Article
Chemistry, Physical
David W. Kastner, Aditya Nandy, Rimsha Mehmood, Heather J. Kulik
Summary: Non-heme iron halogenases and hydroxylases catalyze the functionalization of diverse biological products by activating inert C-H bonds. Crystallographic and spectroscopic data analysis shows that hydroxylases and halogenases exhibit different substrate positioning preferences. Molecular dynamics simulations guided by experimental information reveal the key substrate interaction partners and the impact of the protein environment on the substrate approach angles.
Article
Chemistry, Physical
David W. Kastner, Aditya Nandy, Rimsha Mehmood, Heather J. Kulik
Summary: Non-heme iron halogenases and hydroxylases regulate the formation of diverse biological products under physiological conditions. Crystallographic and spectroscopic data showed that hydroxylases prefer an acute angle while halogenases prefer a more obtuse angle. Molecular dynamics simulations revealed that the protein environment in halogenases prevents the sampling of acute angles observed in hydroxylases and vice versa.
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
Chemistry, Physical
Rimsha Mehmood, Vyshnavi Vennelakanti, Heather J. Kulik
Summary: Researchers investigate substrate/active-site dynamics of nonheme iron halogenases like BesD and WelO5 using experimental and computational methods, revealing the importance of active-site configurational isomerization for selective halogenation in WelO5. They also find distinct patterns of substrate-protein interactions for these enzymes, and discuss how optimal substrate/active-site geometry plays a crucial role in facilitating chemoselectivity in halogenases. Their work demonstrates different substrate-dependent strategies used to promote selectivity in halogenases.
Article
Chemistry, Inorganic & Nuclear
Yuji Mikata, Yuri Aono, Chihiro Yamamoto, Hiromi Nakayama, Arimasa Matsumoto, Fukue Kotegawa, Masafumi Harada, Hajime Katano, Yoshio Kobayashi, Sachiko Yanagisawa, Minoru Kubo, Atsushi Kajiwara, Masahito Kodera
Summary: In this study, a bis(mu-oxo)diiron(IV,IV) complex was synthesized as a model for intermediate Q in the methane monooxygenase reaction cycle. The structure of the complex was characterized by X-ray crystallography and spectroscopic techniques, and its high reactivity was demonstrated through hydrogen abstraction reactions.
INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Hiromu Ito, Hiromi Kurokawa, Hirofumi Matsui
Summary: Mitochondria, essential organelles for energy production in eukaryotes, generate reactive oxygen species during the process which play pivotal roles in cell signaling and iron homeostasis regulation. The regulation of iron transportation, involving proteins like HCP1, DMT1, and mitoferrin, is increasingly understood in relation to mitochondrial reactive oxygen species and diseases.
ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS
(2021)
Article
Nutrition & Dietetics
Davit Pipoyan, Seda Stepanyan, Meline Beglaryan, Alberto Mantovani
Summary: This study aimed to analyze the intake of Fe and its dietary sources among adults in Armenia. The results showed that a high proportion of adults had a lower intake of Fe than the average requirements. Bread, fruits, and vegetables were the main sources of Fe, while heme Fe intake was very low. Females had lower Fe intake compared to males, and there were significant differences in Fe intake between regions. Comprehensive nutritional strategies are needed to reduce iron deficiency in Armenia.
Article
Chemistry, Applied
Irwan Iskandar Roslan, Hongwei Zhang, Kian-Hong Ng, Stephan Jaenicke, Gaik-Khuan Chuah
Summary: A wide array of polysubstituted 1-bromo and chloronaphthalenes are obtained through coupling of allylbenzenes and polyhalomethanes mediated by iron metal under visible light irradiation. The reaction proceeds through a Kharasch addition intermediate followed by intramolecular Fe-III mediated Friedel-Crafts alkylation, leading to the formation of two Csp(2)-Csp(2) bonds. This method provides easy access to 1-halonaphthalenes with substituents at C-5 to C-8 that are otherwise difficult to synthesize.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Cell Biology
Dandan Zhong, Lingling Quan, Chang Hao, Jingshuo Chen, Ranran Qiao, Tengfei Lin, Changjiang Ying, Dong Sun, Zhanjun Jia, Ying Sun
Summary: The study found that blocking mPGES-2 may be a promising therapeutic strategy for AKI. Deficiency of mPGES-2 can reduce renal dysfunction and morphological damage and inhibit ferroptosis through heme-dependent regulation.
