $\text{qualitatively}$ different for each compound. This is attributed to an indirect spin-spin interaction between nearest-neighbour Ga atom pairs. A model giving reasonable quantitative agreement with experiment is presented.     

Solid state NMR characterisation of crystalline Na2OZrO2SiO2 phases

The NMR interactions of crystalline phases in the system Na₂O-ZrO₂-SiO₂ have been studied by a combination of static and magic angle spinning NMR methods for the first time. A full multinuclear (¹⁷O, ²³Na, ²⁹Si and ⁹¹Zr) approach has been employed that allows the phases to be clearly identified. NMR interactions such as ²⁹Si isotropic chemical shift correlate with the known structural units present. For ²³Na the different sites can often be distinguished on the basis of differing quadrupolar interactions.     

A 69Ga, 115In NQR study of polytypes of GaS,GaSe and InSe

Pulsed Fourier transform NQR spectroscopy has been used to study polytypism in the monochalcogenides GaS, GaSe and InSe at 77 K. The spectrum of GaS was consistent with a major contribution from the β phase but showed evidence of higher polytypes, possibly due to ? or γ type faulting. The GaSe spectrum is simply interpreted as an equal mixture of ? and γ types. The four InSe spectra ($\text{I}\text{=}\text{9}\text{2}$¹¹⁵In), showed a multiplicity of lines. The sharpness of the NQR lines of all spectra suggests the existence of regions with a hitherto overlooked high degree of order.     

N NMR in AlN and BN

A characterisation by ¹⁴N NMR of the binary nitrides AlN and BN is presented. Both the static and magic angle spinning (MAS) lineshapes have been investigated in order to determine, or set upper limits on, the nuclear quadrupole coupling (C_q) at the nitrogen site. Additional data are given for the C_q values at the Al and B sites. A comparison is made with other similar (mainly wurtzite) binary compounds for which C_q is known at each atomic site.     

Zn NMR investigation of zinc halides

⁶⁷Zn NMR has been used as a probe to measure the electric field gradients at the metal site in the zinc halides ZnF₂, γ-ZnCl₂, ZnBr₂ and ZnI₂ and Rb₂ZnCl₄ at room temperature. In addition two hydration states have been detected for ZnSO₄. For ZnF₂ and γ-ZnCl₂ an ab initio calculation of the electric field gradient at the Zn site using the W 97 code agrees well with the experimentally observed values.     

Cytotoxic Isoprenylated Flavonoids from the Roots of Sophora flavescens

Three new flavonoids, which are isoprenylated by fused 2,2‐dimethyl‐3,4‐dihydro‐2H‐pyran moieties, were isolated from the roots of Sophora flavescens and named flavenochromanes A–C ( 1 – 3 ). Their structures were elucidated by spectroscopic methods, including 2D‐NMR techniques. Flavenochromane C ( 3 ) showed strong cytotoxic activity against A549 (lung carcinoma), 1A9 (ovarian carcinoma), KB (epidermoid carcinoma of the nasopharynx), and KB‐Vin (drug‐resistant variant KB) cell lines with IC₅₀ values ≤1.7 μM , and significant activity against the MCF‐7 (breast adenocarcinoma) cell line with an IC₅₀ value of 3.6 μM . Flavenochromane B ( 2 ) displayed slightly lower inhibitory effects (IC₅₀ 3.2–6.9 μM ) as compared with 3 .     

Solid-state NMR characterisation of the thermal transformation of a Hungarian white illite

(1)H, (27)Al, (29)Si and (39)K solid-state NMR are reported from a Hungarian illite 2:1 clay for samples heated up 1600 degrees C. This single-phase sample has a small amount of aluminium substitution in the silica layer and very low iron-content ( approximately 0.4wt%). Thermal analysis shows several events that can be related to features in the NMR spectra, and hence changes in the atomic scale structure. As dehydroxylation occurs there is increasing AlO(4) and AlO(5)-contents. The silica and gibbsite layers become increasingly separated as the dehydroxylation progresses. Between 900 and 1000 degrees C the silica layer forms a potassium aluminosilicate glass. The gibbsite-layer forms spinel/gamma-Al(2)O(3) and some aluminium-rich mullite. Then on heating to 1600 degrees C changes in the (29)Si and (27)Al MAS NMR spectra are consistent with the aluminosilicate glass increasing its aluminium-content, the amount of mullite increasing probably with its silicon-content also increasing, and some alpha-Al(2)O(3) forming.     

