Oxyfunctionalisation of anisole and its selected reaction products by unspecific peroxygenases

IF 2.2 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY
Essi Rytkönen , Janne Jänis , Anu Koivula , Juha Rouvinen
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引用次数: 0

Abstract

Unspecific peroxygenases (UPOs) are fungal enzymes capable of oxidizing hundreds of different organic compounds using hydrogen peroxide as the sole co-substrate. Aromatic ethers are among the less-studied substrates for UPOs, even though they offer a potential route to valuable phenolic compounds, such as those derived from the depolymerized lignin as a feedstock. Consequently, the oxyfunctionalisation potential of a panel of 30 UPO enzymes, along with Agrocybe aegerita UPO, was investigated using a simple aromatic ether, anisole. Anisole oxyfunctionalisation by the studied UPOs involved up to four consecutive reactions, resulting in the detection of 14 different products. Aromatic hydroxylation was the primary reaction pathway, leading to methoxyphenols or methoxybenzenediols. O-Demethylation also occurred, as phenol and benzenediols were identified among the products. As expected, different UPOs produced varying products and yields; however, guaiacol and 4-methoxyphenol were detected with every enzyme. The effect of ascorbic acid as a radical scavenger was also assessed, given that radical reactions leading to oligomerisation can occur with phenolic products. Generally, the presence of ascorbic acid broadened the product range, potentially due to the detection of trace products and a reduction in quinone formation. Owing to the broad product scope with anisole, biotransformations were also carried out with the identified phenolic intermediates to evaluate further oxidation routes. Based on these findings, a reaction pathway for anisole was proposed, offering insights into potential applications of UPOs in the tailored oxyfunctionalisation of phenolic substrates.
非特异性过氧酶对苯甲醚及其反应产物的氧化官能化作用
非特异性过氧酶(UPOs)是一种真菌酶,能够以过氧化氢作为唯一的共底物氧化数百种不同的有机化合物。芳香醚是研究较少的UPOs底物之一,尽管它们提供了有价值的酚类化合物的潜在途径,例如从解聚木质素中提取的酚类化合物作为原料。因此,用一种简单的芳香醚苯乙烯醚研究了30种UPO酶的氧化官能化电位,以及Agrocybe agerita UPO。通过所研究的upo,苯甲醚的氧化官能化涉及多达四个连续的反应,从而检测到14种不同的产物。芳香族羟基化反应是主要反应途径,生成甲氧基酚或甲氧基苯二醇。o -去甲基化也发生了,因为在产物中发现了苯酚和苯二醇。正如预期的那样,不同的upo产生不同的产品和产量;每种酶均可检出愈创木酚和4-甲氧基酚。抗坏血酸作为自由基清除剂的作用也被评估,因为自由基反应会导致酚类产物的寡聚化。一般来说,抗坏血酸的存在扩大了产品范围,可能是由于痕量产品的检测和醌形成的减少。由于苯甲醚的产品范围很广,我们还对所鉴定的酚类中间体进行了生物转化,以评估进一步的氧化途径。基于这些发现,作者提出了苯甲醚的反应途径,为UPOs在酚类底物的定制氧化官能化中的潜在应用提供了见解。
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来源期刊
Biochemistry and Biophysics Reports
Biochemistry and Biophysics Reports Biochemistry, Genetics and Molecular Biology-Biophysics
CiteScore
4.60
自引率
0.00%
发文量
191
审稿时长
59 days
期刊介绍: Open access, online only, peer-reviewed international journal in the Life Sciences, established in 2014 Biochemistry and Biophysics Reports (BB Reports) publishes original research in all aspects of Biochemistry, Biophysics and related areas like Molecular and Cell Biology. BB Reports welcomes solid though more preliminary, descriptive and small scale results if they have the potential to stimulate and/or contribute to future research, leading to new insights or hypothesis. Primary criteria for acceptance is that the work is original, scientifically and technically sound and provides valuable knowledge to life sciences research. We strongly believe all results deserve to be published and documented for the advancement of science. BB Reports specifically appreciates receiving reports on: Negative results, Replication studies, Reanalysis of previous datasets.
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