Article
Chemistry, Physical
Wei Peng, Xiaoyang Qu, Sason Shaik, Binju Wang
Summary: This study deciphers the catalytic cycle of pMMO in the presence of the physiological reductant duroquinol (DQH(2)), revealing that O-2 activation is initiated by the Cu-C(ii)-DQH(-) species. The research also uncovers the important roles of the phenol co-substrate for O-2 activation.
Review
Chemistry, Multidisciplinary
Rahul Banerjee, John D. Lipscomb
Summary: Rigorous substrate selectivity in enzyme catalysis is attributed to the favorable process of substrate binding to the enzyme active site based on complementary physiochemical characteristics. However, this selectivity becomes more difficult to rationalize for diminutive molecules with too narrow a range of physical characteristics.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Ecology
Christina S. Kang-Yun, Xujun Liang, Philip Dershwitz, Wenyu Gu, Aloys Schepers, Andrew Flatley, Josef Lichtmannegger, Hans Zischka, Lijie Zhang, Xia Lu, Baohua Gu, Joshua C. Ledesma, Daly J. Pelger, Alan A. DiSpirito, Jeremy D. Semrau
Summary: Aerobic methanotrophy is strongly regulated by copper, with different methanotrophs utilizing various mechanisms for copper uptake, including secreting methanobactin or utilizing proteins like MopE. Certain methanotrophs are able to steal methanobactin from others, enhancing their ability to degrade methylmercury. Understanding these strategies may help manipulate methanotrophic communities to reduce methane emissions and enhance mercury detoxification.
Article
Engineering, Environmental
Hyesung Lee, Choah Kwon, Changjoon Keum, Hee-Eun Kim, Hyunjoo Lee, Byungchan Han, Sang-Yup Lee
Summary: Inspired by the active site of particulate methane monooxygenase (pMMO), a copper-doped zeolitic imidazolate framework-7 (Cu/ZIF-7) was synthesized and showed catalytic activity in converting methane to various products without overoxidation.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Microbiology
Kangli Guo, Anna Hakobyan, Timo Glatter, Nicole Paczia, Werner Liesack
Summary: High NH4+ load inhibits bacterial methane oxidation by competing with CH4 for the active site of pMMO. Methylocystis sp. strain SC2 shows cellular acclimatization response to high NH4+ levels involving stress-responsive proteins, synthesis of compatible solutes, and induction of glutathione metabolism pathway. Increased NH4+ load leads to increased pMMO-based oxidation of NH3 to toxic hydroxylamine, resulting in accumulation of NO2- and N2O.
Article
Engineering, Environmental
Yulu Wang, Chun-Yu Lai, Mengxiong Wu, Xuanyu Lu, Shihu Hu, Zhiguo Yuan, Jianhua Guo
Summary: This study showed that increasing copper concentration significantly enhanced the perchlorate reduction rate in a methane-based membrane biofilm reactor, as well as promoted methane oxidation and perchlorate reduction rates through adjusting the abundance of functional genes. A higher copper concentration also increased microbial community diversity and facilitated the synergistic association between methanotrophs and perchlorate reducers.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Review
Biotechnology & Applied Microbiology
Noemi Poma, Andrea Bonini, Federico Vivaldi, Denise Biagini, Mariagrazia Di Luca, Daria Bottai, Fabio Di Francesco, Arianna Tavanti
Summary: Climate change due to increased greenhouse gas emissions has had a significant impact on the sustainability of life on Earth. Methane, a greenhouse gas, is increasing in concentration and its measurement is important for the environment and safety. The use of methane-oxidizing bacteria in biosensing systems shows promise for methane quantification and monitoring.
APPLIED MICROBIOLOGY AND BIOTECHNOLOGY
(2023)
Article
Multidisciplinary Sciences
Wafa Ali Eltayb, Mohnad Abdalla, Amr Ahmed EL-Arabey, Ahmed Boufissiou, Mohammad Azam, Saud I. Al-Resayes, Mahboob Alam
Summary: Researchers used bioinformatics tools and molecular docking studies to analyze the structure of pMMO and its interactions with quinone, duroquinone, and P450 enzymes. They discovered that pMMO can produce methanol without Cu in the presence of quinone and duroquinone, and that pmoB1 interacts with P450. This study highlights the importance of studying the membrane of pMMO for understanding its functions.
JOURNAL OF KING SAUD UNIVERSITY SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Gabriela C. Schroder, William B. O'Dell, Simon P. Webb, Pratul K. Agarwal, Flora Meilleur
Summary: Metalloproteins catalyze redox reactions using their metallocofactors. Lytic polysaccharide monooxygenases (LPMOs) are copper-dependent enzymes that degrade recalcitrant polysaccharides. Neutron protein crystallography reveals the initial steps of oxygen activation in Neurospora crassa LPMO9D, with His157 identified as the proton donor. His1 and His161 also display conformational flexibility.
