Article
Chemistry, Multidisciplinary
Dumei Ma, Libo Zhang, Yingwu Yin, Qian Wang
Summary: The study found that the structure of substrates significantly impacts the product type of cytochrome P450 OleT(SA) catalyzed decarboxylation/hydroxylation reactions, even in a remote distance from the carboxyl group. Molecular docking analysis revealed potential interactions between carboxylate groups of different probes and the enzyme active center, which may contribute to the bifurcative chemistry.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Physical
Tabish Iqbal, Subhashini Murugan, Kalpana Rajendran, Jagpreet Singh Sidhu, Debasis Das
Summary: UndB is a highly valuable enzyme that can convert fatty acids into 1-alkenes. This study provides insights into the catalytic mechanism and function of UndB, establishing its efficiency in producing industrially valuable medium-chain 1-alkenes.
Article
Chemistry, Multidisciplinary
Ran Ge, Pengpeng Zhang, Xuetian Dong, Yuanying Li, Zhoutong Sun, Yongyi Zeng, Bishuang Chen, Wuyuan Zhang
Summary: This study demonstrates a method to synthesize fatty epoxides from renewable fatty acids using fatty acid photodecarboxylase. The enzyme allows for high selectivity in the synthesis of various fatty epoxides. Additionally, the combination of the enzyme with other enzymes enables the transformation of oleic acid and its triglyceride into different fatty compounds.
Article
Chemistry, Physical
Hao Chen, Mengfei Huang, Wenliang Yan, Wen-Ju Bai, Xiqing Wang
Summary: Directed evolution of a P450 hydroxylase leads to a highly selective engineered enzyme capable of catalyzing the oxyfunctionalization of fatty acids. This biocatalyst displays high reactivity and can convert a variety of fatty acids to optically pure beta-hydroxy fatty acids, offering a chemoenzymatic strategy to access valuable fatty acid derivatives. Molecular docking studies provide insight into the regio- and enantioselectivity of this reaction.
Article
Chemistry, Organic
Maria J. Gonzalez, Felix Bauer, Bernhard Breit
Summary: A novel methodology for accessing versatile vinylboronic esters through a cobalt-catalyzed hydroboration reaction is reported, utilizing ligand-controlled reduction of Co(II) by H-BPin to generate catalytically active Co(I) hydride complexes. This approach eliminates the need for stoichiometric amounts of base and avoids the generation of boron-containing byproducts, resulting in high functional group tolerance and atom economy.
Article
Chemistry, Physical
Keita Omura, Yuichiro Aiba, Kazuto Suzuki, Shinya Ariyasu, Hiroshi Sugimoto, Osami Shoji
Summary: The self-sufficient enzyme P450BM3 was reconstituted with manganese protoporphyrin IX, resulting in Mn-BM3. This artificial enzyme was found to catalyze the monooxygenation of various substrates by activating molecular oxygen. The study also revealed the involvement of a radical intermediate in the hydroxylation process.
Article
Chemistry, Physical
Keita Omura, Yuichiro Aiba, Kazuto Suzuki, Shinya Ariyasu, Hiroshi Sugimoto, Osami Shoji
Summary: This research reports the successful translation of P450BM3 to Mn-BM3 which catalyzes the monooxygenation reaction of substrates, demonstrating the involvement of radical intermediates in the hydroxylation reaction and further confirming the generality of this reaction mechanism. Experimental and computational results indicate that the activation barrier of Mnporphine in the rebound step is higher, consistent with the experimental results.
Article
Chemistry, Physical
Hiroki Onoda, Shota Tanaka, Yoshihito Watanabe, Osami Shoji
Summary: CYP152A1 is a fatty acid peroxygenase with catalase activity, which prevents enzyme deactivation when no substrate is available for oxidation.
FARADAY DISCUSSIONS
(2022)
Article
Chemistry, Multidisciplinary
Kazuto Suzuki, Joshua Kyle Stanfield, Keita Omura, Yuma Shisaka, Shinya Ariyasu, Chie Kasai, Yuichiro Aiba, Hiroshi Sugimoto, Osami Shoji
Summary: Catching the structure of cytochrome P450 enzymes in flagrante is crucial for the development of P450 biocatalysts. We report the crystal structure of P450BM3 mimicking the state in the precise moment preceding epoxidation, which is in perfect agreement with the experimentally observed stereoselectivity. This method serves as a powerful tool for predicting and modelling the stereoselectivity of P450 reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Li Zong, Yan Zhang, Zhengkang Shao, Anita Ljubic, Charlotte Jacobsen, Renjun Gao, Bekir Engin Eser, Yingwu Wang, Zheng Guo
Summary: Enzymatic hydroxylation of fatty acids by a newly discovered self-sufficient CYP102 enzyme, BAMF0695, offers a sustainable and green production route for high-value hydroxy fatty acids (HFAs). BAMF0695 exhibits preference for hydroxylation at the sub-terminal positions of fatty acids and has broad temperature optimum and high thermostability, making it compatible for bioprocesses. Through mutagenesis, high regioselectivity variants of BAMF0695 were isolated, enabling the production of single HFA regioisomers with high selectivities.
