Article
Chemistry, Multidisciplinary
Baoling Tian, Shujuan Li, Shulai Lei, Liangxu Lin, Wenyue Guo, Hao Ren
Summary: This study investigates the structure-dependent resonance Raman signals of different reaction intermediates, providing insights into the details and dynamics of the dialumene species involved in CO2 capture reaction. The spectral features obtained through Raman spectroscopy not only offer structural information of intermediate species, but also enable a deeper understanding of the catalytic process dynamics.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Armel F. T. Waffo, Christian Lorent, Sagie Katz, Janna Schoknecht, Oliver Lenz, Ingo Zebger, Giorgio Caserta
Summary: This study used cryogenic infrared and electron paramagnetic resonance spectroscopy to decipher the structural basis of the Ni-a-L intermediates in the regulatory [NiFe]-hydrogenase from Cupriavidus necator, revealing the importance of the protein scaffold in fine-tuning proton and electron dynamics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Christian Lorent, Vladimir Pelmenschikov, Stefan Frielingsdorf, Janna Schoknecht, Giorgio Caserta, Yoshitaka Yoda, Hongxin Wang, Kenji Tamasaku, Oliver Lenz, Stephen P. Cramer, Marius Horch, Lars Lauterbach, Ingo Zebger
Summary: A new experimental setup was developed to study metalloenzymes in detail, allowing the controlled preparation and characterization of catalytic intermediates using various spectroscopic techniques. By investigating two O-2-tolerant [NiFe]-hydrogenases as model systems, detailed insights into the catalytic mechanisms and vibrational fingerprints were revealed. Additionally, the study highlighted the importance of complementing X-ray crystallographic data with spectroscopic analyses.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Christian Hess
Summary: Raman spectroscopy is a powerful vibrational spectroscopic technique that has been widely used for the characterization of catalysts and catalytic reactions. It provides important information on catalyst structures, adsorbates, and reaction intermediates, offering key insights into studying working catalysts.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Takeshi Hiromoto, Koji Nishikawa, Seiya Inoue, Hideaki Ogata, Yuta Hori, Katsuhiro Kusaka, Yu Hirano, Kazuo Kurihara, Yasuteru Shigeta, Taro Tamada, Yoshiki Higuchi
Summary: This study reports that [NiFe]-hydrogenase from Desulfovibrio vulgaris Miyazaki F can recover its catalytic activity by reacting with H2 under anaerobic conditions after being inactivated in the presence of O2. Neutron structure analysis revealed that a part of the Ni ion dissociates from the active site Ni-Fe complex and forms a new square-planar Ni complex, accompanied by rearrangement of the coordinated thiolate ligands. The analysis also found that the Cys17(S) thiolate forms an unusual hydrogen bond with the main-chain amide N atom of Gly19(S), providing insights into the redox reaction of the Fe-S cluster.
Review
Chemistry, Inorganic & Nuclear
Giorgio Caserta, Lidia Zuccarello, Catarina Barbosa, Celia M. Silveira, Elin Moe, Sagie Katz, Peter Hildebrandt, Ingo Zebger, Smilja Todorovic
Summary: The universe of known biological FeS clusters is expanding with novel and unprecedented structures, including unique coordination and heteronuclear clusters that play versatile physiological roles. Some structures with distorted geometries or atypical ligations exhibit novel functions. Resonance Raman spectroscopy plays a key role in unraveling remarkable features in FeS centers and understanding their unusual structures and functions.
COORDINATION CHEMISTRY REVIEWS
(2022)
Review
Chemistry, Inorganic & Nuclear
Seiji Ogo, Takeshi Yatabe, Hidetaka Nakai
Summary: This review discusses whether the ligand design used in catalysts mimicking O2-tolerant [NiFe] hydrogenase can be applied to ligand design in catalysts for C-C bond forming reactions. It explores the possibility of applying the ligand design methodology in reductive C-C coupling and C-H arylation reactions.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Multidisciplinary Sciences
Weixuan Xu, Shuangyan Lang, Kaiyang Wang, Rui Zeng, Huiqi Li, Xinran Feng, Mihail R. Krumov, Seong-Min Bak, Christopher J. Pollock, Jingjie Yeo, Yonghua Du, Hector D. Abruna
Summary: This study comprehensively investigates the catalytic mechanisms of a cobalt single-atom electrocatalyst on the redox processes of lithium-sulfur batteries using operando techniques. Real-time observations reveal that the electrocatalyst efficiently accelerates the lithium-sulfur reactions with zero-order kinetics. Under galvanostatic discharge conditions, the catalysis transforms the typical stepwise mechanism of the reactions to a concurrent pathway. Additionally, operando XAS studies elucidate the potential-dependent evolution of cobalt's oxidation state and the formation of cobalt-sulfur bonds.
