Article
Chemistry, Multidisciplinary
Rui-Ning Li, Shi-Lu Chen
Summary: Selective halogenation plays a crucial role in synthetic chemistry. BesD, a new member of the non-heme Fe(II)/alpha-ketoglutarate (alpha KG)-dependent halogenase family, is capable of activating sp(3) C-H bond and halogenating lysine without the presence of a carrier protein. Density functional calculations reveal the proposed chlorination mechanism in BesD, which involves the formation of Cl-Fe(IV)=O, the isomerization of Cl-Fe(IV)=O, hydrogen abstraction by Fe(IV)=O, and chloro rebound to the substrate carbon radical. The bromination and azidation reactions of lysine catalyzed by BesD follow the same mechanism as chlorination.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Energy & Fuels
Yuna Kim, Desiree Leistenschneider, Arno de Klerk, Weixing Chen
Summary: This study examined the potential of producing carbon fibers from asphaltenes, investigated the effects of various pretreatment methods on properties, and identified factors affecting melt spin productivity.
Article
Chemistry, Multidisciplinary
Pritam Mondal, Izumi Ishigami, Syun-Ru Yeh, Gayan B. Wijeratne
Summary: This study investigates the mechanism of action of mammalian nitric oxide synthase (NOS) through a NOS model system. The findings provide evidence that heme peroxo intermediates play a crucial role in the oxidation of oximes, leading to the formation of ketones and nitroxyl anions. The results are consistent with previous studies and are supported by recent enzymatic research.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Biochemistry & Molecular Biology
Atefeh Afsar, Maria del Carmen Chacon Castro, Adedamola Saidi Soladogun, Li Zhang
Summary: Alzheimer's disease (AD) is a progressive neurodegenerative disorder characterized by neurofibrillary tangles, amyloid beta plaque deposition, and neurodegeneration. Genetic mutations, inflammation, blood-brain barrier impairment, mitochondrial dysfunction, oxidative stress, and metal ion imbalance are associated with AD progression. Recent studies have shown a link between altered heme metabolism and AD. Understanding the underlying mechanisms and identifying therapeutic targets is crucial for AD drug development. This review discusses common alterations in AD, potential therapeutic targets, mathematical models, and treatment strategies.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Hanna Kwon, Jaswir Basran, Chinar Pathak, Mahdi Hussain, Samuel L. Freeman, Alistair J. Fielding, Anna J. Bailey, Natalia Stefanou, Hazel A. Sparkes, Takehiko Tosha, Keitaro Yamashita, Kunio Hirata, Hironori Murakami, Go Ueno, Hideo Ago, Kensuke Tono, Masaki Yamamoto, Hitomi Sawai, Yoshitsugu Shiro, Hiroshi Sugimoto, Emma L. Raven, Peter C. E. Moody
Summary: Oxygen activation in heme enzymes requires the formation of high oxidation states of iron, known as ferryl heme, with two intermediates known as Compound I and Compound II. Recent crystal structure studies of Compound II in cytochrome c peroxidase and ascorbate peroxidase reveal differences in iron-oxygen bond lengths, suggesting fine-tuning of the ferryl species across closely related peroxidase enzymes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Agricultural Engineering
Misa Mojca Cajnko, Jost Oblak, Miha Grilc, Blaz Likozar
Summary: Enzymes play a crucial role in lignin valorization, with different enzymes involved in various elementary reaction mechanisms. Degradation of lignin depends on enzyme activity and the interaction with proteins in ways that target specific covalent bonds in lignin. Various factors influence enzymatic activity, which must be taken into consideration for optimal functionality and synthesis yields.
BIORESOURCE TECHNOLOGY
(2021)
Article
Chemistry, Physical
Wanyi Liao, Qin Zhao, Shanshan Wang, Yiling Ran, Hong Su, Rong Gan, Shun Lu, Yan Zhang
Summary: The high energy consumption in water electrolysis systems is attributed to the slow kinetics of the oxygen evolution reaction (OER). Substituting thermodynamically advantageous small molecule oxidation reactions for OER can significantly improve energy conversion efficiency. Studying the in-depth reaction mechanism of complex substrates is necessary due to their elemental composition. This review focuses on the electrooxidation mechanism of different substrate molecules, such as ethanol, urea, and hydrazine, and introduces design ideas and strategies for high-performance electrocatalysts in relation to reaction path selectivity. The challenges in achieving industrial transformation in this field are also discussed.
JOURNAL OF CATALYSIS
(2023)
Article
Environmental Sciences
Seira Takahashi, Fumiko Taguchi, Katsutoshi Hori
Summary: The purpose of this study is to investigate whether carbon nanotubes (CNTs) can be degraded by bacterial enzymes. The study found that oxidized single-walled CNTs (O-SWCNTs) can be degraded through a Fenton reaction catalyzed by bacterial enzymes. The same phenomenon was observed with horseradish peroxidase (HRP), indicating that the degradation of O-SWCNTs by HRP is also mainly due to the Fenton reaction. These findings highlight the importance of the Fenton reaction in CNT degradation and provide insights for the development of a simple disposal method for CNTs.
