A neutron scattering and nuclear magnetic resonance study of the structure of GeO2-P2O5 glasses

Germanophosphate (GeO2-P2O5) glasses were studied with neutron diffraction, phosphorus, and oxygen nuclear magnetic resonance, calorimetry, viscosity measurements, and first-principles calculations. These data sets were combined to propose a structural model of GeO2-P2O5 glasses, which includes tetrahedrally coordinated phosphorus, formation of octahedrally coordinated germanium as P2O5 content increases, an absence of trigonally coordinated oxygen, and hence an absence of rutile-like GeO2 domains. The structural model was then used to propose explanations for both the observed composition dependence of the glass transition temperature and the fragility of the GeO2-P2O5 liquids.     

Spectroscopic studies on the effect of temperature on pH-induced folded states of human serum albumin

Human serum albumin (HSA) is a very important multi-domain transporter protein in the circulatory system responsible for carriage of various kinds of ligands within the physiological system. HSA is also known to undergo conformational transformation at different pH(s) and temperatures. In this report we have studied the binding interactions of a photosensitizing drug, protoporphyrin IX (PPIX) with various conformers of HSA at different temperatures using picosecond time-resolved fluorescence spectroscopy. Also, using dynamic light scattering (DLS) and circular dichroism (CD) spectroscopy we have followed the structural transition of various conformers of HSA at different temperatures. Ensuring the intact binding of PPIX to various conformers of HSA at different temperatures as revealed through time-resolved fluorescence anisotropy decay and significant spectral overlap of emission of Trp214 residue (donor) in domain-IIA and absorption of PPIX (acceptor) bound to domain-IB of HSA, we have applied F?rster's resonance energy transfer (FRET) technique to determine the interdomain separation under various environmental conditions. The alkali-induced conformer of HSA shows almost no change in donor-acceptor distance in contrast to the native and acid-induced conformers of HSA, which show a decrease in distance with increase in temperature. Through this study the non-covalently bound PPIX is shown to be an efficient FRET probe in reporting the different temperature-induced folded states of HSA in buffer solutions of widely differing pH values.     

The investigation of industrial plant processes using radiotracer techniques

Additional plant has been commissioned at the Springfields Works of BNFL to obtain increased production of uranium tetrafluoride. A programme of investigational work was undertaken during production to improve our understanding of the process. This paper describes some of the radiometric techniques used in the project, including passive gamma and neutron measurements and experiments using radioactive tracers.     

Versatile multilayer thin film preparation using hydrophobic interactions, crystallization, and chemical modification of poly(vinyl alcohol)

Multilayer thin film coatings were prepared on silicon substrates. Poly(vinyl alcohol) was adsorbed from aqueous solution to propyldimethylsilyl-modified silicon wafers. This thin semicrystalline coating was chemically modified using acid chlorides to form thicker, hydrophobic coatings. The products of the modification reactions allowed adsorption of a subsequent layer of poly(vinyl alcohol) that could subsequently be hydrophobized. This two-step process (adsorption/chemical modification) allows layer-by-layer deposition to prepare coatings with thickness, chemical structure, and wettability control.     

21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Greatly Expands Mass Spectrometry Toolbox

We provide the initial performance evaluation of a 21 Tesla Fourier transform ion cyclotron resonance mass spectrometer operating at the Environmental Molecular Sciences Laboratory at the Pacific Northwest National Laboratory. The spectrometer constructed for the 21T system employs a commercial dual linear ion trap mass spectrometer coupled to a FTICR spectrometer designed and built in-house. Performance gains from moving to higher magnetic field strength are exemplified by the measurement of peptide isotopic fine structure, complex natural organic matter mixtures, and large proteins. Accurate determination of isotopic fine structure was demonstrated for doubly charged Substance P with minimal spectral averaging, and 8158 molecular formulas assigned to Suwannee River Fulvic Acid standard with root-mean-square (RMS) error of 10 ppb. We also demonstrated superior performance for intact proteins; namely, broadband isotopic resolution of the entire charge state distribution of apo-transferrin (78 kDa) and facile isotopic resolution of monoclonal antibody under a variety of acquisition parameters (e.g., 6 s time-domains with absorption mode processing yielded resolution of approximately 1 M at m/z?=?2700).

