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1.
Rachel L. Weller 《Tetrahedron letters》2004,45(30):5807-5810
Ethyl (E)-4,5-dibromo-2-pentenoate readily reacts with an assortment of primary amines in the presence of DBU to afford the corresponding conjugated aziridines in good to moderate yields. That the reaction is compatible with a nucleoside-derived amine suggests a broad scope of application. 相似文献
2.
Biocatalytic cascades that involve enzymatic oxidation as one or more key steps are powerful tools to access valuable chemicals with various functionalizations starting from simple substrates, without the isolation of intermediates. This review discusses the recent advances in oxidative cascades, with perspectives given on the current limitations and future developments. The strategies employed to achieve efficient supply of redox cofactors are also highlighted. The examples include cascades that begin with alkene epoxidation, alkane hydroxylation, alcohol oxidation or amine oxidation. These oxidative steps are followed by a variety of enzyme-catalyzed functionalizations, producing a diverse range of high-value products. 相似文献
3.
Beatrice Battistella Dr. Thomas Lohmiller Dr. Beatrice Cula Prof. Dr. Peter Hildebrandt Dr. Uwe Kuhlmann Prof. Dr. Holger Dau Dr. Stefan Mebs Prof. Dr. Kallol Ray 《Angewandte Chemie (International ed. in English)》2023,62(12):e202217076
In class Ib ribonucleotide reductases (RNRs) a dimanganese(II) cluster activates superoxide (O2⋅−) rather than dioxygen (O2), to access a high valent MnIII−O2−MnIV species, responsible for the oxidation of tyrosine to tyrosyl radical. In a biomimetic approach, we report the synthesis of a thiolate-bound dimanganese complex [MnII2(BPMT)(OAc)2](ClO)4 (BPMT=(2,6-bis{[bis(2-pyridylmethyl)amino]methyl}-4-methylthiophenolate) ( 1 ) and its reaction with O2⋅− to form a [(BPMT)MnO2Mn]2+ complex 2 . Resonance Raman investigation revealed the presence of an O−O bond in 2 , while EPR analysis displayed a 16-line St=1/2 signal at g=2 typically associated with a MnIIIMnIV core, as detected in class Ib RNRs. Unlike all other previously reported Mn−O2−Mn complexes, generated by O2⋅− activation at Mn2 centers, 2 proved to be a capable electrophilic oxidant in aldehyde deformylation and phenol oxidation reactions, rendering it one of the best structural and functional models for class Ib RNRs. 相似文献
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Sebastian Schaupp Francisco J. Arriaza-Gallardo Dr. Nicole Paczia Kenichi Ataka Dr. Seigo Shima 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(6):e202316478
[Fe]-hydrogenase harbors the iron-guanylylpyridinol (FeGP) cofactor, in which the Fe(II) complex contains acyl-carbon, pyridinol-nitrogen, cysteine-thiolate and two CO as ligands. Irradiation with UV-A/blue light decomposes the FeGP cofactor to a 6-carboxymethyl-4-guanylyl-2-pyridone (GP) and other components. Previous in vitro biosynthesis experiments indicated that the acyl- and CO-ligands in the FeGP cofactor can scramble, but whether scrambling occurred during biosynthesis or photolysis was unclear. Here, we demonstrate that the [18O1-carboxy]-group of GP is incorporated into the FeGP cofactor by in vitro biosynthesis. MS/MS analysis of the 18O-labeled FeGP cofactor revealed that the produced [18O1]-acyl group is not exchanged with a CO ligand of the cofactor, indicating that the acyl and CO ligands are scrambled during photolysis rather than biosynthesis, which ruled out any biosynthesis mechanisms allowing acyl/CO ligands scrambling. Time-resolved infrared spectroscopy indicated that an acyl-Fe(CO)3 intermediate is formed during photolysis, in which scrambling of the CO and acyl ligands can occur. This finding also suggests that the light-excited FeGP cofactor has a higher affinity for external CO. These results contribute to our understanding of the biosynthesis and photosensitive properties of this unique H2-activating natural complex. 相似文献
6.
