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31.
32.
N(alpha)-Methylamino acid containing peptides exhibit interesting therapeutic profiles and are increasingly recognized as potentially useful therapeutics. Unfortunately, their synthesis is hampered by the high price and unavaibility of many N(alpha)-methylamino acids. An efficient and practical preparation of N(alpha)-methyl-N(alpha)-(o-nitrobenzenesulfonyl)-alpha-amino acids without extensive purification is described. The procedure is based on the well-known N-alkylation of N(alpha)-arylsulfonylamino esters which was improved by using dimethyl sulfate and DBU as base. Ester cleavage is efficiently achieved by using an S(N)2-type saponification with lithium iodide, avoiding racemization observed with lithium hydroxide hydrolysis. Compatibility of the synthesized N(alpha)-methylamino acids with Fmoc solid-phase peptide synthesis is demonstrated by using normal coupling conditions to efficiently prepare N-methyl dipeptides. The described procedure allows the preparation of N(alpha)-methylamino acids in a very short period of time and a rapid synthesis of N-methyl peptides using Fmoc solid-phase peptide synthesis. 相似文献
33.
The high pressure behaviour of InI is studied by DFT‐calculations and compared with experimental data. The existence of a 5s2 electron pair in In+ represents an unfavourable bonding situation for high symmetry structures because of effective closed shell repulsion. Since cations with a ns2 electron pair are highly polarizable and the electronic situation is more favourable in the low symmetry structure InI prefers a TlI‐type structure at ambient pressure. A pressure induced transition to the more densely packed high symmetry CsCl‐type structure takes place at about 19 GPa according to our calculations. At ambient pressure the interactions are predominantly ionic. However with increasing pressure the distances between In+ cations in the TlI‐type structure diminish drastically, mainly due to the changing space requirement of the lone electron pair. Apart from ionic interactions further bonding interactions between the In+ cations occur. At elevated pressure the electron localization function (ELF) as well as the band structure diagrams suggest metallic bonding between the In+ within the zigzag chain, i. e. increasing bonding interactions between the In+ cations due to the electron pair and its s‐p‐mixing. At ambient pressure In‐In interactions are rather weak and the space requirement of the lone electron pair mainly determines the characteristic arrangement of the ions. At elevated pressure the In‐In interactions become stronger and stabilise themselves additionally the specific structural arrangement. 相似文献
34.
35.
Max Ziegler und Horst Winkler 《Fresenius' Journal of Analytical Chemistry》1959,166(4):241-242
Zusammenfassung Durch die Anwendung eines H2S-haltigen Laufmittels werden die Ionen Cu2+, Pb2+, Bi3+ und Hg2+ am Startpunkt des Chromatogramms als Sulfide fixiert, während Cd2+ nach kurzer Laufzeit in scharf begrenzter Zone als Sulfid im Chromatogramm nachgewiesen wird. Als Arbeitsgefäße dienen Reagensgläser. Die Spezifitäten liegen für 5 g Cd bei Cd2+Cu2+=12000, Cd2+Pb2+=12000, Cd2+Bi3+=12000, Cd2+Hg2+=1100.Herrn Prof. Dr. O. Glemser, Direktor des Anorganisch-chemischen Insituts der Universität Göttingen, danken wir für Unterstützung der Arbeit. 相似文献
36.
Two separate peaks are observed for narrow polymer standards in both isocratic and gradient HPLC. One peak appears around the solvent front (the "solvent-plug peak" or "breakthrough peak"), whereas the second peak is retained significantly--or even highly. Although the effect has been observed many times before, it has never been rigorously explained. In this paper we provide a detailed explanation for the breakthrough peak. The two completely separate peaks are demonstrated not to represent to different fractions of the sample (e.g., the low- and high-molecular-mass parts of the distribution). Both peaks are representative of the entire polymeric sample for narrow polymer standard. Because the amount of the polymer in the breakthrough peak may vary, the quantitative analysis of the polymers by LC is jeopardized. The effects of the sample solvent, the (initial) mobile phase composition, the injection volume, the injected sample concentration, the column temperature, and the analyte structure and molecular mass on the breakthrough peak were investigated in LC experiments involving standards of polystyrene and poly(methyl methacrylate). Three necessary and sufficient conditionsare suggested for the breakthrough phenomenon to be observed. Recommendations to avoid the breakthrough phenomenon are given, culminating in a structured method for selecting the best possible sample solvents. 相似文献
37.
