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排序方式: 共有833条查询结果,搜索用时 234 毫秒
1.
H. Falk R. Geerling B. Hattendorf K. Krengel-Rothensee K. P. Schmidt 《Analytical and bioanalytical chemistry》1997,359(4-5):352-356
An ICP-MS method for the determination of ultra-traces of 24 Elements (Li, Be, Mg, Al, Cr, Mn, Co, Zn, Cu, Ga, As, Se, Rb, Sr, Mo, Ag, Cd, Sn, Sb, Ba, Tl, Pb, Bi, U) at ng/L to μg/L levels in highly saline solutions (up to 30 g/L NaCl) was developed. Calculated to the salt content of the samples, limits of detection at the sub-μg/kg level were obtained. This allows the measurement of samples like sea water, or clinical samples like urine, serum and whole blood, with few or without sample preparation and a drastic improvement to the limits of detection. Compared to the determination in solutions of 1 g/L NaCl the limits of detection in the original sample were improved by one order of magnitude. Improvements in instrumental stability are achieved by the use of an additional gas, that is introduced to the aerosol stream and avoids salt deposition in the aerosol tube of the torch, the use of High Matrix Content (HMC) cones, that show no clogging even at NaCl-concentrations up to 50 g/L. With this setup the long term stability for measurements with changing matrix concentrations is < 10% without and < 5% with use of an internal standard for the individual samples. Cleaning up is necessary after 2 days of operation. The direct analysis of the Nearshore Seawater Reference Material NRC-CNRC CASS3 showed a good agreement with the certified and measured concentrations. Elements, that do not suffer from an isobaric overlap of matrix compounds can be determined clearly at ng/L levels. Measurement of different matrix concentrations showed, that acceptable results can be achieved with a single calibration for concentrations from 5 g/L NaCl to 30 g/L NaCl, though matrix matching shows the best results. 相似文献
2.
Benjamin Falk Santiago M. Vallinas James V. Crivello 《Journal of polymer science. Part A, Polymer chemistry》2003,41(4):579-596
This article describes the development of optical pyrometry (OP) as a new analytical technique for the continuous monitoring of the progress of both free‐radical and cationic photopolymerizations. The method is rapid, reproducible, and very easy to implement. A temperature profile of a photopolymerization can be obtained. Preliminary studies have shown that the temperatures of some polymerizing monomers can easily reach temperatures in excess of 250 °C. The effects of the mass and reactivity of the monomer, light intensity, structures, and concentrations of the photoinitiators and monomers as well as the presence or absence of oxygen on various free‐radical and cationic photopolymerizations were examined with this method. Coupling of real‐time infrared spectroscopy with OP provides a convenient method for simultaneously monitoring both the chemical conversion and the temperature of a photopolymerization. This combined technique affords new insights into the effects of temperature‐induced autoacceleration on the course of photopolymerizations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 579–596, 2003 相似文献
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Summary N-Arylsubstituted ureas undergo exchange of the N-residue upon reaction with amines. Using kinetic measurements, investigation of product distribution, regioselectivity, catalysis, and substrate influences, it was shown that this reaction proceeds via a second order nucleophilic substitution at the urea carbonyl center. By means of semiempirical calculations using the MNDO method the alternative mechanism of fragmentation was investigated.
Zur Synthese N-substituierter Harnstoffe II: Nucleophile Substitution von Harnstoffen an der Carbonylgruppe
Zusammenfassung N-Arylsubstituierte Harnstoffe erleiden bei der Reaktion mit Aminen einen Austausch des N-Restes. Durch kinetische Messungen, Untersuchung der Produktverteilung, Regioselektivität, Katalyse und des Einflusses des Edukts konnte abgeleitet werden, daß es sich hiebei um eine nucleophile Substitution zweiter Ordnung am Carbonylzentrum des Harnstoffs handelt. Durch semiempirische Rechnungen mit Hilfe der MNDO Methode wurde der alternative Reaktionsmechanismus einer Fragmentierung untersucht.相似文献
5.
Heinz Falk Ernst Haslinger Thomas Schlederer 《Monatshefte für Chemie / Chemical Monthly》1979,110(6):1287-1294
The1H-NMR spin lattice relaxation times of aetiobiliverdin-IV- and biliverdindimethylester were determined using the inversion recovery technique. The relaxation times of protons attached to the terminal rings A and D are longer than those situated at the rings B and C which points to a higher mobility of rings A and D. Moreover these measurements allowed an independent assignment of the1H-NMR-signals of the methyl groups of biliverdindimethylester.
