ABSTRACT
The nature of the elusive muonium centre in sulphur is re-examined in the light of new data on its level-crossing resonance and spin-lattice relaxation. The aim is to provide a model for the solid-state chemistry of interstitial hydrogen in this element, which is as yet unknown, as well as to solve one of the longest standing puzzles in µSR spectroscopy, namely the surprisingly strong depolarization of muons mimicking ion-implanted protons in this innocuous non-magnetic material. The paramagnetic muonium (and by inference hydrogen) centre is confirmed to have the character of a molecular radical, but with huge anisotropy at cryogenic temperatures and a striking shift of the resonance at ordinary temperatures, the hyperfine parameters appearing to collapse and vanish towards the melting point. New density-functional supercell calculations identify a number of possible structures for the defect centre, including a novel form of bond-centred muonium in a closed-ring S(8)Mu complex. Simulations of the spin dynamics and fits to the spectra suggest a dynamical equilibrium or chemical exchange between several configurations, with occupancy of the bond-centre site falling from unity at low cryogenic temperatures to zero near the melting point.
Subject(s)
Hydrogen/chemistry , Mesons , Spectrophotometry/methods , Anisotropy , Biochemistry/methods , Computer Simulation , Hydrogen Sulfide/chemistry , Models, Statistical , Molecular Conformation , Semiconductors , Surface Properties , TemperatureABSTRACT
Infrared and Raman spectra of sequentially extracted primary cell walls and their pectic polymers were obtained from five angiosperm plants. Fourier-transform Raman spectrometry was shown to be a powerful tool for the investigation of primary cell-wall architecture at a molecular level, providing complementary information to that obtained by Fourier-transform infrared microspectroscopy. The use of an extraction procedure using imidazole instead of cyclohexane trans-1,2-N,N,N[prime],N[prime]-diaminotetraacetate allows the extension of the infrared spectral window for data interpretation from 1300 to 800 cm-1, to 2000 to 800 cm-1, and allows us to obtain Raman spectra from extracted cell-wall material. Wall constituents such as pectins, proteins, aromatic phenolics, cellulose, and hemicellulose have characteristic spectral features that can be used to identify and/or fingerprint these polymers without, in most cases, the need for any physical separation. The Gramineae (rice [Oryza sativa], polypogon [Polypogon fugax steud], and sweet corn [Zea mays]) are spectroscopically very different from the nongraminaceous monocotyledon (onion [Allium cepa]) and the dicotyledon (carrot [Daucus carota]); this reflects differences in chemical composition and cross-linking of the walls. The possibility of a taxonomic classification of plant cell walls based on infrared and Raman spectroscopies and the use of spectral fingerprinting for authentication and detection of adulteration of products rich in cell-wall materials are discussed.
ABSTRACT
A method for the measurement of o-tyrosine in irradiated chicken has been developed. The procedure involves the solvent extraction and removal of free o-tyrosine, which is present in unirradiated tissue, followed by acid hydrolysis of bound o-tyrosine in the proteinaceous residue and measurement of the cleaved residues by HPLC with fluorescence detection. Bound o-tyrosine was not detected above 0.01 mg/kg in unirradiated tissue but was observed, in increasing amounts of up to 5.18 mg/kg, when the tissue was irradiated at doses of between 2.5 and 20 kGy. The precision of the analysis was assessed by duplicate determinations, the agreement between duplicates and their respective means averaged 1.7% as defined by the term [(a-b)/(a+b)] x 100% where a and b are the repeat determination values.
