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Rhodium complex-anchored and supramolecular polymer-grafted CdS nanoflower for enhanced photosynthesis of H_(2)O_(2) and photobiocatalytic C–H bond oxyfunctionalization

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Frontiers of Chemical Science and Engineering 2024年第10期18卷 73-82页

作者： Hongwei Jia Xiaoyang Yue Yuying Hou Fei Huang Cuiyao Cao Feifei Jia Guanhua Liu Xiaobing Zheng Yunting Liu Yanjun Jiang School of Chemical Engineering and Technology Hebei University of TechnologyTianjin 300401China National-Local Joint Engineering Laboratory for Energy Conversion in Chemical Process Integration and Resources Utilization School of Chemical Engineering and TechnologyHebei University of TechnologyTianjin 300401China

Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) ***-based semiconductors are promising for the photosynthesis of H_(2)O_(2) owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process,however,they suffer from fast H_(2)O_(2) decomposition on the surface of pristine ***,[Cp*Rh(bpy)H_(2)O]2+,a highly selective proton-coupled electron transfer catalyst,was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H_(2)O_(2),mitigating the surface issue of pristine CdS,increasing light absorption,accelerating photonic carrier separation,and enhancing oxygen reduction reaction selectivity to H_(2)O_(2).This photocatalyst promoted the light driven H_(2)O_(2) generation rate up to 1345μmol·L^(-1)·g^(-1)·h^(-1),which was 2.4 times that of pristine *** constructed heterojunction photocatalyst could supply H_(2)O_(2) in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene,achieving a yield of 81%and an ee value of 99%under optimum conditions.A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system,achieving the corresponding chiral alcohols in good yield(51%–88%)and excellent enantioselectivity(90%–99%ee).

关键词： cadmium sulfide unspecific peroxygenases photobiocatalysis hydrogen peroxide oxyfunctionalization

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Biocatalytic oxyfunctionalization of unsaturated fatty acids to oxygenated chemicals via hydroxy fatty acids

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BIOTECHNOLOGY ADVANCES 2025年 79卷 108510页

作者： Oh, Deok-Kun Lee, Tae-Eui Lee, Jin Shin, Kyung-Chul Park, Jin-Byung Konkuk Univ Dept Biosci & Biotechnol 120 Neungdong Ro Seoul 05029 South Korea Hankuk Univ Foreign Studies Dept Biosci & Biotechnol Yongin 17035 Gyeonggi Do South Korea Ewha Womans Univ Dept Food Sci & Biotechnol 52 Ewhayeodae Gil Seoul 03760 South Korea

The selective oxyfunctionalization of unsaturated fatty acids is difficult in chemical reactions, whereas regio- and stereoselective oxyfunctionalization is often performed in biocatalytic synthesis. Fatty acid oxygenases, including hydratases, lipoxygenases, dioxygenases, diol synthases, cytochrome P450 monooxygenases, peroxygenases, and 12-hydroxylases, are used to convert C16 and C18 unsaturated fatty acids to diverse regio- and stereoselective mono-, di-, and trihydroxy fatty acids via selective oxyfunctionalization. The formed hydroxy fatty acids or hydroperoxy fatty acids are metabolized to industrially important oxygenated chemicals such as lactones, green leaf volatiles, and bioplastic monomers, including omega-hydroxy fatty acids, alpha,omega-dicarboxylic acids, and fatty alcohols, by biocatalysts. For increased oxyfunctionalization of unsaturated fatty acids, enzyme engineering, functional and balanced expression in recombinant cells, selection of suitable catalyst types, and reaction engineering have been suggested. This review describes biocatalysts involved in the oxyfunctionalization of unsaturated fatty acids and the production of hydroxy fatty acids and oxygenated chemicals.

关键词： Biotransformation Fatty acid oxygenases Hydroxy fatty acids Oxygenated chemicals oxyfunctionalization Unsaturated fatty acids

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Toward Kilogram-Scale Peroxygenase-Catalyzed oxyfunctionalization of Cyclohexane

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ORGANIC PROCESS RESEARCH & DEVELOPMENT 2023年第7期27卷 1384-1389页

作者： Hilberath, Thomas van Oosten, Remco Victoria, Juliet Brasselet, Hugo Alcalde, Miguel Woodley, John M. Hollmann, Frank Delft Univ Technol Dept Biotechnol NL-2629 HZ Delft Netherlands Tech Univ Denmark Dept Chem & Biochem Engn DK-2800 Lyngby Denmark Atlant Innov NL-2611 EH Delft Netherlands CSIC Inst Catalysis Dept Biocatalysis Madrid 28049 Spain

Mol-scale oxyfunctionalization of cyclohexane to cyclohexanol/cyclohexanone(KA-oil) using an unspecific peroxygenase is reported. Using AaeUPO from Agrocybe aegerita and simple H2O2 as an oxidant, cyclohexanolconcentrations of more than 300 mM (>60% yield) at attractive productivities(157 mM h(-1), approx. 15 g L-1 h(-1)) were achieved. Current limitations of the proposedbiooxidation system have been identified paving the way for futureimprovements and implementation.