Article
Chemistry, Multidisciplinary
Stefan Weber, Daniel Zobernig, Berthold Stoeger, Luis F. Veiros, Karl Kirchner
Summary: The Mn-catalyzed hydroboration of terminal alkenes and the 1,2-diboration of terminal alkynes with pinacolborane have been successfully achieved. The most active pre-catalyst is a bench-stable alkyl bisphosphine Mn-I complex. The catalytic process involves migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate, which further undergoes B-H bond cleavage or C-H bond cleavage for alkenes and alkynes, respectively, forming active Mn-I boryl and acetylide catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Melanie Nolden, Mark J. I. Paine, Ralf Nauen
Summary: Pyrethroid resistance in Anopheles funestus is a major threat to the eradication of malaria. This study identified the enzymes CYP6P9a and CYP6P9b as major drivers of pyrethroid resistance in An. funestus, and investigated their interactions with azole-fungicides and pyrethroids. The study found that the mutation V310I in CYP6P9b increased its metabolic activity towards pyrethroids, particularly permethrin. Additionally, the study discovered the first metabolites of permethrin and deltamethrin, which were also suitable substrates for the CYP6P9 variants and were depleted to a higher extent than their parent compounds. Furthermore, it was confirmed that CYP6P9a and CYP6P9b are capable of metabolizing pyrethroids. These findings provide new insights into the molecular mechanisms of pyrethroid resistance in An. funestus.
INSECT BIOCHEMISTRY AND MOLECULAR BIOLOGY
(2022)
Article
Chemistry, Physical
Cheri Louise Jacobs, Rodolpho do Aido-Machado, Carmien Tolmie, Martha Sophia Smit, Diederik Johannes Opperman
Summary: Selective oxyfunctionalization of non-activated C-H bonds is a significant challenge in synthetic chemistry. In this study, the biocatalytic hydroxylation of medium-chain n-alkanes by the bacterial enzyme CYP153A71 was characterized. The enzyme was found to convert 1-alkanols to aldehydes, fatty acids, and alpha,omega-diols. The crystal structure of the enzyme bound to octanoic acid provided insights into its regioselectivity and substrate binding orientation.
Article
Food Science & Technology
Matthew C. Hamilton, Melissa M. Heintz, Marisa Pfohl, Emily Marques, Lucie Ford, Angela L. Slitt, William S. Baldwin
Summary: The study showed that PFOS induces CYP2B6 but does not alleviate PFOS toxicity, likely due to increased retention. In ND-fed mice, CYP2B6 can protect from PFOS-induced steatosis, but when treated with a high-fat diet, it exacerbates steatosis.
FOOD AND CHEMICAL TOXICOLOGY
(2021)
Review
Immunology
Ameena Mohammed, Arunasree M. Kalle, Pallu Reddanna
Summary: This review provides an overview of the synthesis and role of eicosanoids in the resolution of inflammation in the context of Corona Virus infection, focusing on their regulation of cytokine production.