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Metal---metal bond formation promoted by steric effects: The structural chemistry of μ-dichlorobis(di-t-butyl-p-tolylphosphine)tetracarbonyldiruthenium(I)

The bulky teratiary phosphines P-t-Bu₂Ph and P-t-Bu₂-p-tol, provide binuclear ruthenium(I) complexes. An X-ray analysis of [Ru₂Cl₂(CO)₄(P-t-Bu₂-p-tol)₂] shows the RuCl₂Ru bridge to be non-planar and to have an Ru---Ru distance of 2.632Å.     

Chiral pyridin-3-ones and pyridines: syntheses of enantiopure 2,4-disubstituted 6-hydroxy-1,6-dihydro-2H-pyridin-3-ones, 2,3-disubstituted 4-iodopyridines, and enantiopure 2,3-disubstituted 4-pyridinemethanols

The development of an innovative method to access enantiopure 2,4-disubstituted 6-hydroxy-1,6-dihydro-2H-pyridin-3-ones starting from D-glucal via the aza-Achmatowicz transformation has been described. These highly functionalized pyridin-3-ones have been utilized for the synthesis of contiguously substituted pyridines through a rapid and efficient Et(3)N/Ac(2)O promoted cyclo-elimination, aromatization cascade, allowing the facile assembly of important pyridine-based building blocks like 2-substituted 3-acetoxy-4-iodopyridines and enantiopure 2-substituted 3-acetoxy-4-pyridinemethanols possessing benzylic stereogenic centers, whose synthesis otherwise would be tedious. The utilization of commercially available sugars as starting materials, mild reaction conditions, catalytic transfer hydrogen (CTH) of α-furfuryl azide derivatives, transfer of chiral aryl/alkyl methanols from enulosides to pyridin-3-ones and pyridines, high yields, and short reaction times are key features of this method. The utility of the method has been further exemplified by demonstrating the usage of the 2-substituted 3-acetoxy-4-iodopyridine for the construction of biologically significant molecules like 2,7-disubstituted furo[2,3-c]pyridines and 7,7'-disubstituted 2,2'-bifuro[2,3-c]pyridines.     

Hydroxyl-directed cyclizations of 1,6-enynes

The palladium-catalyzed, hydroxyl-directed cyclization reactions of 1,6-enynes provide a highly diastereoselective process for the syntheses of stereochemically defined cyclopentanes. Consistently high levels of cis-selectivity are possible using homopropargyl alcohols in contrast to the corresponding propargyl alcohols. Hydroborylative enyne cyclizations coupled with this directing group effect provide a useful method for the syntheses of multifaceted compounds bearing all carbon quaternary centers.     

FTIR analysis of the hydrolysis rate in the sol–gel formation of gadolinia-doped ceria with acetylacetonate precursors

This study reveals that Fourier transform infrared is an effective analytical tool in probing the extent of hydrolysis of cerium and gadolinium acetylacetonates dissolved in methanol. It is found that these acetylacetonates have relatively fast hydrolysis rates at the early stage of hydrolysis (<6 h). However, their hydrolysis rates become very slow beyond 6-h of hydrolysis and decrease to near zero after 55-h of hydrolysis. As a result, hydrolysis cannot be completed even after 170 h at room temperature. These phenomena suggest that the first and second acetylacetone ligands chelated to Ce³⁺ and Gd³⁺ ions can actually be hydrolyzed with relative ease at room temperature, similar to alkoxide ligands. It is the last acetylacetone ligand that is very difficult to be hydrolyzed.     

In situ analysis of solvents on breath and blood: a selected ion flow tube mass spectrometric study

We report measurements of residual vapour levels of xylenes and trimethylbenzenes, present following a floor re-surfacing procedure, using the technique of selected ion flow tube mass spectrometry (SIFT-MS). A subject exposed to controlled amounts of xylene and mesitylene was monitored by direct breath exhalation over a 4-hour period after exposure to the volatile organic compounds (VOCs) had stopped. The headspace gases above 5 mL blood samples taken over this period were also monitored. The decays of the solvent levels with time were fitted to a two-compartment model with residence times for xylene and mesitylene of 0.37 h and 0.38 h, respectively (compartment one) and 2.5 h and 2.8 h, respectively (compartment two).