关键词： biocatalysis peroxygenase oxyfunctionalization cyclohexane upscaling bulk chemical

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Unlocking lignin valorisation: oxyfunctionalization of lignin dimer model compounds by unspecific peroxygenases

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ENZYME AND MICROBIAL TECHNOLOGY 2025年 189卷 110661页

作者： Rytkonen, Essi Rouvinen, Juha Janis, Janne Univ Eastern Finland Dept Chem & Sustainable Technol POB 111 Joensuu 80101 Finland

Lignin is an abundantly available biopolymer composed of three structural units, linked by a complex network of bonds, including a high proportion of beta-O-4 ether linkages. As a renewable carbon source, it can be depolymerised into a variety of small aromatic compounds such as monophenols. Enzymatic bioprocessing offers a promising alternative to traditional chemical lignin degradation strategies, potentially producing value-added compounds, such as monoaromatics. Unspecific peroxygenases (UPOs) are promising enzymes for lignin bioprocessing due to their ability to catalyse aromatic oxidation and demethylation reactions, which are critical for lignin valorisation. In this study, thirteen different UPOs were evaluated for their oxidation potential with two lignin dimer model compounds, guaiacylglycerol-beta-guaiacyl ether and veratrylglycerol-beta-guaiacyl ether. Both compounds were successfully processed, yielding a wide range of products, e.g., via C alpha-oxidation, demethylation, and bond cleavage reactions. Notably, the cleavages frequently occurred at the C beta-O ether bond, a major linkage between the lignin monomers, being beneficial for lignin degradation and subsequent valorisation. Some of the identified products, such as vanillin, are of interest either as valuable end-products or as precursors for further conversion into specialty chemicals.

关键词： Unspecific peroxygenase oxyfunctionalization Lignin Hydroxylation Dealkylation Bond cleavage

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Characterization of Pt/g-C3N4-Catalyzed Methanol Oxidation to Drive Peroxygenase-Catalyzed oxyfunctionalization of Hydrocarbons

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ACS SUSTAINABLE CHEMISTRY & ENGINEERING 2022年第37期10卷 12156-12164页

作者： Shen, Qianqian Zhang, Chen Chen, Lei Huang, Boqiang Yu, Yunsong Zhang, Zaoxiao Zhang, Wuyuan Xian Jiaoton Univ Sch Chem Engn & Technol Xian 710049 Peoples R China Chinese Acad Sci Tianjin Inst Ind Biotechnol Tianjin 300308 Peoples R China Natl Technol Innovat Ctr Synthet Biol Tianjin 300308 Peoples R China

The photobiocatalysis combining photocatalysts and enzymes provides new strategies for organic synthesis and energy conversion. However, the available photocatalysts used in photobiocatalysis are still limited. Herein, highly dispersed Pt nanoparticles supported on graphitic carbon nitride (Pt/g-C3N4) were designed and applied for the light-driven in situ generation of H2O2, which was subsequently supplied to peroxygenase for selective oxyfunctionalization of C-H bonds. Substrates with activated and non-activated C-H bonds were hydroxylated into the corresponding alcohols with an enantiomeric excess of up to 99% and a turnover number of 133,000, which was about four times higher than that of unsupported g-C3N4 catalysts. Further mechanistic study by UV-vis, static photoluminescence spectroscopy, and DFT calculations revealed that the effective absorption of visible light by Pt nanoparticles on the surface of g-C(3)N(4 )and the strong interaction between O-2 and the g-C3N4 surface were advantageous to improve the performance of photobiocatalysis. This research provides new insights into the fabrication of efficient photocatalysts compatible with peroxyzymes, paving the way for synergistic photobiocatalysis for selective oxyfunctionalization of hydrocarbons.

