Separation of sodiated isobaric disaccharides and trisaccharides using electrospray ionization-atmospheric pressure ion mobility-time of flight mass spectrometry

A series of isobaric disaccharide-alditols, four derived from O-linked glycoproteins, and select trisaccharides were rapidly resolved using tandem high resolution atmospheric pressure ion-mobility time-of-flight mass spectrometry. Electrospray ionization was used to create the gas-phase sodium adducts of each carbohydrate. Using this technique it was possible to separate up to three isobaric disaccharide alditols and three trisaccharides in the gas phase. Reduced mobility values and experimentally determined ion-neutral cross sections are reported for each sodium-carbohydrate complex. These studies demonstrated that ion mobility separations at atmospheric pressure can provide a high-resolution dimension for analysis of carbohydrate ions that is complementary to traditional mass spectral (m/z) ion analysis. Combining these independent principles for separation of ions provides a powerful new bioanalytical tool for the identification of isomeric carbohydrates.     

Artificial red cells with crosslinked hemoglobin membranes

Artificial cells containing concentrated hemoglobin (Hb) solution were prepared by interfacial polymerization of Hb with glutaraldehyde (GA) in liquid membrane capsules (LMC). A solution containing 30% of Hb was emulsified in mineral oil as red cell-size microdroplets, and this emulsion was dispersed in an aqueous phase containing glutaraldehyde to form LMC. The LMC were semipermeable templates that held the microdroplets of Hb in suspension while GA diffused through the oil to the microdroplet surfaces. The GA crosslinked Hb at the surface of each microdroplet to form an artificial red-cell membrane encapsulating Hb solution. A water-soluble surfactant was used to eject the cells from the LMC and suspend them in saline. Several surfactants were evaluated. Cell size was controlled by agitation speed during preparation of the original emulsion. Cells of 2.52 = ±1.69 μm were prepared. The encapsulated Hb retained capacity to bind and release O₂. The cells had aP ₅₀ of 8.9 torr (1200 Pa) and a capacity of 0.55 cc O₂/g of total Hb, indicating that the crosslinked portion of the Hb did not contribute to O₂ transport.     

Double indication in catalytic-kinetic analysis: simultaneous photometric and thermometric indication of the iodine-azide reaction in closed and flow systems

The iodine—azide reaction catalyzed by sulphur-containing compounds is followed simultaneously by optical and thermometric measurements in closed and flowing systems. In the closed system, thiosulphate can be determined in the range 32.4–324 μg ml^-1, by observing the turbidity caused by the nitrogen formed during the reaction and the temperature changes. With the flow apparatus, thiosulphate can be determined in the range 112–1120 μg ml^-1 by continuously mixing the sample and reagent solutions. H₂S in nitrogen 5–100 ppm) is measured by sweeping the gas into the reaction Cuvette. In a third flow procedure, H₂S is liberated continuously from sodium sulphide solutions (0.1–10 μg S^2- ml^-1) by ascorbic acid, and swept to the measuring cuvette with nitrogen.     

Verwendung eines Ge(Li)-Detektors in der radiochemischen Analyse

Zusammenfassung Zur Bestimmung der U- und Th-Gehalte in 0,5–1,5mg wiegenden Mikroproben von ThO₂-UO₂-Kernbrennstoffen wurde die Neutronenaktivierungsanalyse mit zerstörungsfreier-Spektrometrie eingesetzt. Bei Gehalten über 0,1% beträgt die relative Standardabweichung 6%. Der Th-Gehalt der Mikroproben wird durch-spektrometrische Messung des²³³Pa ermittelt; bei Natur-Uran enthaltenden Proben wird der U-Gehalt über²³⁹Np bestimmt, bei hochangereichertes UO₂ enthaltenden Proben über¹³¹J. Mit der beschriebenen Methode können sowohl unbestrahlte als auch bestrahlte ThO₂-UO₂-Kernbrennstoffe untersucht werden.

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Use of a Ge(Li) detector in radiochemical analysisII. determination of U and Th contents in microsamples of ThO²-UO² nuclear fuels

Neutron activation analysis with non-destructive-spectrometry has been used to determine U and Th in microsamples (0.5–1.5 mg) from ThO₂-UO₂ nuclear fuels. With U contents of more than 0.1% the relative standard deviation amounts to 6%. Th in the microsamples is estimated by measuring²³³Pa; in natural UO₂ containing samples²³⁹Np ist measured for U determination, in highly enriched UO₂ samples¹³¹J. Fresh und spent ThO₂-UO₂ nuclear fuels can be investigated by the method described.

