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The potential of ionic liquids as solvents for headspace gas chromatography was investigated. Three compounds with boiling points above 200 [degrees]C were selected to demonstrate the feasibility of the concept described. 2-Ethylhexanoic acid, formamide, and tri-n-butylamine as examples of acidic, neutral, and basic analytes were dissolved in acidic 1-n-butyl-3-methylimidazolium hydrogen sulfate (1), neutral 1-n-butyl-2,3-dimethylimidazolium dicyanamide (2), and 2 containing 1,8-diazabicyclo[5.4.0]undec-7-ene to adjust basic conditions. All analytes could be determined with limits of detection and limits of quantification in the low-ppm concentration range.

Herein we describe a possibility of selective dissolution of xylan, the most important type of hemicellulose, from Eucalyptus globulus kraft pulp using ionic liquids (ILs). On the basis of the IL 1-butyl-3-methylimidazolium dimethyl phosphate, which is well-known to dissolve pulp, the phosphate anion was modified by substituting one oxygen atom for sulfur and selenium, respectively. This alteration reduces the hydrogen bond basicity of the IL and therefore prevents dissolution of cellulose fibers, whereas the less ordered xylan is still dissolved. (1)H NMR spectra of model solutions and Kamlet-Taft parameters were used to quantify the solvent polarity and hydrogen bond acceptor properties of the ILs. These parameters have been correlated to their ability to dissolve xylan and cellulose, which was monitored by (13)C NMR spectroscopy. It was found that the selectivity for xylan dissolution increases to a certain extent with decreasing hydrogen-bond-accepting ability of anions of the ILs.

Tosylmethyl isocyanide was used to convert 7,8-didehydro-6-ketomorphinans to 6,7-didehydromorphinan-6-carbonitriles with retainment of the 4,5-epoxy ring. However, ring opening occurred in the presence of NaH giving 5,6,7,8-tetradehydromorphinan-6-carbonitriles. Addition of nucleophiles such as Li diisopropylamide or Grignard reagents to the acrylonitrile substructure yielded ring-opened 5,6-didehydro products. Seven products were characterized by X-ray crystal structure analysis and revealed insight into the mechanistic diversity of the van Leusen reaction.

On the basis of the structural features of the Dmt-Tic pharmacophore, a new motif leading to a fairly potent mu-opioid antagonist is described. This motif contains the 4-amino-1,2,4,5-tetrahydro-2-benzazepine-3-one skeleton as a substitute for the Tic residue, which provides the conformational constraint compatible with the mu-opioid receptor. The stereoselective synthesis of four stereoisomers is performed starting from homochiral 2',6'-dimethyltyrosine (Dmt) and o-aminomethylphenylalanine.

X-ray structure determinations of two different single crystals of octamethylferrocenium tetrafluoroborate (OMFc(+)BF(4)(-)) revealed conformational polymorphism with ligand twist angles of 180 degrees and 108 degrees , respectively. Their concomitant occurrence could be explained by the small lattice energy difference of 3.2 kJ mol(-1). Temperature-dependent Moessbauer spectroscopy of (57)Fe-labeled OMFc(+)BF(4)(-) over the range 90 < T < 370 K did not show the anomalous sudden increase in the motion of the metal atom as observed in neutral OMFc. Broadened absorption curves characteristic of relaxation spectra were obtained with an isomer shift of 0.466(6) mm s(-1) at 90 K. The temperature dependence of the isomer shift corresponded to an effective vibrating mass of 79 +/- 10 Da and, in conjunction with the temperature dependence of the recoil-free fraction, to a Moessbauer lattice temperature of 89 K. The spin relaxation rate could be better described by an Orbach rather than a Raman process. At 400 K, a reversible solid-solid transition to a plastic crystalline mesophase was noted.

Arsenate reductase (ArsC) encoded by Staphylococcus aureus arsenic-resistance plasmid pI258 reduces intracellular As(V) (arsenate) to the more toxic As(III) (arsenite), which is subsequently extruded from the cell. ArsC couples to thioredoxin, thioredoxin reductase, and NADPH to be enzymatically active. A novel purification method leads to high production levels of highly pure enzyme. A reverse phase method was introduced to systematically analyze and control the oxidation status of the enzyme. The essential cysteinyl residues and redox couple in arsenate reductase were identified by a combination of site-specific mutagenesis and endoprotease-digest mass spectroscopy analysis. The secondary structures, as determined with CD, of wild-type ArsC and its Cys mutants showed a relatively high helical content, independent of the redox status. Mutation of Cys 10, 82, and 89 led to redox-inactive enzymes. ArsC was oxidized in a single catalytic cycle and subsequently digested with endoproteinases ArgC, AspN, and GluC. From the peptide-mass profiles, cysteines 82 and 89 were identified as the redox couple of ArsC necessary to reduce arsenate to arsenite.