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11.
Methyl oleate (18∶1) and linoleate (18∶2) were readily transformed to the correspondinggem-dichlorocyclopropane derivatives in high yield, using triethylbenzylammonium chloride as the phase-transfer catalyst in the
presence of aqueous NaOH and CHCl3. Reaction of dichlorocarbene with methyl 12-hydroxystearate furnished methyl 12-chlorostearate (49%) and 12-O-formylstearate (19%). The hydroxy group in methyl ricinoleate was protected (O-tetrahydropyran-2′-yl) prior to dichlorocyclopropanation of the ethylenic bond. Removal of the protecting group allowed the
hydroxy group to be converted to a chloride,O-acetyl, azido orO-formyl function. Treatment of methyl ricinoleate with thionyl chloride, followed by the reaction with dichlorocarbene gave
the corresponding 12-chloro-dichlorocyclopropane derivative. The dichlorocyclopropane derivative of oleic acid was transformed
to a C19 allenic fatty acid when treated witht-butyl lithium. However, the remaining dichlorocyclopropane derivatives, containing an additional functional group in the
alkyl chain, failed to yield the corresponding allenic derivatives. All derivatives were characterized by a combination of
spectroscopic and chromatographic techniques, including infrared,1H nuclear magnetic resonance (NMR), and13C NMR spectroscopy. 相似文献
12.
Malware-Autoren setzen zunehmend Verschleierungsmechanismen wie Komprimierung, Verschlüsselung oder sich selbst modifizierenden
Programmcode ein, welche das Auffinden der Malware durch herk?mmliche Virenerkennungsverfahren wie zum Beispiel die signaturbasierte
Suche sehr mühsam und teilweise sogar erfolglos erscheinen lassen. Ein erfolgversprechender Ansatz, um auch unbekannte Viren,
Würmer oder Trojaner zu erkennen, ist die heuristische Analyse 相似文献
13.
Kalinnik Natalia Kiesel Robert Rauber Thomas Richter Marcel Rünger Gudula 《The Journal of supercomputing》2021,77(4):3484-3515
The Journal of Supercomputing - Scientific application codes are often long-running time- and energy-consuming parallel codes, and the tuning of these methods towards the characteristics of a... 相似文献
14.
Kallwass Helmut K.W.; Surewicz Witold K.; Parris Wendy; Macfarlane Emma L.A.; Luyten Marcel A.; Kay Cyril M.; Gold Marvin; Jones J.Bryan 《Protein engineering, design & selection : PEDS》1992,5(8):769-774
Lactate dehydrogenases are of considerable interest as stereospecificcatalysts in the chemical preparation of enantiomerically pure-hydroxyacid synthons. For such applications in synthetic organicchemistry it would be desirable to have enzymes which tolerateelevated temperatures for prolonged reaction times, to increaseproductivity and to extend then applicability to poor substrates.Here, two examples are reported of significant thermostabilizations,induced by sitedirected mutagenesis, of an already thermostableprotein, the L-lactate dehydrogenase (EC 1.1.1.27
[EC]
, 35 kDa permonomer subunit) from Bacillus stearothermophilus. Thermal inactivationof this enzyme is accompanied by irreversible unfolding of thenative protein structure. The replacement of Argl71 by Tyr stabilizesthe enzyme against thermal inactivation and unfolding. Thisstabilizing effect appears to be based on improved interactionsbetween the subunits in the core of the active dimeric or tetramericforms of the enzyme. The thermal stability of L-lactate dehydrogenasevariants with an active site Arg residue, either in the 171(wild-type) or in the 102 position, is further increased bysulfate ions. The two stabilizing effects are additive, as foundfor the Argl71Tyr/ Gln1O2Arg double mutant, for which the stabilityof the protein in 100 mM sulfate solution reaches that of L-lactatedehydrogenases from extreme thermophiles. All mutant proteinsretain significant catalytic activity, both in the presenceand absence of stnhilfoing salts, and are viable catalysts inpreparative scale reactions. 相似文献
15.
Rodrigo F. Ortiz-Meoz Liping Wang Rosalie Matico Anna Rutkowska-Klute Martha De la Rosa Sabrina Bedard Robert Midgett Katrin Strohmer Douglas Thomson Cunyu Zhang Makda Mebrahtu Jeffrey Guss Rachel Totoritis Thomas Consler Nino Campobasso David Taylor Tia Lewis Kurt Weaver Marcel Muelbaier John Seal Richard Dunham Wieslaw Kazmierski David Favre Giovanna Bergamini Lisa Shewchuk Alan Rendina Guofeng Zhang 《Chembiochem : a European journal of chemical biology》2021,22(3):516-522
Indoleamine-2,3-dioxygenase 1 (IDO1) is a heme-containing enzyme that catalyzes the rate-limiting step in the kynurenine pathway of tryptophan (TRP) metabolism. As it is an inflammation-induced immunoregulatory enzyme, pharmacological inhibition of IDO1 activity is currently being pursued as a potential therapeutic tool for the treatment of cancer and other disease states. As such, a detailed understanding of the mechanism of action of IDO1 inhibitors with various mechanisms of inhibition is of great interest. Comparison of an apo-form-binding IDO1 inhibitor (GSK5628) to the heme-coordinating compound, epacadostat (Incyte), allows us to explore the details of the apo-binding inhibition of IDO1. Herein, we demonstrate that GSK5628 inhibits IDO1 by competing with heme for binding to a heme-free conformation of the enzyme (apo-IDO1), whereas epacadostat coordinates its binding with the iron atom of the IDO1 heme cofactor. Comparison of these two compounds in cellular systems reveals a long-lasting inhibitory effect of GSK5628, previously undescribed for other known IDO1 inhibitors. Detailed characterization of this apo-binding mechanism for IDO1 inhibition might help design superior inhibitors or could confer a unique competitive advantage over other IDO1 inhibitors vis-à-vis specificity and pharmacokinetic parameters. 相似文献
16.