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Teil I siehe [3].

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Herrn G. Hofmann danken wir für die Entnahme der Mikro-Bohrproben aus den bestrahlten und unbestrahlten Brennstoffschliffen.     

Influence of increasing zinc contents in brass in the early stages of corrosion investigated by in-situ TM-AFM and SIMS

In-situ tapping mode atomic force microscopy (TM-AFM), a powerful, high-resolution imaging technique for determining the structure of surfaces and ex-situ secondary ion mass spectroscopy (SIMS), a multielement, high-depth-resolution method, were used to examine the influence of increasing zinc contents in brass in the early stages of corrosion. Four different samples (pure Cu, pure Zn, Cu/Zn=90/10 wt% and Cu/Zn=70/30 wt%) were studied in order to determine their chemical behaviour under various atmospheric conditions. The in-situ TM-AFM investigations were carried out in synthetic air with 60% relative humidity (RH) and 80% RH with 250 ppb SO(2). The samples for the ex-situ SIMS experiments were weathered over a period of 60 h in 80% RH and 250 ppb SO(2). The in-situ TM-AFM investigations have shown that an increasing Zn content in brass increases the corrosion rate.     

Polymerization in the crystalline state. IX. Relation between the velocity of radiation-induced in-source polymerization and post-polymerization

A general relation is derived between the polymerization velocities to be expected for crystalline monomers during irradiation at a polymerization temperature and the post-polymerization observed in samples irradiated at very low temperatures and subsequently warmed outside the irradiation source. For acrylamide, the experimental data are in satisfactory agreement with the theoretical relationship. The possible reasons for a deviation from this relationship are discussed.     

Chemical biology of protein lipidation: semi-synthesis and structure elucidation of prenylated RabGTPases

Rab/Ypt guanosine triphosphatases (GTPases) represent a family of key membrane traffic regulators in eukaryotic cells. For their function Rab/Ypt proteins require double modification with two covalently bound geranylgeranyl lipid moieties at the C-terminus. Generally, prenylated proteins are very difficult to obtain by recombinant or enzymatic methods. We generated prenylated RabGTPases using a combination of chemical synthesis and protein engineering. This semi-synthesis depends largely on the availability of functionalized prenylated peptides corresponding to the proteins' native structure or modifications. We developed solution phase and solid phase strategies for the generation of peptides corresponding to the prenylated C-terminus of Rab7 GTPase in preparative amounts enabling us to crystallize the mono-prenylated Ypt1:RabGDI complex. The structure of the complex provides a structural basis for the ability of RabGDI to inhibit the release of nucleotide by Rab proteins and a molecular basis for understanding a RabGDI mutant that causes mental retardation in humans.     

Heating in a stream of oxidizing or reducing gas for the qualitative analysis of inorganic substances

Summary Observation of the phenomena resulting from heating a substance first in air and then in hydrogen is recommended for the preliminary examination of small specimens of inorganic matter. It may permit immediate identification of simple compounds of the heavy metals. Reduction by heating in hydrogen is also recommended for the investigation of acid insoluble residues.

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Zusammenfassung Das Verhalten beim Erhitzen in Luft und dann in einer Wasserstoff-atmosphäre eignet sich für die Vorprüfung kleiner Mengen anorganischer Substanz. In einzelnen Fällen können einfache Verbindungen der Schwermetalle daran erkannt werden. Die Reduktion durch Erhitzen in einer Wasserstoffatmosphäre empfiehlt sich ferner für die Untersuchung säureunlöslicher Rückstände.

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Résumé L'observation du phénomène résultant du chauffage d'une substance dans l'air puis dans l'hydrogène est recommandée comme examen préliminaire de petits échantillons minéraux. Elle peut permettre l'identification immédiate de composés simples des métaux lourds. La réduction par chauffage dans l'hydrogène est également recommandée pour l'examen de résidus insolubles dans les acides.

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Dedicated to Prof.Hans Lieb on occasion of his 70th birthday.