Review
Chemistry, Organic
Yaseen Hussain, Pankaj Chauhan
Summary: The imine umpolung strategy has shown significant progress in catalytic asymmetric synthesis. Chiral catalysts are used to generate 2-azaallyl anion intermediates, driving the umpolung addition/substitution reactions and achieving an excellent level of asymmetric induction. This approach has successfully been applied to the synthesis of amino-acid derivatives and other useful chiral amines, including drugs and potentially bioactive molecules.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Biochemical Research Methods
Jens-Christoph Matuszczyk, Gerben Zijlstra, David Ede, Navid Ghaffari, Joannes Yuh, Veronica Brivio
Summary: The two major challenges in modern bioprocesses are process economics and in-depth process understanding. Online process data acquisition helps in understanding process dynamics and monitoring critical process parameters (CPPs). Raman spectroscopy has emerged as a versatile tool for noninvasive measurements and accessing a wide range of analytes. This article reviews the latest applications of Raman spectroscopy in established protein production bioprocesses and explores its potential in virus, cell therapy, and mRNA processes.
CURRENT OPINION IN BIOTECHNOLOGY
(2023)
Article
Spectroscopy
Elisabeth Siebert, Andrea Schmidt, Stefan Frielingsdorf, Jacqueline Kalms, Uwe Kuhlmann, Oliver Lenz, Patrick Scheerer, Ingo Zebger, Peter Hildebrandt
Summary: This study combined resonance Raman spectroscopy, protein engineering, and X-ray crystallography to investigate the structural properties of iron-sulfur centers and address challenges in spectral analysis of metalloproteins. By using techniques such as protein engineering and selective reduction, the researchers successfully transformed the proximal and medial clusters of the protein variant into standard cubane-type [4Fe-4S] clusters.
JOURNAL OF RAMAN SPECTROSCOPY
(2021)
Article
Chemistry, Multidisciplinary
Cejun Hu, Yanfang Hu, Chenghao Fan, Ling Yang, Yutong Zhang, Haixia Li, Wei Xie
Summary: In this study, label-free surface-enhanced Raman spectroscopy was used to monitor the oxygen evolution reaction process on Ni3FeOx nanoparticles, revealing that Fe atoms are responsible for the initial OH- to O-O- oxidation, and the O-O- species undergo further oxidation between neighboring Fe and Ni sites.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Victoria Davis, Nina Heidary, Amandine Guiet, Khoa Hoang Ly, Maximilian Zerball, Claudia Schulz, Norbert Michael, Regine von Klitzing, Peter Hildebrandt, Stefan Frielingsdorf, Oliver Lenz, Ingo Zebger, Anna Fischer
Summary: The oxygen tolerance of membrane-bound [NiFe] hydrogenase (MBH) from Cupriavidus necator makes it an attractive electrocatalyst for hydrogen energy conversion devices. By immobilizing MBH with affinity tags on a tin-rich indium tin oxide (ITOTR) electrode, hydrogen oxidation and an unusually high proton reduction current were observed, suggesting bidirectionality in unidirectional [NiFe] hydrogenases. The favorable enzyme-semiconductor interactions contribute to this behavior.
Article
Chemistry, Multidisciplinary
Manav Bhati, Sergei A. Ivanov, Thomas P. Senftle, Sergei Tretiak, Dibyajyoti Ghosh
Summary: Using ab initio molecular dynamics (AIMD) simulations, the effects of thermal fluctuations on the structural and vibrational properties of non-stoichiometric cadmium selenide (CdSe) nanoclusters were investigated. The results showed that the excess atoms on the surface tended to fluctuate more, and the optical phonon modes were mainly composed of Se atoms dynamics, regardless of the composition. Furthermore, Cd-rich QDs exhibited faster non-radiative recombination, as suggested by non-adiabatic molecular dynamics (NAMD) simulations. Overall, this study provides insights into the dynamic electronic properties of non-stoichiometric QDs and explains the optical stability and superiority of cation-rich candidates for light emission applications.