A simple, highly efficient, and economical biphasic cell-free system was developed for biocatalytic reduction of prochiral aromatic ketones to furnish enantiopure alcohols. This system is characterized by using endogenous enzymes of the cell-free extract to form enzyme-coupled NADPH recycling system. Besides, it offered much higher productivity than whole cells and greatly simplified the preparation process of biocatalysts in comparison with isolated enzymes. Various prochiral aromatic ketones, especially α-substituted acetophenone derivatives, were reduced to chiral alcohols with excellent enantiomeric excess (ee) and moderate to good yield by this cell-free system. 相似文献
7.
Selmihan Sahin Olivier N. Lemaire Mélissa Belhamri Julia M. Kurth Cornelia U. Welte Tristan Wagner Ross D. Milton 《Angewandte Chemie (International ed. in English)》2023,62(45):e202311981
Massive efforts are invested in developing innovative CO2-sequestration strategies to counter climate change and transform CO2 into higher-value products. CO2-capture by reduction is a chemical challenge, and attention is turned toward biological systems that selectively and efficiently catalyse this reaction under mild conditions and in aqueous solvents. While a few reports have evaluated the effectiveness of isolated bacterial formate dehydrogenases as catalysts for the reversible electrochemical reduction of CO2, it is imperative to explore other enzymes among the natural reservoir of potential models that might exhibit higher turnover rates or preferential directionality for the reductive reaction. Here, we present electroenzymatic catalysis of formylmethanofuran dehydrogenase, a CO2-reducing-and-fixing biomachinery isolated from a thermophilic methanogen, which was deposited on a graphite rod electrode to enable direct electron transfer for electroenzymatic CO2 reduction. The gas is reduced with a high Faradaic efficiency (109±1 %), where a low affinity for formate prevents its electrochemical reoxidation and favours formate accumulation. These properties make the enzyme an excellent tool for electroenzymatic CO2-fixation and inspiration for protein engineering that would be beneficial for biotechnological purposes to convert the greenhouse gas into stable formate that can subsequently be safely stored, transported, and used for power generation without energy loss. 相似文献
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辅因子是蛋白质或酶结构的重要组成部分,在许多酶的功能中发挥重要乃至关键作用。在科研和教学中,现有的辅因子概念及其分类系统不够清晰准确。本文从化学本质和功能上将辅因子分为催化型、载体型和底物型3类,并以若干典型的辅因子为例讨论辅因子的特异性及再生性等问题。 相似文献
9.
Hassler BL Dennis M Laivenieks M Zeikus JG Worden RM 《Applied biochemistry and biotechnology》2007,143(1):1-15
Bioelectronic interfaces that facilitate electron transfer between the electrode and a dehydrogenase enzyme have potential
applications in biosensors, biocatalytic reactors, and biological fuel cells. The secondary alcohol dehydrogenase (2° ADH)
from Thermoanaerobacter ethanolicus is especially well suited for the development of such bioelectronic interfaces because of its thermostability and facile
production and purification. However, the natural cofactor for the enzyme, β-nicotinamide adenine dinucleotide phosphate (NADP+), is more expensive and less stable than β-nicotinamide adenine dinucleotide (NAD+). PCR-based, site-directed mutagenesis was performed on 2° ADH in an attempt to adjust the cofactor specificity toward NAD+ by mutating Tyr218 to Phe (Y218F 2° ADH). This mutation increased the K
m(app) for NADP+ 200-fold while decreasing the K
m(app) for NAD+ 2.5-fold. The mutant enzyme was incorporated into a bioelectronic interface that established electrical communication between
the enzyme, the NAD+, the electron mediator toluidine blue O (TBO), and a gold electrode. Cyclic voltammetry, impedance spectroscopy, gas chromatography,
mass spectrometry, constant potential amperometry, and chronoamperometry were used to characterize the mutant and wild-type
enzyme incorporated in the bioelectronic interface. The Y218F 2° ADH exhibited a fourfold increase in the turnover ratio compared
to the wild type in the presence of NAD+. The electrochemical and kinetic measurements support the prediction that the Rossmann fold of the enzyme binds to the phosphate
moiety of the cofactor. During the 45 min of continuous operation, NAD+ was electrically recycled 6.7 × 104 times, suggesting that the Y218F 2° ADH-modified bioelectronic interface is stable. 相似文献
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