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  • 1985-1989  (5)
  • 1
    ISSN: 1365-2222
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Medicine
    Notes: Asthmatic patients have a deficiency of concanavalin A-(Con A) induced suppressor cell function. We tested whether oral colchicine 0·5 mg twice daily for 7 days could correct this immunoregulatory abnormality. Peripheral blood mononuclear cells were incubated with Con A and then suppression of proliferation was measured by co-culture of these cells with healthy volunteers’mononuclear cells and phytohaemagglutinin. Sixteen asthmatic patients had significantly (P 〈 0·002) decreased Con A-induced suppressor cell function (17·0±17·2%, mean ± s.d.) as compared to 13 healthy volunteers (37·9±14·9%). Oral colchicine significantly (P 〈 0·05) increased, though only partially corrected, these 16 asthmatic patients’Con A-induced suppressor cell function (28·1±14·3%). Asthmatic patients had an increased number of monocytes (691±289 vs 388±271/mm3 for normals, P 〈 0·01) and a normal number of lymphocytes, Leu 4+ total T cells, Leu 3+ helper/inducer T cells, and Leu 2+ suppressor/cytotoxic T cells as well as a normal Leu 3/Leu 2 ratio. Oral colchicine significantly (P 〈 0·005) decreased the number of monocytes (451±255/mm3) without significantly affecting the number of lymphocytes, Leu 4+, Leu 3+, or Leu 2+ T cells, or the Leu 3/Leu 2 ratio. These results are consistent with the hypothesis that the deficiency of Con A-induced suppressor cell function in asthmatic patients may be due, in part, to an increased number and/or abnormal activity of monocytes. If so, then oral colchicine may have partially corrected the deficiency of Con A-induced suppressor cell function by decreasing the number and/or modulating the activity of monocytes.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Clinical & experimental allergy 17 (1987), S. 0 
    ISSN: 1365-2222
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Medicine
    Notes: Twenty patients with bronchial asthma, on long-term oral therapy with theophylline, demonstrated an increased number of suppressor T-cells and impaired graft vs host reaction. Ten asthmatics on other therapy, not including theophylline, as well as ten normal healthy controls, failed to show similar findings. Elimination of suppressor T-cells corrected the above immunological abnormalities in the theophylline-treated patients, while addition of serum from theophylline-treated asthmatic patients to lymphocytes from normal healthy controls, affected the graft vs host reaction of these lymphocytes. We conclude that theophylline induces quantitative as well as qualitative immunological alterations by increasing the number and activity of suppressor T-cells, which most probably secrete a serum factor, responsible for some of the abnormalities observed.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' Zeitschrift für analytische Chemie 323 (1986), S. 330-333 
    ISSN: 1618-2650
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Im Rahmen von kinetischen Untersuchungen zur Olefinpolymerisation mußten geringe Doppelbindungskonzentrationen in Polymeren mit stark differierender Struktur und Konsistenz exakt bestimmt werden. Die quantitative FTIR-Analyse der unterschiedlichen Doppelbindungen wurde dadurch optimiert, daß die Substanzen in der Schmelze vermessen wurden, die IR-Bandengruppen mittels rechnerisch erzeugter Bandenprofile entzerrt und die integralen Absorbanzen der olefinischen Banden bestimmt wurden. Die durch Analyse von Modellsubstanzen ermittelten integralen Extinktionskoeffizienten, bezogen auf 1 cm Schichtdicke und auf eine Doppelbindung pro 105 C-Atome liegen bei 0.93 (Vinyl), 0.95 (trans-Vinylen) und 1.04 (Vinyliden).