The anti-neoplastic activity of ethylamine-carboxyborane and triphenylphosphine-carboxyborane in L-1210 lymphoid leukemia cells

Studies on the mode of action of two boroncontaining anti-neoplastic agents, ethylamine-carboxyborane and triphenylphosphine-carboxyborane, are reported. The major site of inhibition was in the pyrimidine de nove synthetic pathway at orotidine monophosphate decarboxylase activity. Additional sites which may facilitate the inhibition of cell growth were IMP dehydrogenase, thymidine kinase, TMP kinase and TDP kinase, m-RNA, r-RNA and t-RNA polymerase activities as well as topoisomerase II activity. The reduction in enzyme activities led to sufficient reduction of d(NTP) levels to suppress DNA synthesis and cell growth. DNA strand scission was evident in the presence of drug. Multiple modes of action are common with amine-carboxyboranes. Acute toxicity studies in mice showed that both agents were safe in their therapeutic range based on organ weights, histological tissue sections, clinical chemistry values and hematopoietic parameters.     

63Cu NMR analysis of microstructure evolution in Al–Cu–Mg alloys

⁶³Cu NMR spectroscopy has been used to detect metastable Guinier–Preston–Bagaryatsky (GPB) zones and nanoscale precipitates of equilibrium S-phase (Al₂CuMg) in dilute alloys of aluminium containing copper and magnesium with compositions which lie in the α?+?S phase field. The GPB zones are observed to form rapidly at room temperature with a time development closely related to the Vickers hardness. The final development of S-phase in the alloy has been confirmed by the observation of a line shape in the alloy identical to that observed in a specimen prepared from stoichiometric Al₂CuMg. Analysis of the hyperfine structure of the ⁶³Cu line shape observed for S-phase shows clearly that two Cu sites are present with approximately equal population. This result suggests that possibly two crystallographically distinct Al₂CuMg phases are present. The addition of small amounts of silver to Al–Cu–Mg alloys in the α?+?θ phase field is known to induce the formation of Ω-phase: a slight distortion of tetragonal θ-phase Al₂Cu. A hyperfine-structured ⁶³Cu line shape assigned to Ω-phase, indicating one distinct Cu site, has been observed in two separate Al–1.7?at.%?Cu–0.33?at.%?Mg alloys containing 0.1 and 0.18?at.%?Ag, but not in the same Al–Cu–Mg alloy without Ag.     

Strong interaction of an Al2Cu intermetallic precipitate with its boundary

NMR, X-ray diffraction (XRD) and transmission electron microscopy (TEM) experiments have been undertaken to establish the nature of Ω-platelets which form during heat treatment of aluminium alloys containing Cu, Mg (Mg lean) and Ag of the order of 0.1 at. % [1]. The platelets lie on (111) planes of the Al host lattice, separated from the Al on either face by a thin layer, one or two atoms thick, of Mg and Ag atoms. At temperatures between 185°C and 250°C the platelets have been previously shown to coarsen (thicken) slowly with time but more rapidly at 300°C [2,3]. TEM observations are described which confirm that the platelets remain on (111)_α for heat treatments up until at least 5?h at 300°C. The NMR and XRD results indicate that for thick platelets the bulk of the platelet material, sufficiently distant from the two bounding interfaces, is exactly tetragonal Al₂Cu θ-phase, but that platelets of the order of 2–4?nm thick (e.g. 100?h at 185°C) have a structure strongly influenced by interaction with the platelet boundary, which removes the axial symmetry of the Cu atom. Both NMR and XRD observations have shown a gradual transition between these two limits.