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  • 1-Formylalkanesulfonates  (1)
  • Bioinorganic chemistry  (1)
  • Cyclic diphosphoglycerate  (1)
  • 1
    ISSN: 1432-072X
    Keywords: Key words Methanogenic archaea ; Formyltransferase ; Cyclohydrolase ; N5 ; N10-Methenyltetrahydromethanopterin ; Formylmethanofuran ; Halophilic enzymes ; Thermophilic enzymes ; 2-Phosphoglycerate kinase ; Cyclic diphosphoglycerate ; synthase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Enzymes involved in methane formation from carbon dioxide and dihydrogen in Methanopyrus kandleri require high concentrations (〉 1 M) of lyotropic salts such as K2HPO4/KH2PO4 or (NH4)2SO4 for activity and for thermostability. The requirement correlates with high intracellular concentrations of cyclic 2,3-diphosphoglycerate (cDPG; ≈ 1 M) in this hyperthermophilic organism. We report here on the effects of potassium cDPG on the activity and thermostability of the two methanogenic enzymes cyclohydrolase and formyltransferase and show that at cDPG concentrations prevailing in the cells the investigated enzymes are highly active and completely thermostable. At molar concentrations also the potassium salts of phosphate and of 2,3-bisphosphoglycerate, the biosynthetic precursor of cDPG, were found to confer activity and thermostability to the enzymes. Thermodynamic arguments are discussed as to why cDPG, rather than these salts, is present in high concentrations in the cells of Mp. kandleri.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Ligands, tridentate ; Nickel ; Thioethers ; Bioinorganic chemistry ; Racemization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexation behavior of three chiral, tripodal N,O,S-ligands with nickel(II) salts was examined. It was found that the coordination mode of the ligands (bidentate N,O and N,S; tridentate N,O,S) and of the central nickel ion (square-planar vs. pseudo-octahedral) is not simply an intrinsic property of the ligand-metal combination, but also a function of the counter ions and of the solvent of crystallization. In the case of one ligand, a diamagnetic square-planar and a paramagnetic pseudo-octahedral form could be switched back and forth, by just changing the solvent of crystallization from methanol to ethanol. By using an enantiomerically pure tripodal N,O,S-ligand, a metal induced racemization was unveiled which would have otherwise remained undetected.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1147-1151 
    ISSN: 0009-2940
    Keywords: 1-Formylalkanesulfonates ; 1-Diazoalkanesulfonates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1-Formyl- und 1-DiazoalkansulfonateDurch Deprotonierung der Neopentyl-, Isobutyl- und Isopropylester der Methan- und Ethansulfonsäure mit n-Butyllithium und nachfolgende Reaktion mit Ameisensäure-ethylester wurden die entsprechenden 1-Formylalkansulfonsäureester in 77-90% Ausbeute erhalten. Am Beispiel des 1-Formylethansulfonsäure-neopentylesters wurde gezeigt, daß durch weitere Umsetzung mit Dimethylsulfat und Base 1-(Methoxymethylen)alkansulfonsäureester zugänglich sind. Die 1-Formylalkansulfonsäureester konnten mit Arylsulfonylaziden durch entformylierende Diazogruppen-übertragung in 28-65% Ausbeute zu den stabilen 1-Diazoalkansulfonsäureestern umgesetzt werden. Die chemischen Eigenschaften dieser neuen Diazoverbindungen gleichen denen der 1-Diazoalkanphosphonsäureester, so führt z. B. die Entschützung zum Sulfonatanion zur spontanen Stickstoffabspaltung. Die Thermolyse des 1-Diazoethansulfonsäure-isobutylesters in inertem Lösungsmitel ergab Vinylsulfonsäure-isobutylester als Hauptprodukt.
    Notes: The deprotonation of the neopentyl, isobutyl and isopropyl esters of methane- and ethanesulfonic acid with n-butyllithium and subsequent reaction with ethyl formate afforded the corresponding 1-formylalkanesulfonates in 77-90% yield. 1-(Methoxymethylene)alkanesulfonates could be obtained by additional treatment with dimethyl sulfate and base, as examplified in the case of neopentyl 1-formylethanesulfonate. Furthermore, the formylated sulfonates were converted into the stable 1-diazoalkanesulfonates in 28-65% yield employing arylsulfonyl azides as diazo group transfer reagents. The chemical behaviour of the novel 1-diazoalkanesulfonates resembles that of 1-diazoalkanephosphonates, e.g., deprotection to the 1-diazoalkanesulfonate anion resulted in rapid denitrogenation. The thermolysis of isobutyl 1-diazoethanesulfonate in an inert solvent afforded isobutyl vinylsulfonate as the major product.
    Type of Medium: Electronic Resource
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