FRONTIERS IN ENVIRONMENTAL SCIENCE
(2023)
Article
Biochemistry & Molecular Biology
Barindra Sana, Ding Ke, Eunice Hui Yen Li, Timothy Ho, Jayasree Seayad, Hung A. Duong, Farid J. Ghadessy
Summary: Halogenation of peptides can be achieved through selective halogenase enzymes, providing potential for post-synthesis/expression halogenation. The C-terminal (G/S)GW motif is identified as the preferred substrate. Improved halogenation of the (G/S)GW motif can be achieved through rational design of PyrH halogenase mutants.
Article
Chemistry, Multidisciplinary
Yamila A. Perez Sirkin, Manuel Vigil De Maio, Mario Tagliazucchi
Summary: The theoretical model of an enzymatic nanochannel biosensor is proposed and applied to previous experimental studies. The predictions are in agreement with experimental observations, and strategies to improve the sensor performance are identified.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Christopher M. Lemon, Michael A. Marletta
Summary: This study demonstrates that by incorporating fluorescent phosphorus corrole into heme proteins, their fluorescence properties can be enhanced, offering a pathway for the development of novel fluorescent proteins.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Shobhit S. Chaturvedi, Rajeev Ramanan, Jian Hu, Robert P. Hausinger, Christo Z. Christov
Summary: The reaction of the ethylene-forming enzyme is influenced by the conformation of L-Arg and the coordination mode of 2OG, determining whether the reaction proceeds towards ethylene formation or L-Arg hydroxylation.
Article
Biochemistry & Molecular Biology
Takeshi Uchida, Issei Omura, Sayaka Umetsu, Koichiro Ishimori
Summary: The low pH preference of DyP enzyme is mainly determined by the hydrogen bond between His178 and Asp138, rather than distal amino acid residues or the hydrogen bond with Thr278.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Physical
Jifang Zhang, Qiyuan Lin, Zhenlei Wang, Haowen Liu, Xuanzhang Li, Yuegang Zhang
Summary: The study proposes that water oxidation on hematite can proceed via mixed reaction paths, contrary to the traditional assumption of a single reaction path. By isolating absorption signals of surface states responsible for water oxidation, the research highlights the significant contribution of direct hole transfer, especially for highly doped hematite. This finding challenges existing experimental techniques that rely on oversimplified models and theories.
Article
Chemistry, Multidisciplinary
Yang Wei, Melissa Conklin, Yong Zhang
Summary: Engineered heme protein biocatalysts provide an efficient and sustainable approach for the synthesis of amine-containing compounds through C-H amination. A quantum chemical study reveals that nitrene formation is the rate-determining step in the overall reaction, and the catalyst with a serine ligand exhibits the highest reactivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jiakun Xu, Chunlan Wang, Zhiqi Cong
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Chemistry, Physical
Shinya Ariyasu, Yusaku Kodama, Chie Kasai, Zhiqi Cong, Joshua Kyle Stanfield, Yuichiro Aiba, Yoshihito Watanabe, Osami Shoji
Review
Chemistry, Multidisciplinary
Durga Mahor, Zhiqi Cong, Martin J. Weissenborn, Frank Hollmann, Wuyuan Zhang
Summary: The oxidation of alkanes into valuable chemical products is a crucial reaction in organic synthesis but is challenging due to the inertness of C-H bonds. Although transition metal catalysts are commonly used, nature has also developed powerful oxidative enzymes capable of transforming C-H bonds under mild conditions. This Minireview provides an overview of enzyme classes capable of small alkane oxyfunctionalization, describing catalytic mechanisms and current preparative applications.
Article
Chemistry, Physical
Xuan Zhang, Yiping Jiang, Qianqian Chen, Sheng Dong, Yingang Feng, Zhiqi Cong, Sason Shaik, Binju Wang
Summary: Understanding the molecular basis of controlled H2O2 activation is crucial for peroxide-driven catalysis by metalloenzymes. This study demonstrates the significant influence of substrates and dual-functional small molecules (DFSM) on H2O2 activation, with hydrogen bonding networks playing key roles in dictating the process.
Article
Chemistry, Physical
Nana Ma, Wenhan Fang, Chuanfei Liu, Xiangquan Qin, Xiling Wang, Longyi Jin, Binju Wang, Zhiqi Cong
Summary: By employing a protein engineering strategy, the research group successfully enhanced the peroxidase activity of the modified P450 system and demonstrated excellent oxidation activity towards various substrates. This engineered system achieves the best peroxidase activity reported for any P450 to date and holds significant potential for practical applications.
Article
Biochemistry & Molecular Biology
Siyu Di, Shengxian Fan, Fengjie Jiang, Zhiqi Cong
Summary: This article summarizes the importance of the design, mechanism, evolution, application, and perspective of these novel non-natural P450 peroxygenases for the oxidation of non-native substrates.
