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71.
Michael Hartmann Rudolf Christian Erich Zbiral 《Monatshefte für Chemie / Chemical Monthly》1991,122(1-2):111-125
Summary While the reaction of the 4-oxo-Neu 5 Ac derivative2 a with tributoxy methyl zirconate led exclusively to equatorial 4-C-methyl derivative3 a, the analogous reaction with tetramethyl zirconate yielded a 3:2 mixture of both diastereoisomeres3 a and4 a. After removal of protecting groups the 5-acetamido-3,4-dideoxy-4-C-methyl-D-glycero-D-galacto-2-nonulosonic acid5 a and 5-acetamido-3,4-dideoxy-4-C-methyl-D-glycero-D-talo-2-nonulosonic acid6 a were obtained. The 4-C-methylene derivative was prepared by treatment of the same 4-oxo-derivative with CH2I2/Zn/Cp
2ZrCl2. Subsequent hydrogenation led to both epimeric 4-deoxy-4-C-methyl derivatives8 a and9 a. Final removal of protecting groups gave the 5-acetamido-3,4,5-trideoxy-4-C-methyl-D-glycero-D-galacto-2-nonulosonic acid10 a respectively the 5-acetamido-2,7-anhydro-4-C-methyl-3,4,5-trideoxy-D-glycero-D-talo-2-nonulosonic acid11 a. The -methylketosides of the 4-deoxy-4-C-methyl- (16) and 4-C-methylene-Neu 5 Ac (15) were prepared via the peracetylated derivatives to obtain modell substrates for enzymatic studies. Thus all free acids were tested for inhibition of CMP-sialate synthease. Only the 4-C-methylene compound15 showed most unexpectedly a strong competitive inhibition of this enzyme.
Strukturelle Abwandlungen an N-Acetylneuraminsäure, 19. Mitt.: Synthese der beiden Epimerenpaare der 4-C-Methyl- und 4-Deoxy-4-C-methyl- sowie des -Methylketosids der 4-Deoxy-4-C-methylen-N-acetylneuraminsäure. Verhalten gegenüber CMP-Sialat-Synthase
Zusammenfassung Während die Umsetzung des 4-Oxoderivates2 a mit (BuO)3 MeZr ausschließlich zur equatorialen 4-C-Methylverbindung3 a führt, wurde bei der Reaktion mitMe 4Zr ein 3:2-Gemisch der beiden Diastereomeren3 a und4 a erhalten. Das 4-C-Methylenderivat7 a wurde durch Reaktion derselben 4-Oxoverbindung mit CH2I2/Zn/Cp 2ZrCl2 erhalten. Eine anschließende Hydrierung (H2-Pd/C) führte zu einem trennbaren Germisch der beiden 4-Deoxy-4-C-methylderivative8 a und9 a. Diese Verbindungen konnten durch das Entfernen der Schutzgruppen einerseits in die 5-Acetamido-3,4,5-trideoxy-4-C-methyl-D-glycero-D-galacto-2-nonulosonsäure10 a und 5-Acetamido-2,7-anhydro-4-C-methyl-3,4,5-tridoxy-D-glycero-D-talo-2-nonulosonsäure11 a umgewandelt werden. Die Verbindungen Methyl-5-acetamido-4-C-methylen-3,4,5-trideoxy--D-manno-2-nonulopyranosidonat (15) und Methyl-5-acetemido-4-C-methyl-3,4,5-tridoxy--D-glycero-D-talo-2-nonulopyranosidonat (16) wurden als Modellverbindungen für enzymatische Untersuchungen über peracetylierte Zwischenstufen hergestellt. Überraschenderweise zeigte nur die 4-C-Methylenverbindung15 eine starke kompetitive Hemmung gegenüber CMP-Sialat-Synthase.相似文献
72.
Guerrero L Smart OS Woolley GA Allemann RK 《Journal of the American Chemical Society》2005,127(44):15624-15629
Control of DNA binding of HDH-3, a 18-residue polypeptide based on the recognition helix of the Q50K engrailed homeodomain, has been achieved. HDH-3 was linked to an azobenzene cross-linker through two cysteine residues in an i, i + 11 spacing. For the thermodynamically stable trans configuration of the cross-linker, the dark-adapted peptide (dad-HDH-3) adopted a mainly alpha-helical structure as judged by circular dichroism (CD) spectroscopy. After irradiation with light of 360 nm, the helical content of the peptide (irrad-HDH-3) was reduced significantly and the CD spectrum of the irradiated peptide resembled that of the largely unstructured, unalkylated peptide. Despite lacking helices-1 and -2 and the N-terminal arm of Q50K engrailed, dad-HDH-3 bound to its natural DNA target sequence TAATCC (QRE) with high affinity (K(D) = 7.5 +/- 1.3 nM). The binding affinity for the mutant DNA sequence, TAATTA (ERE), was reduced significantly (K(D) = 140 +/- 11 nM). Unlike irrad-HDH-3, which like the unalkylated parent peptide displayed only marginal DNA binding specificity, dad-HDH-3 specified base pairs 5 and 6 of QRE with an accuracy rivaling that of the intact wild-type Q50K engrailed homeodomain, making dad-HDH-3 the most specific designed DNA binding miniature homeodomain reported to date. Moreover, DNA binding affinity and specificity of HDH-3 could be controlled externally by irradiation with light. 相似文献
73.
