Determination of boron in glass by the nuclear track technique

Summary Determination of Boron in Glass by the Nuclear Track Technique The nuclear track technique using the¹⁰B(n)⁷Li reaction, has been applied to determine boron in concentration ranges (1.59 to 7.75%) ordinarily considered high for nuclear determinations. Factors limiting the overall precision of the method and restricting the linear dependence of track density on boron concentration are examined. Boron alpha track densities are used to construct planar profiles of boron distribution within the surface region of bulk glass and CVD films. Calibration curves for quantitative lateral profiling of surfaces are constructed and show the selective corrosion of borosilicate glass surface resulting in boron depletion.     

Oxidative addition of dialkylphosphites to complexes of iridium(I) and rhodium(I)

The PH bond of dialkylphosphites (dimethylphosphite, 5,5-dimethyl-1,3-dioxa-2-phosphorinane and 4,4,5,5-tetramethyl-1,3-dioxa-2-phospholane) oxidatively adds to irClL₂(L = PPh₃, AsPh₃) and IrCl(PMe₂Ph)₃ generated in situ to give six-coordinate hydrido(dialkylphosphonato)iridium(III) complexes, e.g. IrHClL₂[{(MeO)₂-PO}₂H] and IrHCl(PMe₂Ph)₃[PO(OMe)₂]. Addition of triphenylphosphine to a solution containing [IrCl(C₈H₁₄)₂]₂ and dimethylphosphite in a 1:2 mol ratio gives a five-coordinate hydrido (dimethylphosphonato)iridium(III) complex IrHCl(PPh₃)₂{PO(OMe)₂}, from which six-coordinate pyridine and acetylacetonato complexes IrHCl(PPh₃)₂(C₅H₅N){PO(OMe)₂} and IrH(PPh₃)₂(acac){PO(OMe)₂} can be obtained. The ligand arrangements in the various complexes are inferred from IR, ¹H and ³¹P NMR data.     

Siloxane-containing polyenaminoesters

Polyenaminoesters were prepared by condensation of succinyl succinic ester (SSE) and p-bis-carbomethoxy diacetyl benzene (CDB) with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane. Conditions of solvent and temperature were discovered which yielded soluble polymer from SSE after heat treatment. CDB yields only tough, rubbery, insoluble products.     

Gas chromatographic-electron-impact mass fragmentometric determination of lysergic acid diethylamide in urine

A sensitive method for the detection and quantitation of lysergic acid diethylamide (LSD) in urine was developed. After initial solvent extraction, the compound was further purified by liquid-liquid extraction or by solid-phase extraction. The trimethylsilyl derivative of LSD was detected by gas chromatography-mass spectrometry (GC-MS) operated in the electron-impact mode with selected-ion monitoring. The presence of LSD was confirmed by comparing retention times and relative abundances of ions of unknowns with that of a standard. The recovery of this procedure was greater than 89%. The intra-run and inter-run coefficients of variation were less than 5% and less than 7%, respectively. This procedure allows detection of LSD concentrations as low as 29 pg/ml. Quantitation of LSD was linear over the concentration range 50-2000 pg/ml.     

2,8'-disubstituted-1,1'-binaphthyls: a new pattern in chiral ligands

The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15-->18), followed by functional group transformations, involving C-P and C-N bond formation (18-->19 and 18-->23). Racemic intermediate 22 was resolved by co-crystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product).     

Halide adsorption on single-crystal silver substrates: dynamic simulations and ab initio density functional theory

We investigate the static and dynamic behaviors of a Br adlayer electrochemically deposited onto single-crystal Ag(100) using an off-lattice model of the adlayer. Unlike previous studies using a lattice-gas model, the off-lattice model allows adparticles to be located at any position within a two-dimensional approximation to the substrate. Interactions with the substrate are approximated by a corrugation potential. Using density functional theory (DFT) to calculate surface binding energies, a sinusoidal approximation to the corrugation potential is constructed. A variety of techniques, including Monte Carlo and Langevin simulations, are used to study the behavior of the adlayer. The lateral root-mean-square (rms) deviation of the adparticles from the binding sites is presented along with equilibrium coverage isotherms, and the thermally activated Arrhenius barrier-hopping model used in previous dynamic Monte Carlo simulations is tested.