Article
Chemistry, Physical
Manuel Antonio Ruiz-Rodriguez, Christopher D. Cooper, Walter Rocchia, Mose Casalegno, Yossef Lopez de los Santos, Guido Raos
Summary: This study uses computational methods to determine the possible orientations of [NiFe] hydrogenase on a planar electrode and finds that the solution's salinity and pH have significant effects on the orientation.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Multidisciplinary
Katrin Warm, Alice Paskin, Uwe Kuhlmann, Eckhard Bill, Marcel Swart, Michael Haumann, Holger Dau, Peter Hildebrandt, Kallol Ray
Summary: In this study, a novel S=2 oxoiron(IV) species supported by a unique ligand was generated and characterized. This species exhibited high reactivity in hydrogen atom abstraction reactions and demonstrated a unique oxidative mechanism. Complex 2 can serve as an excellent electronic and functional model for biological oxoiron(IV) intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Fabian Kruse, Anh Duc Nguyen, Jovan Dragelj, Joachim Heberle, Peter Hildebrandt, Maria Andrea Mroginski, Inez M. Weidinger
Summary: Cytochrome c oxidase (CcO) exists in slow and fast forms, which differ in their ability to bind oxygen and ligands. Surface enhanced resonance Raman spectroscopy revealed structural differences between the two forms, including redox states and oxygen ligand sensitivities of specific amino acids.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Electrochemistry
Tomos G. A. A. Harris, Nina Heidary, Stefan Frielingsdorf, Sander Rauwerdink, Abbes Tahraoui, Oliver Lenz, Ingo Zebger, Anna Fischer
Summary: This work demonstrates the control and optimization of biocompatible interfaces on transparent conducting oxide indium tin oxide (ITO) using diazonium electrografting to achieve low charge transfer resistance and efficient electron transfer to immobilized enzymes. Radical scavenger enables interface thickness control, maximizing direct electron transfer processes. Electrografting is proposed as an alternative approach for the functional immobilization of redox-active enzymes on TCO electrodes.
Article
Chemistry, Multidisciplinary
Konstantin Laun, Benjamin R. Duffus, Stefan Wahlefeld, Sagie Katz, Dennis Belger, Peter Hildebrandt, Maria Andrea Mroginski, Silke Leimkuehler, Ingo Zebger
Summary: It is found that the Mo-dependent formate dehydrogenase from Rhodobacter capsulatus can catalyze the oxidation of formate to CO2. Infrared spectroscopy, density functional theory, and inhibition kinetics were used to investigate the interaction between the enzyme and inhibitory molecules. The study reveals potential non-competitive or competitive binding sites for the inhibitors in the secondary coordination sphere of the active site.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Tillmann Utesch, Jana Staffa, Sagie Katz, Guiyang Yao, Jacek Kozuch, Peter Hildebrandt
Summary: The article investigates the effect of electrode potential on the transmembrane potential of lipid bilayers immobilized on gold electrodes. Experimental results and molecular dynamics simulations show good agreement, indicating the promising potential of this combined approach in studying potential-dependent processes at biomimetic interfaces.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Yvonne Rippers, Barbara Procacci, Neil T. Hunt, Marius Horch
Summary: This study presents a computational approach for simulating and analyzing static 2D-IR spectra of [NiFe] hydrogenases and similar organometallic systems. By accurately reproducing experimental spectra, it reveals the crucial role of the [NiFe] core in shaping the enzymatic potential energy surface and provides molecular information not accessible by experiments.
Article
Chemistry, Physical
Konstantin Laun, Benjamin R. Duffus, Hemant Kumar, Jean-Pierre H. Oudsen, Chara Karafoulidi-Retsou, Armel Tadjoung Waffo, Peter Hildebrandt, Khoa Hoang Ly, Silke Leimkuehler, Sagie Katz, Ingo Zebger
Summary: A minimal light-driven approach was developed to study enzymatic CO2 conversion. This approach allows for in situ characterization of the catalytic reaction and provides a new way to regulate enzyme reactions using light.
