Structure of the asparagine-linked sugar chains of porcine kidney and human urine cerebroside sulfate activator protein

The specific sugar residues and their linkages in the oligosaccharides from pig kidney and human urine cerebroside sulfate activator proteins (saposin B), although previously hypothesized, have been unambiguously characterized. Exhaustive sequential exoglycosidase digestion of the trimethyl-p-aminophenyl derivatives, followed by either matrix-assisted laser desorption/ionization and/or mass spectrometry, was used to define the residues and their linkages. The oligosaccharides were enzymatically released from the proteins by treatment with peptidyl-N-glycosidase F and separated from the proteins by reversed-phase high-performance liquid chromatography (HPLC). Reducing termini were converted to the trimethyl-p-aminophenyl derivative and the samples were further purified by normal-phase HPLC. The derivatized carbohydrates were then treated sequentially with a series of exoglycosidases of defined specificity, and the products of each digestion were examined by mass spectrometry. The pentasaccharides from pig kidney and human urine protein were shown to be of the asparagine-linked complex type composed of mannose-alpha 1-6-mannose-beta 1-4-N-acetylglucosamine-N-acetylglucosamine(alpha 1-6-fucose). This highly degraded structure probably represents the final product of intra-lysosomal exoglycosidase digestion. Oligosaccharide sequencing by specific exoglycosidase degradation coupled with mass spectrometry is more rapid than conventional oligosaccharide sequencing. The procedures developed will be useful for sequencing other oligosaccharides including those from other members of the lipid-binding protein class to which cerebroside sulfate activator belongs. (c) 2000 John Wiley & Sons, Ltd.     

A definitive investigation of the reaction of cyclopentadiene with cis-3,4-dichlorocyclobutene: A literature correction

Structural assignments are made to the three adducts derived from the title reaction. ¹H-n.m.r., ¹³C-n.m.r. and euroshift data are used to support the new structures.     

Femtosecond intermolecular electron transfer in condensed systems

We have investigated the ultrafast intermolecular electron transfer (ET) from an electron-donating solvent (aniline (AN) or N, N-dimethylaniline (DMA)) to an excited dye molecule (oxazines (Nile blue and oxazine 1) or coumarins). A non-exponential time dependence was observed in AN and can be explained by solvent reorientation and nuclear motion of the reactants. However, in DMA, a single exponential process was observed for Nile blue (160 fs) and oxazine 1 (280 fs), which can be explained by assuming that the rate of ET is limited mainly by ultrafast nuclear motion. A clear substituent effect on intermolecular ET was observed for the 7-aminocoumarins. When the alkyl chain on the 7-amino group is extended and a hexagonal ring with the benzene moiety is formed, the rate of ET is reduced by three orders of magnitude. This effect can be explained by a change in the free energy difference of the reaction and by the vibrational motion of the amino group.     

Fermi and Coulomb correlations in the 21 S state of the helium isoelectronic sequence

The Fermi and Coulomb holes of the 2¹ S state of the helium isoelectronic sequence are investigated. Several interesting differences between the results obtained and those which might be expected on the basis of the corresponding 2³ S state are pointed out and discussed.     

Dilute sulfuric acid pretreatment of corn stover at high solids concentrations

Applied Biochemistry and Biotechnology - The enzymatic digestibility of a pretreated substrate is enhanced by increasing the severity of the pretreatment conditions, apparently because a greater...     

Comparison of fluorimetric methods of assay for 7 H-Benz(de)anthracen-7-one in airborne particulates and air pollution source effluents

Summary Various modifications of a thin-layer chromatography fluorimetric method for the determination of 7 H-benz(de)anthracen-7-one (BO) and phenalen-1-one (PO) in complex mixtures have been compared. The best modifications consisted of one-dimensional thin-layer chromatography followed by elution, evaporation, solution in trifluoroacetic acid, followed by either spectrophotofluorimetric or fluorimetric assay. In some cases a quenching agent was necessary to quench the fluorescence of the interferences. Urban atmospheres and air pollution source effluents can be analyzed by these micromethods. These methods with slight modification could be applied to the determination of the aza heterocyclic and the other ring-carbonyl compounds found in urban atmospheres and air pollution source effluents.