CELL DEATH & DISEASE
(2023)
Article
Chemistry, Physical
Guoqing Zhai, Rong Gong, Yaxin Lin, Meng Zhang, Jiahui Li, Zixin Deng, Jiazhong Sun, Wenqing Chen, Zhengyu Zhang
Summary: This study reports the crystal structures of the non-heme Fe2+/2OG-dependent halogenase AdaV and reveals its catalytic mechanism. The study also demonstrates the engineering of AdaV variants to produce different halogenated and hydroxylated products, and proposes a dual-controlling mechanism for AdaV catalysis.
Article
Chemistry, Physical
Vyshnavi Vennelakanti, Rimsha Mehmood, Heather J. Kulik
Summary: In this study, the electronic structure of vanadyl mimics and catalytic iron intermediates were compared using density functional theory and correlated wavefunction theory. The calculations revealed crucial structural and energetic differences between the two due to their different spin states. The study also found that there were differences in the energetics for the isomerization and reaction of metal-oxo intermediates between vanadyl and ferryl mimics in non-heme iron enzymes.
Article
Chemistry, Inorganic & Nuclear
Jian Han, Liming Tan, Yanjun Wan, Gang Li, Stephen N. Anderson
Summary: A pincer iron(III) catalyst has been developed for the oxidation and chlorination of C(sp(3))-H bonds. The oxidation of a diagnostic substrate cis-decalin suggests the involvement of a long-lived carbon-centred radical. Mechanistic studies indicate that an Fe-oxo species could be responsible for the rate-determining C-H activation step. This research expands the scope of non-heme catalysts for C-H functionalization.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Amanda Lyn Robinson, Jean-Noel Rebilly, Regis Guillot, Christian Herrero, Helene Maisonneuve, Frederic Banse
Summary: We report two new Fe-III complexes obtained by replacing pyridines by phenolates in a known non-heme aminopyridine iron complex. These complexes demonstrate good O-2 activation ability and can serve as important activators in electrochemical setups to achieve substrate oxidation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Tian Luo, Haozhi Wu, Li-hua Liao, Jie-Ping Wan, Yunyun Liu
Summary: This study presents a novel method for the synthesis of dichlorinated and dibrominated 2-amino-substituted chromanones using enaminones and NCS/NBS under microwave irradiation. The reactions are rapid and do not require any catalyst or additive, offering a practical route to 3,3-dihalogenated 2-aminochromanones.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Physical
Gourab Mukherjee, Jagnyesh K. Satpathy, Umesh K. Bagha, M. Qadri E. Mubarak, Chivukula Sastri, Sam P. de Visser
Summary: Enzymes are efficient catalysts in nature that achieve high stereo-, chemo-, and regioselectivity through substrate binding and positioning in the active site, as well as second-coordination sphere effects. Biomimetic model complexes with similar first-coordination sphere to enzymes have been developed, but sometimes show different reactivity patterns in solution and loss of selectivity. Large catalytic clusters with second-coordination sphere effects have been developed to understand functional differences between enzymes and biomimetic models, influencing spectroscopic features and reactivity patterns for high selectivity in chemical reactions. The biomimetic models show potential for future stereo- and chemoselective synthetic catalytic reactions in biotechnological and engineering applications.
Article
Chemistry, Multidisciplinary
Eaindra Yee, Murphi T. Williams, Ambika Bhagi-Damodaran
Summary: The role of metals in biology and biocatalysis is often underestimated, leading to potential misinformation, especially in relation to vaccines and health products.
JOURNAL OF CHEMICAL EDUCATION
(2022)
Review
Biochemistry & Molecular Biology
Murphi T. Williams, Eaindra Yee, Grant W. Larson, Elizabeth A. Apiche, Anoop Rama Damodaran, Ambika Bhagi-Damodaran
Summary: Microbes use metal cofactor-containing proteins to recognize and respond to redox stresses in their environment. Understanding how these metalloproteins sense redox events and communicate this information to DNA is of great interest to chemists and biologists.
CURRENT OPINION IN CHEMICAL BIOLOGY
(2023)