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1.
Stefan Peterli Dieter Hubmann Urs Squin Helmut Mett Peter Traxler 《Helvetica chimica acta》1994,77(1):59-69
β-Nitrostyrene derivatives of adenosine 5′-glutarates are potent and selective bisubstrate-type inhibitors of the epidermal growth factor receptor protein tyrosine kinase (EGF-R PTK). In an attempt to improve the inhibitory activity, this type of compounds was modified with alkyl spacers of varying length between the nitrostyrene and the glutaryl units. The spacers consisted of 1, 3, 4, and 5 atoms to give compounds of the benzyl, oxyethyl, oxypropyl, and oxybutyl series, respectively (Schemes 1 and 2). Adenosine 5′-esters were prepared in the benzyl and oxypropyl series only. Compared to the compounds in the parent series without spacer (IC50 = 0.7–12 μM ), most of the modified compounds inhibited the EGF-R PTK only marginally or were inactive (IC50 ≥ 100 μM ). The only exceptions were the free acids 19 and 20 with IC50 values of ca. 5 μM . It is noteworthy that esterification of these two hydrogen glutarates with either MeOH or adenosine yielded inactive compounds, which is in contrast to the corresponding substances without spacers. 相似文献
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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
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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
5.
Urs Lang 《Mathematische Zeitschrift》1992,210(1):581-592
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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
8.
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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