关键词： photobiocatalysis peroxygenase oxyfunctionalization biocatalysis photocatalysis

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Visible-light-mediated remote aliphatic C-H oxyfunctionalization over CuCl2 decorated hollowed-TS-1 photocatalysts

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APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY 2022年第0期302卷 120851-120851页

作者： Yin, Hui Su, Feng Luo, Chao Zhu, Lixia Zhong, Wenzhou Mao, Liqiu You, Kuiyi Yin, Dulin Hunan Normal Univ Natl & Local United Engn Lab New Petrochem Mat & Key Lab Chem Biol Tradit Chinese Med Reserach Minist EducColl Chem & Chem Engn Changsha 410081 Peoples R China Xiangtan Univ Coll Chem Engn Xiangtan 411105 Peoples R China

Selective oxygenation of alkanes via C-H bond activation still remains a challenge because the oxygencontaining products are more active than the substrates. Here, we develop a new concept of eco-friendly zeolite-fixed photocatalyst to impart catalytic performance via loading CuCl2 upon visible-light irradiation. Complete selectivity in terms of the final oxidation product KA-oil was obtained with 24% conversion in the application of cyclohexane oxidation. After optimization, the desired ketones and alcohols were also obtained in good to excellent selectivities with broad substrate scope. Multiple experimental studies combined with theoretical calculations demonstrate that the formation of the unique CuCl2/TS-1 hollow structure with isolated CuCl2 species anchored onto the inner and outer surface of TS-1 shells: the function of the major tetrahedral Ti-O4 sites in heterojunctions to isolate energy levels near the conduction and valence bands. In photocatalysis, the presence of Cu-O-Ti-O3 heterojunctions facilitates separation and transfer of photogenerated electrons and holes

关键词： Hollow TS-1 zeolite oxyfunctionalization Alkane Photocatalysis

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Valorization of Small Alkanes by Biocatalytic oxyfunctionalization

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CHEMSUSCHEM 2022年第9期15卷 e202101116-e202101116页

作者： Mahor, Durga Cong, Zhiqi Weissenborn, Martin J. Hollmann, Frank Zhang, Wuyuan Chinese Acad Sci Tianjin Inst Ind Biotechnol Natl Innovat Ctr Synthet Biotechnol 32 West 7th AveTianjin Airport Economic Area Tianjin 300308 Peoples R China Indian Inst Sci Educ & Res Berhampur 760010 Odisha India Chinese Acad Sci Qingdao Inst Bioenergy & Bioproc Technol Qingdao 266101 Shandong Peoples R China Leibniz Inst Plant Biochem Weinberg 3 D-06120 Halle Germany Delft Univ Technol Dept Biotechnol Maasweg 9 NL-2629HZ Delft Netherlands

The oxidation of alkanes into valuable chemical products is a vital reaction in organic synthesis. This reaction, however, is challenging, owing to the inertness of C-H bonds. Transition metal catalysts for C-H functionalization are frequently explored. Despite chemical alternatives, nature has also evolved powerful oxidative enzymes (e. g., methane monooxygenases, cytochrome P450 oxygenases, peroxygenases) that are capable of transforming C-H bonds under very mild conditions, with only the use of molecular oxygen or hydrogen peroxide as electron acceptors. Although progress in alkane oxidation has been reviewed extensively, little attention has been paid to small alkane oxidation. The latter holds great potential for the manufacture of chemicals. This Minireview provides a concise overview of the most relevant enzyme classes capable of small alkanes (C-<6) oxyfunctionalization, describes the essentials of the catalytic mechanisms, and critically outlines the current state-of-the-art in preparative applications.

关键词： alkanes biocatalysis enzymes oxidation oxyfunctionalization

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A Novel Unspecific Peroxygenase from Galatian marginata for Biocatalytic oxyfunctionalization Reactions

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MOLECULAR CATALYSIS 2022年 531卷

作者： Ma, Yunjian Liang, Hongjing Zhao, Zexin Wu, Bin Lan, Dongming Hollmann, Frank Wang, Yonghua South China Univ Technol Sch Food Sci & Engn Guangzhou 510640 Peoples R China Macau Univ Sci & Technol Nehers Biophys Lab Innovat Drug Discovery State Key Lab Qual Res Chinese Med Taipa Macau Peoples R China South China Univ Technol Sch Biosci & Bioengn Guangzhou 510006 Peoples R China Hubei Univ Technol Key Lab Fermentat Engn Hubei Key Lab Ind Microbiol Minist Educ Wuhan 430068 Peoples R China Delft Univ Technol Dept Biotechnol Maasweg 9 NL-2629 HZ Delft Netherlands Guangdong Youmei Inst Inteligent Biomfg Co Ltd Foshan 528200 Guangdong Peoples R China Delft Univ Technol Dept Biotechnol Maasweg 9 NL-2628 BL Delft Netherlands

Unspecific peroxygenases (UPOs, EC 1.11.2.1) are promising oxyfunctionalization catalysts because of their unique stereoselectivity. However, so far only a few UPOs have been reported. In this study, gene mining was used to identify a gene from Galerina marginata that coded for a novel UPO (GmaUPO). GmaUPO was expressed in Pichia pastoris X-33 by scale-up fermentation (the UPO activity of the culture supernatant was 118 U/L). GmaUPO exhibited a molecular weight of 40 kDa and exhibited highest activity at 35 degrees C and pH 9, respectively. Furthermore, GmaUPO was demonstrated to catalyze the epoxidation, sulfoxidation, and hydroxylation of common substrates, particularly fatty acids such as tridecanoic acid. The molecular basis for GmaUPO regiose-lectivity for fatty acid hydroxylation was explored by molecular modelling. The regioselectivity was mostly governed by the architecture of the enzyme's active site.