    Notes: Summary In the course of kinetic investigations on olefin polymerization it was necessary to measure the concentration of double bonds in polymers with very variable structure and consistency as exactly as possible. For that purpose, the quantitative FTIR-analysis of the different double bonds was optimized by measuring the melted substances, by analysis of the groups of IR-bands with the help of computer generated band profiles and by determing the integral absorbances of the olefinic bands. The integral extinction coefficients of the vinyl, the trans-vinylene and the vinylidene double bonds were determined by the analysis of model compounds and values of 0.93, 0.95 and 1.04, respectively, for a sample of 1 cm thickness with one double bond per 105 carbon atoms were obtained.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Cyclic Arsino Sulfur Diimide as an Intramolecular Bridging Ligand: Synthesis and X-Ray Structure Analysis of Os3(CO)10[μ-(t-Bu)As(NSN)2As(t-Bu)]The eight-membered sulfur diimide heterocycle (t-Bu)As(NSN)2As(t-Bu) (8) can be incorporated into a trinuclear carbonylosmium cluster either as a mono- or as a bidentate ligand. Reaction of the kinetically labile acetonitrile complex Os3(CO)11(CH3CN) with 8 in CH2Cl2 solution leads to a monosubstituted derivative of Os3(CO)12 of composition Os3(CO)11[(t-Bu)As(NSN)2As(t-Bu)] (9) which still contains one uncoordinated arsenic atom; addition of a second [Os3(CO)11] fragment to 9 was not observed. However, Me3NO-induced substitution of a carbonyl group in 9 results in coordination of the ligand 8 to the triosmium cluster through both arsenic atoms. The structure of the product Os3(CO)10[μ-(t-Bu)As(NSN)2As(t-Bu)](10)1 was determined by an X-ray structure analysis. I n the triangulo-triosmiumcarbonyl cluster 10, the ligand 8 occupies two equatorial positions at two adjacent osmium atoms, being coordinated through the arsenic atoms with Os — As distances of 2.403(1) Å The cluster molecule 10 possesses a 2-symmetry of crystallographic origin. The [Os3(CO)10] fragment and the eight-membered heterocyclic ligand are not changed significantly in their structures as compared with Os3(CO)10 and free 8, respectively. Nevertheless, coordination of 8 imposes its lower 2-symmetry upon the [Os3(CO)10] fragment. The reduction of mm2- to 2-symmetry (C2v to C2) for the cyclic arsino sulfur diimide 8 is more pronounced in the complex 10 than in the free state. The As … As distance in 10 (8.878(4) A) is considerably enlarged its compared to 8 (3.683(1) Å).
    Notes: Der achtgliedrige Schwefeldiimid-Heterocyclus (t-Bu)As(NSN)2As(t-Bu) (8) läßt sich als ein- oder zweizähniger Ligand in einen dreikernigen Osmiumcarbonyl-Cluster einbauen. Die Reaktion des kinetisch labilen Acetonitril-Komplexes Os3(CO)11(CH3CN) (5) mit 8 in CH2Cl2-Lösung führt zu einem monosubstituierten Derivat von Os3(CO)12 der Zusammensetzung Os3(CO)11[(t-Bu)As(NSN)2As(t-Bu)] (9), das noch ein unkomplexiertes Arsenatom enthält; die Anlagerung eines weiteren [Os3(CO)11]-Fragments an 9 konnte nicht beobachtet werden. Durch Me3NO-induzierte Substitution einer CO-Gruppe in 9 kann jedoch der Ligand 8 auch über das zweite Arsenatom an den Triosmiumcarbonyl-Cluster gebunden werden. Die Struktur des so gebildeten Produktes Os3(CO)10[μ-(t-Bu)As(NSN)2As(t-Bu)] (10)Decacarbonyl-μ-(3, 7-di-tert-butyl-3H,7H-1λ4,5λ4,2,4,6,8,3,7-dithiatetrazadiarsocin-As,As′)-triangulo-triosmium wurde durch eine Röntgenstrukturanalyse bestimmt. Der Ligand 8 besetzt im triangulo-Triosmiumcarbonyl-Cluster 10 zwei equatoriale Positionen an zwei benachbarten Osmiumatomen; er ist über die beiden Arsenatome koordiniert; die Os—As-Abstände betragen 2,403(1) Å. Das Clustermolekül 10 besitzt eine kristallographisch vorgegebene 2-Symmetrie; das [Os3(CO)10]-Fragment und der heterocyclische Achtring-Ligand sind gegenüber Os3(CO)12 bzw. freiem 8 strukturell nicht gravierend verändert. Allerdings zwingt 8 dem [Os3(CO)10]-Fragment seine niedrigere zweizählige Symmetrie auf. Die Erniedrigung der Symmetrie von mm2 nach 2 (C2v nach C2) ist für das cyclische Arsinoschwefeldiimid 8 im Komplex 10 noch stärker ausgeprägt als im freien Zustand. Der As…As-Abstand ist in 10 (3,878(2) Å) gegenüber 8 (3,683(1) Å) deutlich aufgeweitet.
