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51.
G Schwedt 《Analytica chimica acta》1976,81(2):361-370
Automatic fluorimetric determinations of the O-methylcatecholamines, metanephrine and normetanephrine, by different methods of oxidation and stabilization are compared. Optimal experimental parameters for each method are described. Oxidation with hexacyanoferrate(III) and final stabilization of the fluorophore with ascorbic acid yields the best results. Differential determinations of the amines are possible if the oxidation pH values, pumping rates and excitation—emission wavelengths are selected appropriately. 相似文献
52.
Walter Fischer Cyril A. Grob Reinhard Hanreich Georg von Sprecher Adrian Waldner 《Helvetica chimica acta》1981,64(7):2298-2311
The solvolysis rates and products of the 6-exo-substituted 2-exo- 1a - 1u , and 2-endo-norbornyl p-toluenesulfonates 2a - 2u , have been determined. In general, the rate constants for 1 and 2 (log k) correlate well with the inductive constants σ of the substitutents at C(6); however, their sensitivity to σ is much larger in the 2-exo-series 1 than in the 2-endo-series 2 . This differential transmission of polar effects is the cause of decreasing 2-exo/2-endo rate ratios from 2388 for R = t-C4H9 to 0.37 for R = Br, i. e. with increasing electron attraction by the substituent. The high sensitivity of the rate constants for the 2-exo-p-toluenesulfonates 1 to σ indicates an unusually strong inductive interaction between C(6) and the incipient cationic center at C(2). This interaction is ascribed to the participation of the pentacoordinate C(6)-atom, i. e. to 1,3-bridging, a consequence of steric hindrance of nucleophilic solvent participation in norbornanes. Donor substituents enhance 1,3-bridging, lead to faster reactions and to the formation of 2-exo substitution products. Conversely, acceptor substituents reduce 1,3-bridging, decrease rates and facilitate the formation of 2-endo substitution products. Graded 1,3-bridging is discussed in the light of Winstein's nonclassical ion concept. 相似文献
53.
Self-assembled monolayers (SAMs) of methoxy-tri(ethylene glycol)- (EG(3)-OMe) and methyl-terminated alkanethiols (C(16)) adsorbed on polycrystalline gold were investigated by chemical force spectroscopy. Measurements were performed in aqueous electrolyte solutions depending on ionic strength and pH value. Charged and hydrophobic tips were employed as probes to mimic local patches of proteins and to study the interaction at the organic/liquid interface in detail. Force-distance curves reveal information about the origin of the observed interaction and the underlying mechanisms. The measurements confirm an effective negative surface charge to be present at the oligo(ethylene glycol) (OEG) and the methyl interface and suggest that the charges are due to the adsorption of hydroxyl ions from aqueous solution. pH-dependent measurements further support the robustness of the established charge associated with the OEG films. Its sign does not change over the whole range of investigated values between pH approximately 3.5 and approximately 10. In contrast, the hydrophobic self-assembled hexadecanethiol films on gold show an isoelectric point (IEP) around pH 4. While the mechanism of charge establishment appears to be similar for both SA films, the strength of hydrogen bonding to interfacial water, which acts as a template for hydroxyl ion adsorption, is likely to be responsible for the observed difference. 相似文献
54.
Coordinative Anchoring of Nickel Complexes on Hectorite-Layer Silicates through long-chain Diphenylphosphine Groups The treatment of sodium and calcium hectorites with 2-diphenylphosphinoethyltriethoxysilane leads, by condensation of free hydroxyl groups, to functionalized layer silicates with long-chain diphenylphosphine groups onto which nickel chloride can be coordinated. In these modified hectorites the fourth coordination site of the tetrahedrally coordinated nickel is occupied by a labile solvent molecule. On the other hand, the complex bis(2-diphenylphosphinoethyltriethoxysilane)nickel(II) chloride prepared beforehand also reacts with sodium hectorite under condensation; but the square-planar coordination of the four stable ligands (two chloride and two phosphor atoms) is maintained. This finds its expression in a significant activity decrease in catalytic reactions as compared to the aforementioned products. 相似文献
55.
Georg Heinig 《Integral Equations and Operator Theory》1985,8(6):805-824
The concept of partial indices, which is usually associated with matrix-functions, is defined for operators A satisfying rank (AU-VA)< for some fixed U and V (Toeplitz-like operators). A survey of the properties of partial indices is presented, some examples, and the connection with Kronecker indices as well. An application concerning Toeplitz plus Hankel matrices is supplemented. 相似文献
56.
