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Structure-based engineering of strictosidine synthase: auxiliary for alkaloid libraries 总被引:2,自引:0,他引:2
Loris EA Panjikar S Ruppert M Barleben L Unger M Schübel H Stöckigt J 《Chemistry & biology》2007,14(9):979-985
The highly substrate-specific strictosidine synthase (EC 4.3.3.2) catalyzes the biological Pictet-Spengler condensation between tryptamine and secologanin, leading to the synthesis of about 2000 monoterpenoid indole alkaloids in higher plants. The crystal structure of Rauvolfia serpentina strictosidine synthase (STR1) in complex with strictosidine has been elucidated here, allowing the rational site-directed mutation of the active center of STR1 and resulting in modulation of its substrate acceptance. Here, we report on the rational redesign of STR1 by generation of a Val208Ala mutant, further describing the influence on substrate acceptance and the enzyme-catalyzed synthesis of 10-methyl- and 10-methoxystrictosidines. Based on the addition of strictosidine to a crude strictosidine glucosidase preparation from Catharanthus cells, a combined chemoenzymatic approach to generating large alkaloid libraries for future pharmacological screenings is presented. 相似文献
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You X Wang H Goos E Sung CJ Klippenstein SJ 《The journal of physical chemistry. A》2007,111(19):4031-4042
The kinetics of the reaction CO + HO2* --> CO2 + *OH was studied using a combination of ab initio electronic structure theory, transition state theory, and master equation modeling. The potential energy surface was examined with the CCSD(T) and CASPT2 methods. The classical energy barriers were found to be about 18 and 19 kcal/mol for CO + HO2* addition following the trans and cis paths, respectively. For the cis path, rate constant calculations were carried out with canonical transition state theory. For the trans path, master equation modeling was also employed to examine the pressure dependence. Special attention was paid to the hindered internal rotations of the HOOC*O adduct and transition states. The theoretical analysis shows that the overall rate coefficient is independent of pressure up to 500 atm for temperature ranging from 300 to 2500 K. On the basis of this analysis, we recommend the following rate expression for reaction R1 k(cm(3)/mol x s) = 1.57 x 10(5) T(2.18)e(-9030/T) for 300 < or = T < or = 2500 K with the uncertainty factor equal to 8, 2, and 1.7 at temperatures of 300, 1000, and 2000 K, respectively. 相似文献
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Nilufar Z. Mamadalieva Fadia S. Youssef Hidayat Hussain Gokhan Zengin Adriano Mollica Nawal M. Al Musayeib Mohamed L. Ashour Bernhard Westermann Ludger A. Wessjohann 《Molecules (Basel, Switzerland)》2021,26(21)
The antioxidant and enzyme inhibitory potential of fifteen cycloartane-type triterpenes’ potentials were investigated using different assays. In the phosphomolybdenum method, cycloalpioside D (6) (4.05 mmol TEs/g) showed the highest activity. In 1,1-diphenyl-2-picrylhydrazyl (DPPH*) radical and 2,2′-azino-bis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) cation radical scavenging assays, cycloorbicoside A-7-monoacetate (2) (5.03 mg TE/g) and cycloorbicoside B (10) (10.60 mg TE/g) displayed the highest activities, respectively. Oleanolic acid (14) (51.45 mg TE/g) and 3-O-β-d-xylopyranoside-(23R,24S)-16β,23;16α,24-diepoxycycloart-25(26)-en-3β,7β-diol 7-monoacetate (4) (13.25 mg TE/g) revealed the highest reducing power in cupric ion-reducing activity (CUPRAC) and ferric-reducing antioxidant power (FRAP) assays, respectively. In metal-chelating activity on ferrous ions, compound 2 displayed the highest activity estimated by 41.00 mg EDTAE/g (EDTA equivalents/g). The tested triterpenes showed promising AChE and BChE inhibitory potential with 3-O-β-d-xylopyranoside-(23R,24S)-16β,23;16α,24-diepoxycycloart-25(26)-en-3β,7β-diol 2′,3′,4′,7-tetraacetate (3), exhibiting the highest inhibitory activity as estimated from 5.64 and 5.19 mg GALAE/g (galantamine equivalent/g), respectively. Compound 2 displayed the most potent tyrosinase inhibitory activity (113.24 mg KAE/g (mg kojic acid equivalent/g)). Regarding α-amylase and α-glucosidase inhibition, 3-O-β-d-xylopyranoside-(23R,24S)-16β,23;16α,24-diepoxycycloart-25(26)-en-3β,7β-diol (5) (0.55 mmol ACAE/g) and compound 3 (25.18 mmol ACAE/g) exerted the highest activities, respectively. In silico studies focused on compounds 2, 6, and 7 as inhibitors of tyrosinase revealed that compound 2 displayed a good ranking score (−7.069 kcal/mole) and also that the ΔG free-binding energy was the highest among the three selected compounds. From the ADMET/TOPKAT prediction, it can be concluded that compounds 4 and 5 displayed the best pharmacokinetic and pharmacodynamic behavior, with considerable activity in most of the examined assays. 相似文献
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Synthesis and Structure of two Mixed Substituted Dialanes Al2X2{Si(SiMe3)3}2 · 2 THF (X = Cl, Br) The syntheses of tris(trimethylsilyl)silyl (hypersilyl) and halide substituted dialanes Al2X2{Si(SiMe3)3}2 · 2 THF (X = Cl, Br) are presented. The results of the X‐ray diffraction experiments are presented and discussed in comparison to the AlIII compounds AlBr2Si(SiMe3)3 · THF and AlBr3 · OPh2. 相似文献
77.
Michael Arend Bernhard Westermann Nikolaus Risch 《Angewandte Chemie (International ed. in English)》1998,37(8):1044-1070
Important building blocks for the synthesis of drugs or natural products are found in Mannich bases and their derivatives. Modern variants of the Mannich reaction that expand the potential of the classical intermolecular reaction significantly and enable efficient control of the regioselectivity and stereoselectivity are therefore the topic of intensive research. Intramolecular reactions, in particular as part of domino reaction sequences, often afford astoundingly simple and elegant approaches to complex target compounds. 相似文献
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