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of S{NAs(tBu)2[Os3(CO)11]}2. The First Sulphur Diimide with trans,trans Configuration in the Solid StateIn the reaction of bis(di-tert-butylarsino) sulphur diimide, S(NAstBu2)2, with the cluster Os3(CO)11(NCCH3) either one or two [Os3(CO)11] units can be added to the sulphur diimide  -  according to the molar ratio  -  yielding Os3(CO)11As(tBu)2NSNAstBu2 (1) or S{NAs(tBu)2[Os3(CO)11]}2 (2), respectively. The title compound μ-[(trans,trans)-bis(di-tert-butyl-arsino)sulphur diimide-As,As]-bis(undecacarbonyl-triangulo-triosmium) (2) is also obtained upon thermolysis of 1 in refluxing octane; its structure was elucidated by X-ray crystallography. Complex 2 is the first sulphur diimide with a trans,trans configuration in solid state. The trans,trans configuration is forced by the bulky substituents. 2 crystallises with deuterochloroform (1:1) in the monoclinic space group C2/c: a = 25.887(3), b = 8.684(1), c = 26.357(4) Å, β = 103.34(1)°, Z = 4.Due to special positions the SN2 moiety (inversion center) and the chloroform molecule (twofold axis) are disordered statistically. The S=N bond lengths amount 1.50(2) Å on the average, the angle at, sulphur (111(2)°) is smaller in comparison with open-chained sulphur diimides with the cis, trans and cis,cis configuration. The angles a t the K atoms are enlarged (131(2) and 135(2)°), respectively. With exception of small torsions around the S=N bonds the principle of coplanarity for sulphur diimides is also fulfilled for t,he trans, trans form. The amino residues occupy equatorial positions in the triosmium clusters. I n the triosmium triangle two bonds are almost equal in length (2.891(1) and 2.884(1) Å, respectively), the third Os—Os bond is somewhat enlarged (2.939(1) Å).
    Notes: Bei der Umsetzung von Bis(di-tert-butylarsino)schwefeldiimid, S(NAstBu2)2, mit dem Cluster Os3(CO)11(NCCH3) können  -  je nach Molverhältnis  -  ein oder zwei [Os3(CO)11]-Einheiten an das Schwefeldiimid angelagert werden, wobei Os3(CO)11As(tBu)2NSNAstBu2 (1) bzw. S{NAs(tBu)2[Os3(CO)11]}2 (2) entstehen. Die Titelverbindung μ-[(trans,trans)-Bis(di-tert-butylarsino)-schwefeldiimid-As,As]-bis(undecacarbonyl-triangulo-triosmium) (2) wird auch bei der Thermolyse von 1 in siedendem Octan erhalten; ihre Struktur wurde röntgenstrukturanalytisch aufgeklärt. Komplex 2 ist das erste Schwefeldiimid mit einer trans,trans-Konfiguration im festen Aggregatzustand. Die ungewöhnliche Konfiguration wird durch die sterisch anspruchsvollen Substituenten erzwungen. 2 kristallisiert mit Deuterochloroform (1:1) in der monoklinen Raumgruppe C2/c: a = 25,887(3), b = 8,684(1), c = 26,357(4) Å, β = 103,34(1)°; Z = 4. Aufgrund spezieller Lagen sind die SN2-Einheit (Symmetriezentrum) und die Chloroformmolekel (zweizählige Achse) statistisch fehlgeordnet. Die S=N-Bindungslängen betragen im Mittel 1,50(2) Å; der Winkel am Schwefel (111(2)°) ist kleiner als bei offenkettingen Schwefeldiimiden mit cis,trans- und cis,cis-Konfiguration. Die Winkel an den N-Atomen sind aufgeweitet (131(2) bzw. 135(2)°). Abgesehen von geringen Torsionen um die S=N-Bindungen ist auch bei der trans,trans-Form das Koplanaritätsprinzip der Schwefeldiimide erfüllt. Die Arsinoreste besetzen in den Triosmiumcarbonylclustern equatoriale Positionen. Im Osmiumdreieck sind zwei Bindungen etwa gleich lang (2,891(1) und 2,884(1) Å), die dritte Os - Os-Bindung ist etwas aufgeweitet (2,939(1) Å).
    Additional Material: 3 Ill.
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