JOURNAL OF INFLAMMATION RESEARCH
(2022)
Article
Biochemistry & Molecular Biology
Libo Zhang, Yanmei Xu, Thomas M. Makris, Qian Wang
Article
Chemistry, Physical
Konstantin Khivantsev, Alessandro Biancardi, Mahdi Fathizadeh, Fahad Almalki, Job L. Grant, Huynh Ngoc Tien, Abolfazl Shakouri, Douglas A. Blom, Thomas M. Makris, John R. Regalbuto, Marco Caricato, Miao Yu
Article
Biochemistry & Molecular Biology
Caleb R. Schlachter, Leily Daneshian, Jose Amaya, Vincent Klapper, Nicky Wybouw, Tomasz Borowski, Thomas Van Leeuwen, Vojislava Grbic, Miodrag Grbic, Thomas M. Makris, Maksymilian Chruszcz
INSECT BIOCHEMISTRY AND MOLECULAR BIOLOGY
(2019)
Article
Chemistry, Multidisciplinary
Olivia M. Manley, Ruixi Fan, Yisong Guo, Thomas M. Makris
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Biochemistry & Molecular Biology
Safaa Kader, Mehri Monavarian, Danial Barati, Seyedsina Moeinzadeh, Thomas M. Makris, Esmaiel Jabbari
Article
Biochemistry & Molecular Biology
Matthew Blahut, Courtney E. Wise, Michael R. Bruno, Guangchao Dong, Thomas M. Makris, Patrick A. Frantom, Jack A. Dunkle, F. Wayne Outten
JOURNAL OF BIOLOGICAL CHEMISTRY
(2019)
Article
Biochemistry & Molecular Biology
Milda Kaniusaite, Robert J. A. Goode, Ralf B. Schittenhelm, Thomas M. Makris, Max J. Cryle
ACS CHEMICAL BIOLOGY
(2019)
Article
Materials Science, Biomaterials
Libo Zhang, Andrew Beatty, Lin Lu, Akrm Abdalrahman, Thomas M. Makris, Guiren Wang, Qian Wang
MATERIALS SCIENCE AND ENGINEERING C-MATERIALS FOR BIOLOGICAL APPLICATIONS
(2020)
Article
Agricultural Engineering
Libo Zhang, Olivia M. Manley, Dumei Ma, Yingwu Yin, Thomas M. Makris, Qian Wang
BIORESOURCE TECHNOLOGY
(2020)
Article
Chemistry, Physical
Kamolrat Metavarayuth, Otega Ejegbavwo, Gavin McCarver, Michael L. Myrick, Thomas M. Makris, Konstantinos D. Vogiatzis, Sanjaya D. Senanayake, Olivia M. Manley, Amani M. Ebrahim, Anatoly Frenkel, Sooyeon Hwang, Thayalan Rajeshkumar, Juan D. Jimenez, Kexun Chen, Natalia B. Shustova, Donna A. Chen
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2020)
Article
Chemistry, Multidisciplinary
Olivia M. Manley, Haoyu Tang, Shan Xue, Yisong Guo, Wei-chen Chang, Thomas M. Makris
Summary: BesC is a member of an emerging family of diiron enzymes that catalyze an unusual type of carbon-carbon cleavage reaction. It activates O-2 in a substrate-gated manner to generate a diferric-peroxo intermediate, initiating a unique reaction trajectory by cleaving the C4-H bond as the rate-limiting step in a single turnover reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Matthew Dutra, Shannon McElhenney, Olivia Manley, Tom Makris, Vitaly Rassolov, Sophya Garashchuk
Summary: This article presents a computational model for studying the structure of P450, which is relevant for the development of biomimetic catalysts and inhibitors for controlled CH-bond activation in synthetic chemistry. By combining experimental findings and computational efficiency, the differences between the wild-type and mutant forms of OleT P450 decarboxylase are investigated. The study highlights the limitations of single-reference electronic structure methods and emphasizes the importance of using the proper state when modeling the OleT catalyzed hydrogen atom transfer reaction.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Matthew Dutra, Jose A. Amaya, Shannon McElhenney, Olivia M. Manley, Thomas M. Makris, Vitaly Rassolov, Sophya Garashchuk
Summary: This study investigates the hydrogen atom transfer (HAT) reaction by Compound I in the high-valent ferryl cytochrome P450 (CYP) intermediate. The research contributes to the understanding of biomimetic catalysts for controlled C-H bond activation, which is a challenge in synthetic chemistry.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Multidisciplinary
Hannah E. Gering, Xiaojun Li, Haoyu Tang, Paul D. Swartz, Wei-Chen Chang, Thomas M. Makris
Summary: The cytochrome P450 (CYP) AspB is involved in the biosynthesis of the diketopiperazine (DKP) aspergilazine A, and a new mechanism of CYP AspB involving a ferric-superoxide species as a primary oxidant for DKP-assembly is discovered. This finding provides important insight into the reaction mechanism of heme enzymes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Mohammad Jahirul Islam, Kyoung Chul Park, Olivia M. M. Manley, Mark D. D. Smith, Thomas M. M. Makris, Dmitry V. V. Peryshkov
Summary: We describe the synthesis and characterization of a nickel(II) complex with a dicarboranyl CNC dianionic pincer ligand, which can activate acetonitrile through C-C bond cleavage. By deprotonating the relatively acidic C-H bond of coordinated acetonitrile with potassium t-butoxide, a C-bound cyanomethylene ligand is formed at the metal center. Unlike most previously characterized Ni(II) cyanoalkyls, this complex can rapidly transform under aerobic conditions at room temperature to form CNC-ligated nickel(II) cyanide, indicating facile cleavage of the C-CN bond. The cyanoalkyl and cyanide complexes were isolated in excellent yields and characterized by NMR spectroscopy and single-crystal X-ray diffraction.