Article
Biochemistry & Molecular Biology
Sunney Chan, Wei-Hau Chang, Shih-Hsin Huang, Hsin-Hung Lin, Steve S-F Yu
Summary: This focused review describes the 2.5 angstrom cyro-EM structure of particulate methane monooxygenase (pMMO), revealing the locations of copper cofactors and active sites, providing insights into the catalytic machinery capable of methane oxidation with high selectivity and efficiency.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Biochemical Research Methods
Christopher W. Koo, Jasmine M. Hershewe, Michael C. Jewett, Amy C. Rosenzweig
Summary: The study developed a cell-free protein synthesis system based on Escherichia coli lysate, which can be used to express particulate methane monooxygenase (pMMO) in vitro in the presence of nanodiscs. The findings demonstrate that the pMMO complex can form without the need for exogenous translocon machinery or chaperones.
ACS SYNTHETIC BIOLOGY
(2022)
Article
Ecology
Olivia E. Mosley, Emilie Gios, Murray Close, Louise Weaver, Chris Daughney, Kim M. Handley
Summary: The nitrogen cycle plays a crucial role in aquatic ecosystems, including the subsurface. However, the diversity of nitrogen transformations in these environments is not well understood. This study investigated how nitrogen cycling microorganisms respond to different groundwater chemistries. The results showed that regardless of site-specific conditions, nitrogen cycling mechanisms were prevalent and highly redundant in groundwater communities. The study also revealed the presence of oxic-anoxic interfaces and potential synergistic interactions between microorganisms at these interfaces. The findings provide insights into cooperative relationships in groundwater communities and the complexity of metabolic mechanisms leading to nitrogen loss.
Article
Chemistry, Physical
Zhenzhuo Lan, Jacob Toney, Shaama Mallikarjun Sharada
Summary: This study computationally investigates the mechanism and active site identification of methane hydroxylation by monocopper complexes. The results suggest that the oxyl species is the likely active site, and spin crossing may provide a lower energy pathway for hydroxylation.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Amy J. Knorpp, Ana B. Pinar, Christian Baerlocher, Lynne B. McCusker, Nicola Casati, Mark A. Newton, Stefano Checchia, Jordan Meyet, Dennis Palagin, Jeroen A. van Bokhoven
Summary: The research investigates the conversion of methane to methanol using copper-exchanged zeolites, with current productivity levels still too low. By understanding the nature of the active site, more effective catalysts could be designed for this conversion process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Alexander J. Heyer, Dieter Plessers, Augustin Braun, Hannah M. Rhoda, Max L. Bols, Britt Hedman, Keith O. Hodgson, Robert A. Schoonheydt, Bert F. Sels, Edward I. Solomon
Summary: In this study, a mononuclear [CuOH](+) active site in the autoreduced zeolite was unambiguously defined, and its reactivity was compared to the previously defined [Cu2O](2+) active site. The increased reactivity of the binuclear site was attributed to electron delocalization over the two Cu cations via the bridging ligand.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Blaise L. Geoghegan, Yang Liu, Sergey Peredkov, Sebastian Dechert, Franc Meyer, Serena DeBeer, George E. Cutsail
Summary: A combination of Cu K-edge X-ray absorption and Cu K beta valence-to-core X-ray emission spectroscopies can be used to characterize the formal oxidation states of organometallic copper complexes. These methods are crucial for investigating the electronic structures of highly covalent copper complexes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Justin T. Henthorn, George E. Cutsail, Thomas Weyhermueller, Serena DeBeer
Summary: This article investigates the electronic structure and spin states of mixed-valent iron-sulfur dimers and discovers a new interaction that can stabilize high spin states. By studying a series of mixed-valent complexes, complex interactions between antiferromagnetic coupling, Heisenberg double-exchange, and vibronic coupling are revealed.
Article
Electrochemistry
Natalia Levin, Carla Casadevall, George E. Cutsail, Julio Lloret-Fillol, Serena DeBeer, Olaf Ruediger
Summary: In this study, a molecular Ru-based water oxidation catalyst bearing a polypyridinic backbone was investigated using in situ spectroelectrochemistry coupled with EPR and XAS techniques. The study proposed a water nucleophilic attack mechanism for O-O bond formation, and observed intermediates supporting this mechanism, including a Ru(V) oxo intermediate based on the Py(2)Metacn ligand for the first time.
Article
Chemistry, Inorganic & Nuclear
Julia Krueger, Julia Haak, Christoph Woelper, George E. Cutsail, Gebhard Haberhauer, Stephan Schulz
Summary: Stable heavy main group element radicals are challenging to synthesize. Researchers have successfully synthesized a series of two-coordinated pnictogen-centered radical cations by developing new strategies, and characterized and validated them.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Christoph Helling, Julia Haak, Christoph Woelper, George E. Cutsail, Stephan Schulz
Summary: In this study, the stepwise synthesis of boryl-substituted antimony compounds was reported, revealing the formation of metal-metal bonds and the changes in electronic structures. The molecular structures and bonding properties were characterized and analyzed in detail through experimental and computational methods. The results showed that the synthesized compounds exhibited unique spin distribution and asymmetric electronic structures.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Physical
George E. Cutsail, Serena DeBeer
Summary: X-ray spectroscopy plays a significant role in catalysis research by providing essential electronic and geometric structural information. The development of dedicated synchrotron-based X-ray emission spectrometers has expanded experimental capabilities, offering more detailed data. There is a continuous demand for conventional XAS applications and the integration with more advanced techniques.
