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141.
Geciane Toniazzo Débora de Oliveira Cláudio Dariva Enrique Guillermo Oestreicher Octávio A. C. Antunes 《Applied biochemistry and biotechnology》2005,123(1-3):837-844
The main objective of this work was to investigate the biotransformations of (−)α-pinene, (−)β-pinene, and (+) limonene by
Aspergillus niger ATCC 9642. The culture conditions involved—concentration of cosolvent (EtOH), substrate applied, and sequential addition
of substrates—were investigated. Adaptation of the precultures with small amounts of substrate was also studied. The experiments
were performed in conical flasks with liquid cultures. This strain of A. niger was able to convert only (−)β-pinene into α-terpineol. An optimum conversion of (−)β-pinene into α-terpineol of about 4%
was obtained when the substrate was applied as a diluted solution in EtOH and sequential addition of substrate was used. 相似文献
142.
A new method is presented for spectrophotometric micro-determinations of cadmium by means of a triazine dye, called “Cadion”The method is a highly sensitive one, permitting the determination of 0.05 p.p.m. cadmium in the final solution, with satisfactory accuracy and reproducibility.The interference of the main foreign anions and cations is studied, and a way of eliminating the interfering ions is suggestedSome examples are given for the application of the proposed method 相似文献
143.
We report the details of the first total synthesis of erythromycin B using two different strategies for the end game. The first of these follows a classical approach in which the desosamine and cladinose residues are sequentially appended to a macrocyclic lactone, which was formed by cyclization of a seco acid derivative, to give a bis-glycosylated macrolide intermediate that is converted into erythromycin B. The second strategy features an abiotic approach in which a seco acid bearing a desosamine residue is cyclized to give a monoglycosylated macrocyclic lactone that is then transformed into erythromycin B via a sequence of steps involving refunctionalizations and a glycosylation to introduce the cladinose moiety. Attempts to prepare a bis-glycosylated seco acid by de novo synthesis were unsuccessful. The syntheses of the key seco acid intermediates feature the oxidative transformation of a furan containing C(3)-C(10) to provide a dioxabicyclo[3.3.1]nonenone that served as a template on which to create the stereocenters at C(6) and C(8). A stereoselective aldol reaction was used to establish the C(11)-C(15) segment, and a stereoselective crotylation was implemented to introduce the propionate subunit comprising C(1)-C(2). 相似文献
144.
Zusammenfassung Nach den an Hand der Warburg-Technik durchgeführten Autoxydationsversuchen erweisen sich im Einklang mit früheren eigenen Untersuchungen p-Benzochinon, p-Benzohydrochinon sowie p-Benzochinhydron als Antioxydantien unterschiedlicher Wirkungsstärke und verschiedenartiger Wirkart.Chinon, das schwächste Antioxydans, betätigt sich als Retarder, Hydrochinon mit seiner markanten Verlängerung der Induktionsperiode stellt einen echten Inhibitor dar. Chinhydron sind beide Wirkungen als Retarder und Inhibitor zuzuordnen.Durch eingehende systematische Untersuchungen wird gezeigt, daß die Veränderungen von Chinon, Chinhydron und Hydrochinon während der Autoxydation von Äthyllinolat ohne Störung durch gebildete Hydro peroxyde im lipiden System als reduzierbarer bzw. oxydierbarer Anteil auf polarographischem Wege mit gut reproduzierbaren Ergebnissen und sehr befriedigender Empfindlichkeit bestimmbar sind.
Herrn Prof. Dr.-Ing.G. Gorbach zum 60. Geburtstag in glückwünschender Verbundenheit gewidmet. 相似文献
Summary According to the autoxidation experiments carried out by means of the Warburg technique,p-benzoquinone,p-benzohydroquinone, and alsop-benzoquinhydrone, in agreement with previous trials by the present writers, exhibit antioxidant actions of different degrees and kinds of action.Quinone, the weakest antioxidant, acts as retarder. Hydroquinone, with its distinct lengthening of the induction period is a real inhibitor. Quinhydrone can function either as retarder or inhibitor.Extensive systematic trials showed that the changes in quinone, quinhydrone and hydroquinone during the autoxidation of ethyl linolate can be determined polarographically in excellent reproducible fashion and with good sensitivity with no interference from the resulting hydroperoxides in the lipid system as reducible or oxidizable portion.