Wolfgang Marterer Horst Prinzbach Grety Rihs Jakob Wirz Jaques Lecoultre Edgar Heilbronner 《Helvetica chimica acta》1988,71(8):1937-1965
The propensity of the N?N bond to undergo photo [2 + 2] cycloadditions has been further explored. In the specifically designed 1,5-azo/enes 1–3 , no [2 + 2] cycloaddition has been observed upon either direct or sensitized excitation with light of various wave lengths at temperatures down to 77 K, in line with expectations based on X-ray ( 1 : d = 2.71 Å, ω = 129°) and PE measurements ( 1 : I1 = 8.00, I2 = 9.05 eV; 2 ; I1 = 8.00, I2 = 9.25eV). The steric/stereoelectronic demands for the participation of the N?N bond in pericyclic reactions are clearly more stringent than those for the C?C bond. 相似文献
38.
Na5AlF2(PO4)2: Synthesis, Crystal Structure and Ionic Conductivity Two different procedures (precipitation from aqueous solution and solid state reaction) for the synthesis of hitherto unknown Na5AlF2(PO4)2 were optimized. The crystal structure was determined using diffractometer data (P3 , a = b = 10.483(1), c = 6.607(1) Å, MoKα, 1080 independent reflections, Rw = 0.025). PO4-tetrahedra and AlO4F2-“octahedra” are connected via common vertices forming a twodimensionally extended heteropolyanion. Sodium is located in interconnected spacings of the [AlF2(PO4)2]-part of the structure. Ionic conductivity as expected because of these structural features was affirmed experimentally. 相似文献
39.
Horst P. Beck 《Journal of solid state chemistry》1983,47(3):328-332
A high pressure phase BaI2-II, which can be quenched and retained as a metastable form at ambient conditions, is reported. The structure has been determined by X-ray investigations using single crystals. BaI2-II crystallizes in an anti-Fe2P-type arrangement, space group Å, c = 5.173(3)Å, which is slightly denser than the PbCl2-type structure found at normal pressure. Structural features of the two phases are discussed in comparison. 相似文献
40.
Highly efficient capillary electrochromatographic separations of cardiac glycosides and other steroids are presented. Employing butyl-derivatized silica particles as stationary phase resulted in a nearly three times faster electroosmotic flow (EOF) compared to capillary electrochromatography (CEC) with octadecyl silica particles. On-column focusing with a preconcentration factor of 180 was performed and separation efficiencies of up to 240,000 plates per meter were obtained. Using label-free standard UV absorbance, detection limits of 10-80 nM were reached for all steroids tested. For screening of cardiac glycosides, e.g., digoxin and digitoxin in mixtures of steroids, CEC was combined with immunoaffinity extraction using immobilized polyclonal anti-digoxigenin antibodies and F(ab) fragments. Simply adding small amounts of antibody carrying particles to the samples and comparing chromatograms before and after antibody addition allowed screening for high affinity antigens in mixtures with moderate numbers of compounds. Under conditions of competing antigens, affinity fingerprints of immobilized anti-digoxigenin and anti-digitoxin antibodies were obtained, reflecting the cross-reactivity of eleven steroids. The method provides high selectivity due to the combination of bioaffinity interaction with highly efficient CEC separation and UV detection at several wavelengths in parallel. This selectivity was exploited for the detection of four cardiac glycosides in submicromolar concentrations in an untreated urine sample. 相似文献