The origin of olfactory stimuli involved in the host microhabitat location inCotesia flavipes, a parasitoid of stem-borer larvae, was investigated in a Y-tube olfactometer. The response of femaleC. flavipes towards different components of the plant-host complex, consisting of a maize plant infested with two or more larvae of the stem borerChilo partellus, was tested in dualchoice tests. The concealed lifestyle of the stem-borer larvae did not limit the emission of volatiles attractive to a parasitoid. A major source of the attractive volatiles from the plant-host complex was the stem-borer-injured stem, including the frass produced by the feeding larvae. Moreover, the production of volatiles attractive to a parasitoid was not restricted to the infested stem part but occurs systemically throughout the plant. The uninfested leaves of a stem-borer-infested plant were found to emit volatiles that attract femaleC. flavipes. We further demonstrate that an exogenous elicitor of this systemic plant response is situated in the regurgitate of a stem-borer larva. When a minor amount of regurgitate is inoculated into the stem of an uninfested plant, the leaves of the treated plant emit volatiles that attract femaleC. flavipes. 相似文献
17.
A methylene-interrupted C18 keto-acetylenic fatty ester (methyl 12-oxo-9-octadecynoate) was obtained from methyl ricinoleate by bromination-dehydrobromination
followed by oxidation. Reaction of methyl 12-oxo-9-octadecynoate with bis(benzonitrile) palladium(II) chloride, allyl bromide,
or methyl-allyl bromide furnished methyl 8-[5-hexyl-3-allyl-furan-2-yl]-octanoate (1, 56%) or methyl 8-[5-hexyl-3-(2-methyl-allyl)-furan-2-yl]-octanoate (2, 55%). Reaction of methyl 12-oxo-11-chloro-or 11-fluoro-9-octadeyynoate (prepared from methyl santalbate-methyl 11-E-9-octadecynoate, found in sandalwood, Santalum album, seed oil) with bis(benzonitrile) palladium(II) chloride gave methyl 8-(4-fluoro-5-hexyl-furan-2-yl)-octanoate (3, 50%) or methyl 8-(4-fluoro-5-hexyl-furan-2-yl)-octanoate (4, 50%), respectively. And when methyl 12-oxo-11-chloro- or 11-fluoro-9-octadecynoate was treated with a mixture of bis(benzonitrile)
palladium(II) chloride, allyl bromide, or methyl-allyl bromide, the reaction yielded tetrasubstituted C18 furan derivatives, viz, methyl 8-(3-allyl-4-chloro-5-hexyl-furan-2-yl)-octanoate (5, 54%), methyl 8-[4-chloro-5-hexyl-3-(2-methyl-allyl)-furan-2-yl)-octanoate (6, 54%), methyl 8-(3-allyl-4-fluoro-5-hexyl-furan-2-yl]-octanoate (7, 10%), and methyl 8-[4-fluoro-5-hexyl-3-(2-methyl-allyl)-furan-2-yl]-octanoate (8, 10%). The presence of a fluorine atom in the furan derivatives 4, 7, and 8 was readily characterized by the appearance of doublets for carbon nuclei, which were coupled to the fluorine atom
in the 13C NMR spectra. All furan fatty derivatives from this work were characterized by NMR spectroscopic and mass spectrometric analyses.
The yields of compounds 7 and 8 were very low (10%) despite attempts to improve the procedure by increasing the amounts of the reactants and catalyst. 相似文献
18.
Definition of the problem Ethics cafés in long-term geriatric care are considered as ethical education. They allow the participants to have an open discourse in a casual setting about moral issues related to daily work. In the literature, various characteristics are attributed to ethics cafés, e.g., improving analytical skills and communication, increasing ethical sensitivity and authority for making decisions. These characteristics primarily result from theory-based models. Arguments The goal of this study is the empirical investigation of the effectiveness of ethics cafés in the Nursing Homes Mattenhof–Irchelpark, Zurich. Furthermore, the study examined whether the subjective evaluation of characteristics of nurses and other professional groups are different. To capture the characteristics, a questionnaire was constructed in which the participants rated 16 statements during the survey period. A 5-point Likert scale was used for the analysis. One subgroup distinguished between “nursing staff” and “non-nursing staff”. Conclusion The postulated characteristics were confirmed with a very high approval. Therefore, the ethics cafés provide important input which enable the staff to analyze more clearly in difficult situations or to let them decide ethically in a more sensitive manner and to justify decisions made. The interdisciplinary approach supports an understanding of the views and arguments among the various areas and hierarchies. The differences between the two professionals groups are partially highly significant. It can be noted that the assigned characteristics in the questionnaire are generally perceived stronger and more significantly by the nursing staff. Therefore, a distinction must be made when interpreting the results of this study concerning the participants. 相似文献
19.
20.
Johan M. M. van Rooij Marcel E. van Kooten Niekerk Hans L. Bodlaender 《Theory of Computing Systems》2013,52(4):687-718
We consider the Partition Into Triangles problem on bounded degree graphs. We show that this problem is polynomial-time solvable on graphs of maximum degree three by giving a linear-time algorithm. We also show that this problem becomes $\mathcal{NP}$ -complete on graphs of maximum degree four. Moreover, we show that there is no subexponential-time algorithm for this problem on graphs of maximum degree four unless the Exponential-Time Hypothesis fails. However, the Partition Into Triangles problem on graphs of maximum degree at most four is in many cases practically solvable as we give an algorithm for this problem that runs in $\mathcal{O}(1.02220^{n})$ time and linear space. 相似文献