Résumé Les essais d'auto-oxydation effectués d'après la technique de Warburg se montrent en accord avec certaines expériences antérieures réalisées avec lap-benzoquinone, lap-benzohydroquinone ainsi qu'avec lap-benzoquinhydrone comme anti-oxydants agissant avec des actions plus ou moins fortes et suivant des processus différents.La quinone, l'anti-oxydant le plus faible, se comporte comme »retardateur«, l'hydroquinone, qui prolonge de manière très accentuée la période d'induction, se présente comme un véritable »inhibiteur«. La quinhydrone se comporte à la fois comme »retardateur« et comme »inhibiteur«.On montre par des recherches systématiques et approfondies que l'on peut doser les variétés de quinone, de quinhydrone et d'hydroquinone pendant l'auto-oxydation du linoléate d'éthyle, comme éléments »réducteurs« ou »oxydants«, par polarographie, avec de bons résultats reproductibles et une bonne sensibilité, sans interférence avec les hydroperoxydes formés dans le système lipide.
Herrn Prof. Dr.-Ing.G. Gorbach zum 60. Geburtstag in glückwünschender Verbundenheit gewidmet. 相似文献
145.
Ana Cristina Gmez-Herrero Carlos Snchez-Snchez Frdric Chrioux Jose Ignacio Martínez Jos Abad Luca Floreano Alberto Verdini Albano Cossaro Estelle Mazaleyrat Valrie Guisset Philippe David Simone Lisi Jos Angel Martín Gago Johann Coraux 《Chemical science》2021,12(6):2257
Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper. 相似文献
146.
147.
Klara Markova Klaudia Chmelova Srgio M. Marques Philippe Carpentier David Bednar Jiri Damborsky Martin Marek 《Chemical science》2020,11(41):11162
Computational design of protein catalysts with enhanced stabilities for use in research and enzyme technologies is a challenging task. Using force-field calculations and phylogenetic analysis, we previously designed the haloalkane dehalogenase DhaA115 which contains 11 mutations that confer upon it outstanding thermostability (Tm = 73.5 °C; ΔTm > 23 °C). An understanding of the structural basis of this hyperstabilization is required in order to develop computer algorithms and predictive tools. Here, we report X-ray structures of DhaA115 at 1.55 Å and 1.6 Å resolutions and their molecular dynamics trajectories, which unravel the intricate network of interactions that reinforce the αβα-sandwich architecture. Unexpectedly, mutations toward bulky aromatic amino acids at the protein surface triggered long-distance (∼27 Å) backbone changes due to cooperative effects. These cooperative interactions produced an unprecedented double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates to the active site, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. Despite these spatial restrictions, experimental tracing of the access tunnels using krypton derivative crystals demonstrates that transport of ligands is still effective. Our findings highlight key thermostabilization effects and provide a structural basis for designing new thermostable protein catalysts.Illustration of cooperative thermostabilization effects of the double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. 相似文献
148.
Highly diastereoselective protonation of chiral lactam enolates of 4-substituted-1,4-dihydroisoquinolin-3-ones is reported. Protonation and alkylation processes of these lactam enolates derived from phenylglycinol occur with opposite diastereofacial selectivity. This diastereoselective protonation has been applied to the asymmetric synthesis of (4S)-N-methyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline 9 obtained in up to 97% ee. 相似文献
149.
[reaction: see text] Quinodimethanes are highly reactive toward dienophiles since Diels-Alder cycloaddition results in an aromatic product. Density functional-based (13)C, (1)H NMR, NICS, and MO-NICS calculations indicate that the increase of aromatic character of the developing benzenoid ring along the reaction path is especially pronounced after the transition state is reached, even though the number of pi orbitals decreases. The forming aliphatic ring exhibits large ring current effects during the reaction. 相似文献
150.
The enantiomeric separation of some nonsteroidal anti-inflammatory drugs (NSAIDs) was investigated in capillary electrophoresis (CE) using dual systems with mixtures of charged cyclodextrin (CD) derivatives. A significant enhancement of selectivity and resolution could be achieved in the enantioseparation of these analytes in their uncharged form by the simultaneous addition of two oppositely charged CD derivatives to the background electrolyte. The combination of the single-isomer cationic CD, permethyl-6-monoamino-6-monodeoxy-beta-CD (PMMAbetaCD) and the single-isomer polyanionic CD, heptakis-6-sulfato-beta-cyclodextrin (HSbetaCD) in a pH 2.5 phosphoric acid-triethanolamine buffer, was designed and employed for the enantioseparation of profens. The improvement in selectivity and resolution can be attributed to the fact that the two CDs, which lead to independent and enantioselective complexation with the analyte enantiomers, have not only opposite effects on the electrophoretic mobility of these compounds but also opposite affinity patterns towards the enantiomers of these compounds. Binding constants for these enantiomers with each CD were determined using linear regression approach, in order to be able to predict the effect of the concentrations of the two CDs on enantiomeric selectivity and resolution in such dual systems. 相似文献