关键词： Unspecific peroxygenase Galerina marginata Bioinformatics analysis Heterologous expression oxyfunctionalization

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Piezobiocatalysis: Ultrasound-Driven Enzymatic oxyfunctionalization of C-H Bonds

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ACS CATALYSIS 2020年第9期10卷 5236-5242页

作者： Yoon, Jaeho Kim, Jinhyun Tieves, Florian Zhang, Wuyuan Alcalde, Miguel Hollmann, Frank Park, Chan Beum Korea Adv Inst Sci & Technol KAIST Dept Mat Sci & Engn Daejeon 305701 South Korea Delft Univ Technol Dept Biotechnol Delft 2629 HZ Netherlands CSIC Dept Biocatalysis Inst Catalysis Madrid 28049 Spain

Peroxygenases have long inspired the selective oxyfunctionalization of various aliphatic and aromatic compounds, because of their broad substrate spectrum and simplicity of catalytic mechanism. This study provides a proof-of-concept of piezobiocatalysis by demonstrating peroxygenase-catalyzed oxyfunctionalization reactions fueled by piezocatalytically generated H2O2. Bismuth oxychloride (BiOCl) generated H2O2 in situ via an oxygen reduction reaction under ultrasonic wave conditions. Through the simple combination of water, ultrasound, recombinant, evolved unspecific peroxygenase from Agrocybe aegerita (rAaeUPO), and BiOCl, the piezobiocatalytic platform accelerated selective hydroxylation of ethylbenzene to enantiopure (R)-1-phenylethanol [total turnover number of rAaeUPO (TTNrAaeUPO), 2002;turnover frequency, 77.7 min(-1);>99% enantiomeric excess (ee)]. The BiOCl-rAaeUPO couple also catalyzed other representative substrates (e.g., propylbenzene, 1-chloro-4-ethylbenzene, cyclohexane, and cis-beta-methylstyrene) with high turnover frequency and selectivity. We alleviated the oxidative stress of piezocatalytically generated OH center dot on rAaeUPO by spatial separation of rAaeUPO and BiOCl, which resulted in greatly enhanced TTNrAaeUPO of >3900 and the notable prolongation of reaction time. Overall, the BiOCl-rAaeUPO couple serves as a mechanical-to-chemical energy conversion platform for driving peroxygenase-catalyzed reactions under ultrasonic conditions.

关键词： oxidation oxyfunctionalization peroxygenase piezocatalysis piezobiocatalysis

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Selective Electroenzymatic oxyfunctionalization by Alkane Monooxygenase in a Biofuel Cell

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ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 2020年第23期59卷 8969-8973页

作者： Yuan, Mengwei Abdellaoui, Sofiene Chen, Hui Kummer, Matthew J. Malapit, Christian A. You, Chun Minteer, Shelley D. Univ Utah Dept Chem 315 S 1400 E Salt Lake City UT 84112 USA Chinese Acad Sci Tianjin Inst Ind Biotechnol 32 West 7th Ave Tianjin 300308 Peoples R China Univ Reims FARE Lab INRAE F-51100 Reims France

Aliphatic synthetic intermediates with high added value are generally produced from alkane sources (e.g., petroleum) by inert carbon-hydrogen (C-H) bond activation using classical chemical methods (i.e. high temperature, rare metals). As an alternative approach for these reactions, alkane monooxygenase from Pseudomonas putida (alkB) is able to catalyze the difficult terminal oxyfunctionalization of alkanes selectively and under mild conditions. Herein, we report an electrosynthetic system using an alkB biocathode which produces alcohols, epoxides, and sulfoxides through bioelectrochemical hydroxylation, epoxidation, sulfoxidation, and demethylation. The capacity of the alkB binding pocket to protect internal functional groups is also demonstrated. By coupling our alkB biocathode with a hydrogenase bioanode and using H-2 as a clean fuel source, we have developed and characterized a series of enzymatic fuel cells capable of oxyfunctionalization while simultaneously producing electricity.

关键词： alkane monooxygenase biofuel cells C-H activation electroenzymatic catalysis oxyfunctionalization

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