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951.
Manfred Golze 《Accreditation and quality assurance》2003,8(9):420-421
A third-party assessment of reference materials (RMs) and their production is not of the highest priority for RM users. But if RM producers do want a third-party involvement this should be realised within the frame of existing conformity assessment schemes. Nevertheless, the right and responsibility of the laboratories to select the most appropriate RMs for their tasks must not be restricted by accreditation bodies or other interested parties. 相似文献
952.
Tielmann P Boese M Luft M Reetz MT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3882-3887
For the first time FTIR spectroscopy has been applied to the measurement of enantiomeric purity. The underlying concept is based on the use of pseudo-enantiomers that are (13)C-labeled at appropriate positions. Upon applying Lambert-Beer's law in the determination of the concentrations of both enantiomers, the ee values are accessible, accuracy to within +/-5 % of the true values being possible. The application of a commercially available high-throughput FTIR system results in a slightly decreased accuracy (+/-7% for the ee values), but this allows a throughput of up to 10000 samples per day. The method is of interest in the area of combinatorial symmetric catalysis and directed evolution of enantioselective enzymes. 相似文献
953.
The mass spectral retro Diels-Alder-reaction: 1,2,3,4-tetrahydrocarbazole 1,2,3,4-Tetrahydrocarbazole undergoes a retro Diels-Alder-reaction under electron impact. C(2) and C(3) are eliminated as ethylene. This is shown by measuring the deuterated derivatives 1a , 1b and 1c . Furthermore the oxo-1,2,3,4-tetrahydrocarbazole derivatives 3 and 4 are investigated in respect to the mass spectral retro Diels-Alder reaction too. 相似文献
954.
Leufgen K Mutter M Vogel H Szymczak W;TOF-SIMS Study 《Journal of the American Chemical Society》2003,125(29):8911-8915
Structure and orientation of molecules are key properties of functionalized surfaces. Using time-of-flight secondary ion mass spectrometry (TOF-SIMS), here we investigate how to modulate these parameters upon the immobilization process varying the conditions of self-assembly. The molecule of interest, a template-assembled synthetic protein (TASP), consists of a central peptide ring with orthogonally arranged residues. Thioalkane chains allow the directed self-assembly of the molecule on a gold surface; four serine residues on the opposite side of the ring can be used as anchoring sites for various functional sensing molecules. The TASP conformation and its orientation in self-assembled monolayers (SAMs) play a central role for the accessibility of these serine residues. To study the influence of the self-assembly conditions, two series of samples were prepared. Pure TASP monolayers of different surface densities are compared to mixed TASP/alkanethiol monolayers prepared by sequential adsorption varying sequence and particular incubation times as well as by coadsorption modifying incubation times and TASP/alkanethiol mass ratios. Switching the TASP orientation from a state where the molecules are lying flat on the surface to an upright orientation turned out to be possible by inserting the TASP into a preformed alkanethiol monolayer of an appropriate surface density. This study demonstrates that TOF-SIMS is an excellent tool not only to investigate the surface composition, but also the molecular structure of functionalized surfaces. 相似文献
955.
956.
Norbert Kuhn Klaus Eichele Manfred Steimann Ahmed Al‐Sheikh Bernd Doser Christian Ochsenfeld 《无机化学与普通化学杂志》2006,632(14):2268-2275
Hydrogen Bonds with Cyanide Ions? The Structures of 1,3‐Diisopropyl‐4,5‐dimethylimidazolium Cyanide and 1‐Isopropyl‐3,4,5‐trimethylimidazolium Cyanide 1,3‐Diisopropyl‐4,5‐dimethylimidazolium cyanide ( 2a ) and 1‐isopropyl‐3,4,5‐trimethylimidazolium cyanide ( 2b ) are obtained from the reaction of the corresponding 2,3‐dihydrodimethylimidazol‐2‐ylidenes ( 1 ) and hydrogen cyanide in excellent yield. Their crystal structure analyses reveal the presence of ion pairs linked by hydrogen bonds. The crystal structure analysis of 2a reveals a near colinear orientation of the C(1)‐H bond axis and the cyanide ion while in 2b this orientation is perpendicular. In both cases, the interionic distances are in the expected range for hydrogen bonds. Ab‐initio calculations of the total energy of the salts 2 indicate small differences in energy between the colinear and perpendicular orientation of the ions as well as between the colinear C‐H···C‐N and C‐H···N‐C orientations. The comparison of calculated and measured 13C and 15N NMR chemical shifts does not allow the distinction between the possible orientations. 相似文献
957.
A high pressure IR and UV spectroscopic study of the catalysis of hydrogenation of 1-octene by Fe(CO)5 under UV irradiation reveals that Fe(CO)5 and (olefin)Fe(CO)4 are the light absorbing species. The primary photolysis product Fe(CO)4 reacts with H2Fe(CO)4 to give HFe(CO)4 radicals, which are suggested to be the active hydrogenation promoters. 相似文献
958.
Nikolay A. Pushkarevsky Sergey N. Konchenko Manfred Scheer 《Journal of Cluster Science》2007,18(3):606-617
The reaction of K2[Fe3(μ3-Q)(CO)9] (Q = Se (K2[1a]), Te (K2[1b])) with [(dppm)PtCl2] leads to the addition of a [(dppm)Pt]2+ unit to a Fe2Q face of the initial cluster. By this way new heteronuclear clusters [Fe3Pt(μ3-Q)(CO)9(dppm)] were obtained possessing a butterfly-shaped cluster core bridged by a μ4-Q unit. It has been found that the resulting Fe-Pt clusters exist as equilibrium mixtures of two isomeric forms in solution
differing by the dppm coordination mode: as a chelate ligand coordinated to Pt or as a bridging ligand coordinated to Pt and
Fe atoms. The mixtures of isomers can be separated by chromatography and the pure isomers can be isolated as stable crystalline
phases. Solutions of both isomers attain equilibrium at normal conditions in about 1 month as found by NMR.
Dedicated to Professor Dieter Fenske in the occasion of his 65th birthday. 相似文献
959.
960.
Manfred Buck 《Fresenius' Journal of Analytical Chemistry》1963,193(2):101-112
Zusammenfassung In der vorliegenden Arbeit wird eine Methode zur exakten Bestimmung des Fluorgehaltes in Pflanzen beschrieben. Das Verfahren stellt eine Kombination der Willard-Winter-Destillation mit einer von Belcher, Leonard u. West gefundenen und von uns verbesserten colorimetrischen Fluoridbestimmungsmethode dar. Diese positive Farbreaktion des Fluorions ist im Vergleich zu den bisher angewandten Ausbleichreaktionen (z.B. Thorium/Alizarinsulfonsäure- oder Zirkonium/Eriochromcyanin-Verfahren) erheblich spezifischer. Unter den Bedingungen der Pflanzenanalyse ist sie kaum störanfällig. Die aus über 100 Analysen ermittelte Standardabweichung des Verfahrens liegt unter den fixierten Analysen-bedingungen bei Fluorgehalten von 1·10–3% F– im Bereich von 4% (rel.). 相似文献