Controlling the DNA binding specificity of bHLH proteins through intramolecular interactions 总被引:2,自引:0,他引:2
Reversible control of the conformation of proteins was employed to probe the relationship between flexibility and specificity of the basic helix-loop-helix protein MyoD. A fusion protein (apaMyoD) was designed where the basic DNA binding helix of MyoD was stablized by an amino-terminal extension with a sequence derived from the bee venom peptide apamin. The disulfide-stabilized helix from apamin served as a nucleus for a helix that extended for a further ten residues, thereby holding apaMyoD's DNA recognition helix in a predominantly alpha-helical conformation. The thermal stability of the DNA complexes of apaMyoD was increased by 13 degrees C relative to MyoD-bHLH. Measurements of the fluorescence anisotropy change on DNA binding indicated that apaMyoD bound to E-box-containing DNA sequences with enhanced affinity relative to MyoD-bHLH. Consequently, the DNA binding specificity of apaMyoD was increased 10-fold. 相似文献
74.
The reaction of 2 equiv of LiSeCC-n-C(5)H(11) (1) with cis-PtCl(2)(Ph(3)P)(2) (2) gives a mixture of the cis and trans isomers of Pt(Ph(3)P)(2)(SeCC-n-C(5)H(11))(2) (3), which slowly isomerizes in CH(2)Cl(2) to the preferred trans form trans-3. The closely related cis-[Pt(dppf)(2)(SeCC-n-C(5)H(11))(2)] (4) (dppf = bis(diphenylphosphino)ferrocene) was prepared by a similar metathetical reaction using the platinum chloride complex of the chelating dppf to impose the cis geometry. The structures of the cis and trans complexes have been investigated in solution by heteronuclear NMR ((31)P, (77)Se, and (195)Pt) and, in the cases of trans-3 and 4, characterized in the solid state by single-crystal X-ray diffraction. Changing the coordination geometry from cis to trans induces significant changes in the structural and spectroscopic parameters, which do not comply with the previously anticipated donor-acceptor properties of selenolate ligands. 相似文献
75.
Zusammenfassung Es wird eine rasche Methode zur Bestimmung von Magnesium in Aluminium und Aluminiumlegierungen beschrieben. Magnesium wird als CMAB-Oxin-Komplex mit Chloroform extrahiert und nach Rückschüttelung mit einer Boratpufferlösung spektralphotometrisch unter Verwendung von Calmagit als Reagens bestimmt.
Herrn Prof. Dr. W. Leithe danken wir für wertvolle Anregungen und Hinweise, der Direktion der Österreichischen Stickstoffwerke AG für die Erlaubnis zur Veröffentlichung. 相似文献
Summary A quick method is described for the determination of magnesium in aluminium and aluminium alloys. Magnesium is first separated as CMAB-oxine complex in chloroform and after back-extraction into a borate-buffer solution determined spectrophotometrically using Calmagite as reagent.
Herrn Prof. Dr. W. Leithe danken wir für wertvolle Anregungen und Hinweise, der Direktion der Österreichischen Stickstoffwerke AG für die Erlaubnis zur Veröffentlichung. 相似文献
76.