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Zusammenfassung Verschiedene Modifikationen einer dünnschichtchromatographischen, fluorimetrischen Methode zur Bestimmung von 7 H-Benz(de)-anthracen-7-on (BO) und Phenalen-1-on (PO) in komplexen Gemischen wurden verglichen. Am besten bewährte sich eindimensionale Dünnschichtchromatographie, nachfolgende Elution, Abdampfen, Aufnehmen in Trifluoressigsäure und schließlich Bestimmung durch Spektralfluoreszenz-oder Fluoreszenzmessung. In manchen Fällen war es nötig, die Fluoreszenz störender Substanzen mit einem geeigneten Reagens zu löschen. Stadtatmosphäre oder Quellen der Luftverunreinigung können mit diesen Mikromethoden analysiert werden. Sie eignen sich nach geringfügiger Modifikation auch zur Bestimmung von azaheterocyklischen und anderen Ring-Carbonylverbindungen in der Atmosphäre.

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Résumé On a comparé entre elles différentes modifications d'une méthode de fluorimétrie avec chromatographie en couche mince pour le dosage de la benzo-7 H anthracène-one-7 (BO) et de la phénalène-one-1 (PO) en mélanges complexes. Les modifications les meilleures ont consisté en une Chromatographie en couche mince unidimensionnelle suivie d'élution, évaporation, mise en solution dans l'acide trifluoroacétique, opérations suivies d'une recherche spectrophotofluorimétrique ou fluorimétrique. Dans certains cas, un agent d'extinction s'est montré nécessaire pour éteindre la fluorescence due aux interférences. On peut analyser par ces microméthodes les atmosphères urbaines et les écoulements sources de pollution de l'air. Ces méthodes ont pu être appliquées après légère modification au dosage des composés aza hétérocycliques et autres composés carbonyles cycliques trouvés dans les atmosphères urbaines et dans les écoulements sources de pollution de l'air.

     

The isolation and structure determination of cryptomisrine,a novel indolo[3,2-b]quinoline dimeric alkaloid from cryptolepis sanguinolenta

The isolation and structure determination of cryptomisrine, a novel indolo[3,2-b]quinoline dimeric alkaloid obtained from extracts of the roots of the Ghanaian medicinal plant Cryptolepis sanguinolenta is reported. The structure determination was made via a consideration of the spectral data, including uv, ir, nmr, and mass spectra. In particular, one-dimensional proton/carbon nmr, one-dimensional nOe difference nmr, and a series of homonuclear (COSY) and inverse-detected heteronuclear two-dimensional (HMQC, HMBC) experiments were utilized, as well as high resolution FABMS. Cryptomisrine is most unusual in that its two monomeric parts apparently exist in such a C₂ symmetric environment that only one set of proton and carbon nmr resonances are observed. Cryptomisrine is the first example of a dimeric indolo-[3,2-b]quinoline alkaloid to have been isolated from nature.     

Structure and properties of the ion pair charge-transfer complex of octacyanotungstate(IV) with the 2,2′-bipyridinium dication

The X-ray crystal structure of (bpyH2)2[W(CN)8]·4H2 O (bpyH2=2,2-bipyridinium) is described. The [W(CN)8]4– anion has an approximately square antiprismatic (D4d) conformation, seemingly imposed by strong anion–water–cation hydrogen-bonding interactions. Bond distances in the anion are: WC 2.150(5), 2.163(5); CN 1.128(6), 1.145(6)Å and the angles WCN are 177.6(5), 178.3(5)°. The dihydrate and the anhydrous salt are both intensely black solids, exhibiting ion-pair charge-transfer interaction between cation and anion. E.s.r. spectra indicate that 30% of the tungsten is present as WV in the solid state, but that in solution only the WIV complex is present. The electron withdrawing effect of the cation is discussed and compared with that in a series of salts with different bipyridinium cations.