An efficient and concise approach to the synthesis of the macrolide core of the cryptophycins has been developed. A novel macrolactonization utilizing a reactive acyl-beta-lactam intermediate incorporates the beta-amino acid moiety within the 16-membered macrolide core. This modular approach, involving a cyanide-initiated acyl-beta-lactam ring opening followed by cyclization, was successfully applied to the total synthesis of cryptophycin-24. The strategy was also used in an efficient synthesis of the 6,6-dimethyl-substituted dechlorocryptophycin-52. In this case, the cyanide-initiated ring opening of the bis-substituted 2-azetidinone followed by macrolactonization was achieved through a catalytic process. 相似文献
57.
The pentapeptide Z-(L)-Ala-(L)-Phe-Gly-(L)-Phe-Gly-OMe was obtained by reacting the activated dipeptide derivative Z-(L)-Ala-(L)-Phe-OPcp with the amino peptide derivative TFA·H-Gly-(L)-Phe-Gly-OMe at 100–105°C under reduced pressure (10?2-10-?3 Torr) without using solvents. The product obtained by bulk condensation showed no racemization, whereas the product obtained by a matrix mediated condensation contained 5,5 % diastereomer Z-(L)-Ala-(D)-Phe-Gly-(L)-Phe-Gly-OMe. Separation of diastereomers was achieved by HPLC on a silicagel column. 相似文献
58.
Fabian Gerson Georg Gescheidt Reinhart Mckel Alexander Aumüller Peter Erk Siegfried Hünig 《Helvetica chimica acta》1988,71(7):1665-1672
The radical anions of 12 N,N′-dicyanoquinone diimines, a new class of electron acceptors, hace been characterized by their hyperfine data with the use of ESR and ENDOR spectroscopy. The largest coupling constant (0.30–0.45 mT), due to the two 14N nuclei in the exocyclic positions, gives rise to a conspicuous broadening of the peripheral ESR lines by an incomplete averaging of the hyperfine anisotropy. The most plausible interpretation of the experimental results for the radical anions of N,N′-dicyano- 1,4-benzoquinone diimine ( 1 ) and N,N′-Dicyano-9,10-anthraquinone diimine ( 9 ) is in terms of both ‘syn’- and ‘anti’-configurations contributing to the ESR and ENDOR spectra and having equal proton- and 14N-coupling constants. The π-spin distribution in the radical anions of N,N′-dicyanoquinone diimines is compared with those in the analogous ions of tetracyanoquinodimethanes and quinones. 相似文献
59.
We report the synthesis of Fmoc protected single amino acid chelates (SAAC) and their metal complexes. The modified amino acids are suitable for solid-phase peptide synthesis. The use of 4-hydroxymethylbenzoic acid AM (HMBA-AM) resin allows the nucleophilic cleavage of the peptide-metal complexes from the resin without decomplexation. 相似文献
60.
Zusammenfassung Die Reaktionsparameter der Umsetzung von DANS-Cl mit den Catecholaminen Adrenalin, Noradrenalin und Dopamin wurden systematisch untersucht und für eine gemeinsame Derivatisierung optimiert: pH 8–9, 40% Wasser im Aceton/Wasser-Gemisch, 2 fach stöchiometrischer Überschuß an DANS-Cl, 20 min bei 40° C. Die DANS-Catecholamine lassen sich adsorptions- und reverse-phase-chromatographisch trennen, wobei für die Zusammensetzung der mobilen Phasen kurze Analysenzeiten mit optimaler Trennung angestrebt wurden. Vor- und Nachteile der beiden hochdruck-flüssigkeits-chromatographischen Verfahren werden gegenübergestellt.
High-pressure liquid chromatography of the catecholamines as DANS-derivates — Derivatization and separation
The parameters of the reaction of DANS-Cl with the catecholamines adrenaline, noradrenaline, and dopamine were studied systematically and optimized for an simultaneous derivatization: pH 8–9, 40% water in an acetone water mixture, twofold stoichiometric excess of DANS-Cl, 20 min at 40° C.The DANS-catecholamines are separable by adsorption and reverse-phase chromatography. Short analytical times with optimal separation were intended for the composition of the mobile phases. Advantages and disadvantages of the two high-pressure liquid Chromatographic methods are discussed.相似文献