Article
Chemistry, Inorganic & Nuclear
Julia Haak, Julia Kruger, Nikolay V. Abrosimov, Christoph Helling, Stephan Schulz, George E. Cutsail
Summary: Recent successes in isolating and characterizing several bismuth radicals have inspired the development of new spectroscopic approaches. The application of conventional X-band parallel-mode EPR spectroscopy has allowed for the study and analysis of spin systems with S = 1/2, I = 9/2.
INORGANIC CHEMISTRY
(2022)
Article
Biophysics
George Cutsail, Stephan Schott-Verdugo, Lena Mueller, Serena DeBeer, Georg Groth, Holger Gohlke
Summary: This study presents the first spectroscopic characterization of the Cu(I) active site of the plant ethylene receptor ETR1. The findings reveal a low-coordinate Cu(I) site with histidine and cysteine residues playing critical roles in ethylene activity. Furthermore, spectroscopic changes upon ethylene addition suggest modifications in the Cu(I) coordination environment, which may serve as the triggering signal for the transmission of the ethylene response.
BIOPHYSICAL JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Mahendra K. Sharma, Hanns M. Weinert, Bin Li, Christoph Woelper, Justin T. Henthorn, George E. Cutsail III, Gebhard Haberhauer, Stephan Schulz
Summary: Based on DFT calculations, LGa(P2OC)cAAC 2 possesses a delocalized p-type HOMO and p*-type LUMO due to the presence of a 1,2-diphospha-1,3-butadiene moiety. Reaction of 2 with KC8 and dibenzo-18-crown-6 led to the isolation of [LGa(P2OC)cAAC][K(DB-18-c-6)] 3[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene radical anion 3*. Further reactions of 3 with [Fc][B(C6F5)(4)] and TEMPO yielded 2 and [L-HGa-(P2OC)cAAC][K(DB-18-c-6)] 4[K(DB-18-c-6] respectively, with the latter containing the 1,2-diphospha-1,3-butadiene anion 4-. The structures of 2, 3[K(DB-18-c-6], and 4[K(DB-18-c-6] were determined using single crystal X-ray diffraction (sc-XRD).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yang Liu, Sayanti Chatterjee, George E. Cutsail III, Sergey Peredkov, Sandeep K. Gupta, Sebastian Dechert, Serena DeBeer, Franc Meyer
Summary: This study reports the synthesis and characterization of [Cu-4(& mu;(4)-S)](n+) (n = 2, 2; n = 3, 3) clusters, which mimic the two active states of the Cu-Z* site during enzymatic N2O reduction. The structural and electronic properties of these clusters are elucidated using multiple methods. Preliminary reactivity studies demonstrate the nucleophilic character of the central & mu;(4)-S in the fully reduced 0-hole state.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Jann-Louis Hau, Susann Kaltwasser, Valentin Muras, Marco S. Casutt, Georg Vohl, Bjoern Claussen, Wojtek Steffen, Alexander Leitner, Eckhard Bill, George E. Cutsail, Serena Debeer, Janet Vonck, Julia Steuber, Guenter Fritz
Summary: This study reveals that ion pumping in Na+-NQR is driven by large conformational changes coupling electron transfer to ion translocation. This mechanism is of significant importance for NADH oxidation in the human pathogen Vibrio cholerae.
NATURE STRUCTURAL & MOLECULAR BIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Mahendra K. Sharma, Hanns M. Weinert, Bin Li, Christoph Woelper, Justin T. Henthorn, George E. Cutsail, Gebhard Haberhauer, Stephan Schulz
Summary: LGa(P2OC)cAAC2 features a unique structure with conjugated HOMO and LUMO. Compounds containing 1,2-diphospha-1,3-butadiene radical and anion were obtained through reactions. The solid-state structures of these compounds were determined by X-ray diffraction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
George E. Cutsail, Rahul Banerjee, Derek B. Rice, Olivia McCubbin Stepanic, John D. Lipscomb, Serena DeBeer
Summary: In this study, Fe K beta X-ray emission spectroscopy was used to characterize the local spin states of key intermediates in soluble methane monooxygenase (sMMO) and it was discovered that these intermediates contain S-loc = 2 iron sites. This experimental determination will guide future computational and mechanistic studies of sMMO catalysis.
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Bin Li, Blaise L. Geoghegan, Hanns M. Weinert, Christoph Wolper, George E. Cutsail, Stephan Schulz
Summary: This article reports the synthesis of carbene-stabilized group 13 metal radicals and their corresponding cations, which were characterized spectroscopically and by sc-XRD. Quantum chemical calculation provided insights into their electronic structures.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hanns M. Weinert, Christoph Woelper, Julia Haak, George E. Cutsail, Stephan Schulz
Summary: Cyclic voltammetry studies were conducted on two L(X)Ga-substituted dipnictenes, revealing reversible reduction events. The corresponding dipnictenyl radical anions were synthesized and characterized through various techniques, with quantum chemical calculations providing further insights into the chemical bonding nature.