Novel pulsed electron spin resonance system and studies of phosphorus in natural silicon

An X-band pulsed electron spin resonance system has been designed and constructed specifically for studies of decoherence times of phosphorus donor electrons in silicon. The microwave electromagnetic field aspects of the structure have been analysed, and the probe head geometry optimised, through 3D electromagnetic simulations. Results for natural silicon samples at temperatures down to 6 K, are analysed and we obtain an estimate of the isolated spin decoherence time in ^natSi approximately an order of magnitude longer than previously measured.     

Pulsed fm NMR/on studies of single crystal54MnNi and125SbFe

Precision field shift studies of B_appl-8T using pulsed FM NMR/ON along hard directions (eg <100>⁵⁴MnNi, <112>¹²⁵SbFe and the easy axis (<111>⁵⁴MnNi, <100>¹²⁵SbFe) yield no measurable Knight shifts within the uncertainty allowed by current accuracy of the nuclear moments. This is in striking contrast to earlier measurements with the same apparatus that yielded K=+1.5 (4)% for⁶⁰CoFe. The modulation frequency dependences of the pulsed FMNMR/ON signals are investigated for a variety of rf parameters and compared with model predictions.     

A comparative TEM study of the 3D lattice of tellurium nanoclusters fabricated by different techniques in an opal host

An electron-microscope study of synthetic opals containing tellurium introduced into the regular void array either by melt injection or by evaporation from solution is reported. In the first case, a three-dimensional array of tellurium clusters interconnected by bridges was revealed. The clusters retain the same crystallographic orientation as one moves from one cluster to another. This suggests that cooling after inserting tellurium results in its directional crystallization, which is possibly controlled by the interconnecting channels. The second technique of tellurium introduction produces a nonuniform cluster array, with three-dimensional clusters growing not in all voids. The surface of most of the silica spheres is coated by a thin discontinuous layer of tellurium. This structure of the cluster array accounts for the nonlinear current-voltage characteristic of the object as a whole. A possibility of engineering cluster lattices differing in structural parameters has been demonstrated. Fiz. Tverd. Tela (St. Petersburg) 39, 2090–2095 (November 1997)     

Evaluation of a pseudoephedrine linker for asymmetric alkylations on solid phase

[reaction: see text] Immobilized pseudoephedrine amides have been conveniently prepared by attachment of pseudoephedrine to Merrifield resin and acylation on nitrogen. Deprotonation and alkylation of the resin bound amides proceeds smoothly. Products were cleaved from the resin to give ketones and alcohols in high enantiomeric excess and moderate to good overall yield.     

Chemistry of 2,4,6-trimercapto-1,3,5-triazine (TMT): acid dissociation constants and group 2 complexes

The acid dissociation constants of 2,4,6-trimercaptotriazine (H(3)TMT, 1) were determined and now can be employed in the preparation of complexes having specific M-TMT (M = divalent metal; TMT = 2,4,6-trimercapto-1,3,5-triazinide, C(3)N(3)S(3)(3-)) ratios. For example, the combination of H(3)TMT (1) with Mg(OH)(2) at pH 7.1 leads to the crystallization of Mg(H(2)TMT)(2).6H(2)O (4). With the appropriate pH adjustment, the contiguous series of compounds Ba(3)(TMT)(2).8H(2)O (3), Ba(H(2)TMT)(2).7H(2)O (5), and BaHTMT.3H(2)O (6) can be isolated. The compounds were characterized by mp, IR, TGA, elemental analysis, and, in the cases of 4, 5, and 6, crystallography. The comparison of 4 with 5 and 6 offers an interesting view of the difference in hard and soft bonding with TMT. In the saltlike Mg structure of 4, there is extensive hydrogen bonding, but in the Ba structures, 5 and 6, covalent Ba-S bonding dominates.     

Bicyclic and acyclic diamides: comparison of their aqueous phase binding constants with Nd(III), Am(III), Pu(IV), Np(V), Pu(VI), and U(VI)

This report describes affinity measurements for two, water-soluble, methyl-alkylated diamides incorporating the malonamide functionality, N,N,N',N' tetramethylmalonamide (TMMA) and a bicyclic diamide (1a), toward actinide metal cations (An) in acidic nitrate solutions. Ligand complexation to actinides possessing oxidation states ranging from +3 to +6 was monitored through optical absorbance spectroscopy, and formation constants were obtained from the refinement of the spectrophotometric titration data sets. Species analysis gives evidence for the formation of 1, 4, 1, and 2 spectrophotometrically observable complexes by TMMA to An(III, IV, V, and VI), respectively, while for 1a, the respective numbers are 3, 4, 2, and 2. Consistent with the preorganization of 1a toward actinide binding, a significant difference is found in the magnitudes of their respective formation constants at each complexation step. It has been found that the binding affinity for TMMA follows the well-established order An(V) < An(III) < An(VI) < An(IV). However, with 1a, Np(V) forms stronger complexes than Am(III). The complexation of 1a with Np(V) and Pu(VI) at an acidity of 1.0 M is followed by reduction to Np(IV) and Pu(IV), whereas TMMA does not perturb the initial oxidation state for these dioxocations. These measurements of diamide binding affinity mark the first time single-component optical absorbance spectra have been reported for a span of actinide-diamide complexes covering all common oxidation states in aqueous solution.     

High-performance liquid chromatographic determination of nafazatrom in human plasma using fluorescence detection

A rapid, sensitive, and selective high-performance liquid chromatographic assay was developed for determination of the pyrazole derivative nafazatrom (Bay g 6575, NFZ) in human plasma. Separation was obtained using a normal-phase Si-60 column and a mobile phase of methylene chloride--methanol (90:10, v/v) containing 0.25% water. The fluorescence of NFZ was monitored at excitation and emission wavelengths of 232 and 362 nm, respectively. The recovery of NFZ extracted from plasma with methylene chloride was 109 +/- 5% (mean +/- S.D.) in the concentration range from 5.0 to 500 ng/ml. The assay was applied to the determination of plasma concentrations of NFZ following administration of the compound to patients in a Phase I clinical trial.     

Multiple phases in the system MgF2---Nb2O5 an electron microscope study of intergrowths, defects, and disordered crystals

Mixtures of MgF₂·xNb₂O₅ with x = 7 and 14 have, on annealing at high temperatures yielded a wide variety of block structures in which MgF₂ has replaced MeO₂ (Me = Ti⁴⁺, Nb⁴⁺). With F⁻ stabilizing the formation of large blocks, numerous defect structures have been characterized by direct lattice resolution electron microscopy. Features thus observed include planar faults, intergrowths, segregated domain structures, and disordered crystals. Chemical implications of these features are discussed.