Article
Chemistry, Multidisciplinary
Vladimir Pelmenschikov, Delfim Ferreira, Sofia S. Venceslau, Peter Hildebrandt, Ines A. . C. Pereira, Smilja Todorovic, Smilja Todorovic
Summary: In this study, resonance Raman spectroscopy and density functional theory calculations were used to investigate the structural, electronic, and vibrational properties of the noncubane [4Fe-4S] cluster in heterodisulfide reductase (HdrB). Homology modeling was employed to predict the protein environment of the neighboring clusters in DvHdrB. The results showed that the oxidized [4Fe-4S](3+) cluster adopts a closed conformation in the absence of substrate, but transitions to an open structure upon substrate coordination, accompanied by a ligand switch. This study provides valuable insights for future research on enzymes with this unconventional cofactor.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Armel F. T. Waffo, Christian Lorent, Sagie Katz, Janna Schoknecht, Oliver Lenz, Ingo Zebger, Giorgio Caserta
Summary: This study used cryogenic infrared and electron paramagnetic resonance spectroscopy to decipher the structural basis of the Ni-a-L intermediates in the regulatory [NiFe]-hydrogenase from Cupriavidus necator, revealing the importance of the protein scaffold in fine-tuning proton and electron dynamics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Victoria Davis, Nina Heidary, Amandine Guiet, Khoa Hoang Ly, Maximilian Zerball, Claudia Schulz, Norbert Michael, Regine von Klitzing, Peter Hildebrandt, Stefan Frielingsdorf, Oliver Lenz, Ingo Zebger, Anna Fischer
Summary: The oxygen tolerance of membrane-bound [NiFe] hydrogenase (MBH) from Cupriavidus necator makes it an attractive electrocatalyst for hydrogen energy conversion devices. By immobilizing MBH with affinity tags on a tin-rich indium tin oxide (ITOTR) electrode, hydrogen oxidation and an unusually high proton reduction current were observed, suggesting bidirectionality in unidirectional [NiFe] hydrogenases. The favorable enzyme-semiconductor interactions contribute to this behavior.
Review
Biochemistry & Molecular Biology
Peter Hildebrandt
Summary: This review summarizes how resonance Raman and IR spectroscopy contributed to the understanding of the structure, dynamics, and reaction mechanism of phytochromes. It also discusses the challenges faced in experimental and theoretical research and describes strategies to overcome them.
Article
Chemistry, Multidisciplinary
Tarali Devi, Kuheli Dutta, Jennifer Deutscher, Stefan Mebs, Uwe Kuhlmann, Michael Haumann, Beatrice Cula, Holger Dau, Peter Hildebrandt, Kallol Ray
Summary: This study emphasizes the importance of subtle electronic changes and secondary interactions in the stability of biologically relevant metal-dioxygen intermediates. It also shows that the role of the chloride ligand in stabilizing the Fe-III-(OOBu)-Bu-t moiety can extend to other anions, including the thiolate ligand.
Article
Chemistry, Physical
Solomon L. D. Wrathall, Barbara Procacci, Marius Horch, Emily Saxton, Chris Furlan, Julia Walton, Yvonne Rippers, James N. Blaza, Gregory M. Greetham, Michael Towrie, Anthony W. Parker, Jason Lynam, Alison Parkin, Neil T. Hunt
Summary: Ultrafast two-dimensional infrared spectroscopy was used to study the structural and dynamic influence of the protein scaffold on the Fe(CO)(CN)(2) unit of the active site of Escherichia coli Hyd-1 (EcHyd-1). New active site states were observed and assigned using 2D-IR, and the vibrational levels and relaxation dynamics of the CO and CN modes were determined. The results show that the protein scaffold creates a distinct biomolecular environment for the NiFe site that differs from simple models of solvation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Holly A. Reeve, Jake Nicholson, Farieha Altaf, Thomas H. Lonsdale, Janina Preissler, Lars Lauterbach, Oliver Lenz, Silke Leimkuehler, Frank Hollmann, Caroline E. Paul, Kylie A. Vincent
Summary: We present a recycling system utilizing a soluble hydrogenase for synthetic nicotinamide cofactor analogues. With the coupling of an ene reductase, we achieved quantitative conversion of N-ethylmaleimide to N-ethylsuccinimide. The biocatalyst system retained over 50% activity after 7 hours.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Maria Fernandez Lopez, Margarethe Dahl, Francisco Velazquez Escobar, Hernan Ruy Bonomi, Anastasia Kraskov, Norbert Michael, Maria Andrea Mroginski, Patrick Scheerer, Peter Hildebrandt
Summary: This study investigates the structure and mechanistic properties of different types of phytochromes in bacteria using resonance Raman and IR difference spectroscopy, and reveals subtle differences in the photoinduced conversions and proton transfer processes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)