Rudolf Tannenberger 《Fresenius' Journal of Analytical Chemistry》1956,152(1-3):193-203
Zusammenfassung Das Studium der Fällungsbedingungen für Asphalte aus Teeren und Hydrierprodukten hat zur Entwicklung einer Bestimmungsmethodik mit Vorfällung des Asphaltes durch Erdölschmieröle geführt. Die Verwendung des Schmieröles ermöglicht die Abscheidung der Asphaltstoffe in einer für die nachfolgende Extraktion sehr günstigen, großoberflächigen, pulvrigen Form, wenn man dafür sorgt, daß ein Schmelzen oder Klebrigwerden durch zu hohe Temperaturen beim Fällungsvorgang vermieden wird. Die Dispergierung des zu fällenden Produktes wird durch die gute Lösefähigkeit des Erdölschmieröles für die Nichtasphaltstoffe sehr gefördert und ermöglicht eine gute Verteilung. Auf die Zusammensetzung der Teer- bzw. Entschlammungsasphalte wird näher eingegangen und ihre Bedeutung für die Weiterverarbeitung kurz gestreift.Herrn Professor Dr. A. Kurtenacker zum 70. Geburtstag gewidmet.Herrn Friedrich Ganteför und Fräulein Reiher sei an dieser Stelle für die umfangreiche Mitarbeit bei der praktischen Durchführung der Versuche herzlichst gedankt. 相似文献
77.
For symmetry-constrained boranes B10H, B12H, and their valence isoelectronic analogues containing a single hetero atom, completely optimized geometries were obtained using Hartree–Fock SCF calculations with the 3-21G and 6-31G* basis sets. For the anionic and dianionic species, the geometry optimization was also carried out using the 6-31 + G* basis set. Harmonic vibrational frequencies were obtained at HF/3-21G level. The results compare well with experiment where available. 相似文献
78.
1,3-Dipolar cycloaddition of nitrile oxides, generated from nitroethanol and nitroacetaldehyde derivatives 3, 21 and 22, respectively, and of benzonitrile oxide to 4-vinyldioxolanes 1, 2 gave ca 4:1 erythro/threo mixtures of corresponding isoxazolines. LAH reduction of erytho isoxazolines proceeded with similar (ca 4:1) selectivity to furnish protected ribo-amino-polyols 11, 15,19, DL- and D-lividosamines 31 and 33, respectively, as main products. The DL-lividosamine derivative 33 was obtained pure by crystallization. In the D-series, the corresponding ribo/arabino mixture D-31/D-32 was transformed to the known α-methyl D-lividosaminide D-37. 相似文献
79.
Wehmschulte RJ Grigsby WJ Schiemenz B Bartlett RA Power PP 《Inorganic chemistry》1996,35(23):6694-6702
The synthesis and characterization of several sterically encumbered monoterphenyl derivatives of aluminum halides and aluminum hydrides are described. These compounds are [2,6-Mes(2)C(6)H(3)AlH(3)LiOEt(2)](n)() (1), (Mes = 2,4,6-Me(3)C(6)H(2)-), 2,6-Mes(2)C(6)H(3)AlH(2)OEt(2) (2), [2,6-Mes(2)C(6)H(3)AlH(2)](2) (3), 2,6-Mes(2)C(6)H(3)AlCl(2)OEt(2) (4), [2,6-Mes(2)C(6)H(3)AlCl(3)LiOEt(2)](n)() (5), [2,6-Mes(2)C(6)H(3)AlCl(2)](2) (6), TriphAlBr(2)OEt(2) (7), (Triph = 2,4,6-Ph(3)C(6)H(2)-), [2,6-Trip(2)C(6)H(3)AlH(3)LiOEt(2)](2) (8) (Trip = 2,4,6-i-Pr(3)C(6)H(2)-), 2,6-Trip(2)C(6)H(3)AlH(2)OEt(2) (9), [2,6-Trip(2)C(6)H(3)AlH(2)](2) (10), 2,6-Trip(2)C(6)H(3)AlCl(2)OEt(2) (11), and the partially hydrolyzed derivative [2,6-Trip(2)C(6)H(3)Al(Cl)(0.68)(H)(0.32)(&mgr;-OH)](2).2C(6)H(6) (12). The structures of 2, 3a, 4, 6, 7, 9a, 10a, 10b, 11, and 12 were determined by X-ray crystallography. The structures of 3a, 9a, 10a, and 10b, are related to 3, 9, and 10, respectively, by partial occupation of chloride or hydride by hydroxide. The compounds were also characterized by (1)H, (13)C, (7)Li, and (27)Al NMR and IR spectroscopy. The major conclusions from the experimental data are that a single ortho terphenyl substituent of the kind reported here are not as effective as the ligand Mes (Mes = 2,4,6-t-Bu(3)C(6)H(2)-) in preventing further coordination and/or aggregation involving the aluminum centers. In effect, one terphenyl ligand is not as successful as a Mes substituent in masking the metal through agostic and/or steric effects. 相似文献
80.
Dana Kubies Jaroslav Š?udla Rudolf Puffr Antonín Sikora Josef Baldrian Jana Ková?ová Miroslav Šlouf František Rypá?ek 《European Polymer Journal》2006,42(4):888-899
Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σy and yield strain εy, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations. 相似文献