Article
Biochemistry & Molecular Biology
Xiangquan Qin, Yiping Jiang, Jie Chen, Fuquan Yao, Panxia Zhao, Longyi Jin, Zhiqi Cong
Summary: We developed an artificial P450-H2O2 system assisted by dual-functional small molecules (DFSMs) to modify the P450BM3 monooxygenase into its peroxygenase mode. A series of novel DFSMs with various unnatural amino acid groups were designed and synthesized, and they significantly affected the catalytic activity, stereoselectivity, and regioselectivity of the reactions.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Multidisciplinary
Jie Chen, Sheng Dong, Wenhan Fang, Yiping Jiang, Zhifeng Chen, Xiangquan Qin, Cong Wang, Haifeng Zhou, Longyi Jin, Yingang Feng, Binju Wang, Zhiqi Cong
Summary: We report the selective hydroxylation of alkylbenzenes using an engineered P450 peroxygenase driven by a dual-functional small molecule (DFSM). By combining different P450BM3 variants with DFSMs, more than half of all possible hydroxylated products were obtained from each substrate with high regioselectivity (>99%), enantioselectivity (>99% ee), and high total turnover numbers (up to 80963). Synergistic effects between exogenous DFSMs and the protein environment controlled the regio- and enantioselectivity, as revealed by crystal structure analysis, molecular dynamic simulations, and theoretical calculations. This work has implications for exogenous-molecule-modulated enzymatic regiodivergent and enantioselective hydroxylation with potential applications in synthetic chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiling Wang, Xiaodan Lin, Yiping Jiang, Xiangquan Qin, Nana Ma, Fuquan Yao, Sheng Dong, Chuanfei Liu, Yingang Feng, Longyi Jin, Mo Xian, Zhiqi Cong
Summary: The peroxidase activity of cytochrome P450BM3 was increased through protein engineering by introducing site-directed mutations of key active-site residues. This allowed for efficient regulation of substrate access, leading to a decrease in monooxygenation activity and an increase in peroxidase activity. The P450 peroxidase system was successfully applied for the direct nitration of aromatic compounds and terminal aryl-substituted olefins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Fanhui Kong, Jie Chen, Xiangquan Qin, Chuanfei Liu, Yiping Jiang, Li Ma, Huifang Xu, Shengying Li, Zhiqi Cong
Summary: In this study, an environmentally friendly enzymatic approach for the preparation of indigoid compounds from indole derivatives was described. Mutants of P450BM3 were obtained through site-directed, random, and combinatory hot-site mutations with beneficial catalytic efficiency. These mutants efficiently catalyzed the hydroxylation and oxidation reactions of indole, providing a new enzymatic approach for the biosynthesis of indigoid dyes.
Article
Chemistry, Multidisciplinary
Panxia Zhao, Fanhui Kong, Yiping Jiang, Xiangquan Qin, Xiaoxia Tian, Zhiqi Cong
Summary: By modifying the water tunnels, P450 enzymes can have enhanced peroxygenase activity by facilitating the access of H2O2 to the heme center. The H2O2-driven activities of two native P450 enzymes significantly increase and the amount of H2O2 required for an artificial P450 peroxygenase is greatly reduced. This study shows the potential of modifying P450 enzymes to adopt peroxygenase activity through H2O2 tunnel engineering.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiangquan Qin, Yiping Jiang, Fuquan Yao, Jie Chen, Fanhui Kong, Panxia Zhao, Longyi Jin, Zhiqi Cong
Summary: In this study, artificial metalloenzymes (ArMs) were constructed by optimizing the structure of dual-functional small molecules (DFSMs) to enhance their binding affinity with P450 enzymes. This strategy successfully resulted in the formation of P450BM3-based peroxygenases with high catalytic activity and promiscuity. The use of editable organic cofactors as co-catalytic centers allows for a low load requirement and widens the substrate range for peroxygenase reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Panxia Zhao, Jie Chen, Nana Ma, Jingfei Chen, Xiangquan Qin, Chuanfei Liu, Fuquan Yao, Lishan Yao, Longyi Jin, Zhiqi Cong
Summary: The study demonstrates the efficient H2O2-dependent (R)-enantioselective epoxidation of unfunctionalized styrene and its derivatives by site-mutated variants of a unique non-natural P450BM3 peroxygenase in combination with a dual-functional small molecule. The synergistic use of protein engineering and an exogenous DFSM represents an effective strategy to control the enantioselectivity of styrene epoxidation, significantly expanding the chemical scope of P450 enzymes as useful bio-oxidative catalysts.
Review
Chemistry, Multidisciplinary
Xiling Wang, Jie Chen, Nana Ma, Zhiqi Cong
ACTA CHIMICA SINICA
(2020)
Article
Chemistry, Physical
Yihui Jiang, Chunlan Wang, Nana Ma, Jie Chen, Chuanfei Liu, Fang Wang, Jiakun Xu, Zhiqi Cong
CATALYSIS SCIENCE & TECHNOLOGY
(2020)