30. Mitt.:H. Falk undT. Schlederer, Ann. Chem., im Druck. 相似文献
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Zusammenfassung Ringschluß von -bzw. -Phenyl--ferrocenyl-buttersäure liefert die homoannular überbrückten Ketone (- bzw. -Phenyl--ketotetramethylen)-ferrocen (VI, VII, XIV). Die Ermittlung der Absolutkonfiguration dieser Ketone gelang durch Korrelation des Asymmetriezentrums der optisch aktiven -Phenyl--ferrocenyl-buttersäure (deren Absolutkonfiguration primär bestimmt wurde) mit der Konfiguration des planar asymmetrischen Anteils in den optisch aktiven Ketonen.Die erhaltenen Ergebnisse waren auch mit der früher für (+)-1,2-(-Ketotetramethylen)-ferrocen (I) auf unabhängigem Weg ermittelten Konfiguration in Einklang, wie durch Messung des optischen Circulardichroismus erwiesen werden konnte: die rechtsdrehenden Enantiomeren besitzen die (R), die linksdrehenden (S)-Konfiguration.
Mit 1 Abbildung
Über die Verwendung des Ausdruckes Ferrocen-Chiralität (bzw. Chiralitäts-Zentrum und Planar-Chiralität) vgl., Fußnote S. 266.
Vgl. hierzu die Fußnote auf S. 1066
3. Mitt. über Ferrocenasymmetrie, zugleich 24. Mitt. über Ferrocenderivate:H. Falk undK. Schlögl, Mh. Chem.96, 266 (1965). 相似文献
Ring closure of - and -phenyl--ferrocenylbutyric acid yielded the corresponding homoannularily bridged ketones, (- and -phenyl--ketotetramethylene)-ferrocene (VI, VII, XIV), respectively. The absolute configuration of these ketones could be established by correlation of the asymmetric center of the optically active -phenyl--ferrocenylbutyric acid (whose absolute configuration was determined previously) with the configuration of the planar asymmetric part in the optically active ketones.The results obtained support the configuration reported earlier for (+)-1,2-(-ketotetramethylene)-ferrocene (I) and established by an independent route. The configurations could also be supported by use of optical circular dichroism, i. e., the dextrorotatory enantiomers have the (R)-configuration, the laevorotatory the (S)-configuration.
Mit 1 Abbildung
Über die Verwendung des Ausdruckes Ferrocen-Chiralität (bzw. Chiralitäts-Zentrum und Planar-Chiralität) vgl., Fußnote S. 266.
Vgl. hierzu die Fußnote auf S. 1066
3. Mitt. über Ferrocenasymmetrie, zugleich 24. Mitt. über Ferrocenderivate:H. Falk undK. Schlögl, Mh. Chem.96, 266 (1965). 相似文献
9.
During attempts to synthesize rare‐earth nitride tellurides black and bead‐shaped single crystals of the title compound sodium praseodymium(III) ditelluride (NaPrTe2) were obtained as a by‐product by reacting a mixture of praseodymium, sodium azide (NaN3) and tellurium at 900 °C for seven days in evacuated torch‐sealed silica vessels. NaPrTe2 crystallizes cubic (space group: Fd3¯m, Z = 16; a = 1285.51(9) pm, Vm = 79.96(1) cm3/mol, R1 = 0.028 for 146 unique reflections) and exhibits the Na+ and Pr3+ cations in slightly distorted octahedra of six telluride anions (d(Na—Te) = 325 pm, d(Pr—Te) = 317 pm) each. The main characteristics of this new structure type for alkali‐metal rare‐earth(III) dichalcogenides can be derived from the rock‐salt type structure (NaCl, cubic closest‐packed Te2— arrangement, all octahedral voids occupied with Na+ and Pr3+) with alternating layers consisting of Na+ and Pr3+ cations in a ratio of 3:1 and 1:3, respectively, piled along the [111] direction. 相似文献
10.
The luminescence properties of about twentyfive model compounds representing the three main partial structures of bile pigments (namely pyrromethenes, pyrromethenones and methylenepyrrolylmethylenepyrrolinones) as well as tripyrrines and the geometrical isomers of aetiobiliverdin-IV- are reported. In these compounds there is usually only a very faint or even no fluorescence and phosphorescene as the pathway of deexcitation. Vibrational internal conversion and photoisomerizations at the exocyclic double bonds are the main anaerobic paths of radiationless decay of the excited states.
H. Falk, K. Grubmayr, E. Haslinger, T. Schlederer undK. Thirring, Mh. Chem.109, 1451 (1978). 相似文献