Article
Chemistry, Inorganic & Nuclear
Daniel Menia, Holger Kopacka, Klaus Wurst, Thomas Mueller, Petra Lippmann, Ingo Ott, Benno Bildstein
Summary: Cobaltoceniumselenolate coordination with Au(I) metal centers results in highly colored, stable compounds with good anticancer activity against various standard cancer cell lines. Characterization of these complexes was done through various analytical techniques such as NMR, IR, UV-Vis, HR-MS and single crystal XRD.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yan Zhang, Xiao-Fang Qi, Can-Hao Li, Shu-Zhong Zhan
Summary: The newly synthesized mononuclear cobalt complex 1 can serve as a molecular catalyst for the oxygen reduction reaction (ORR), achieving high H2O2 yield. The formation of a cobalt (III)-peroxo species is responsible for the O2 reduction reaction.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Rakesh Kumar, Ayushi Awasthi, Sikha Gupta, Raju Eerlapally, Apparao Draksharapu
Summary: In this study, a synthetic Ru-III-OCl species was reported as a structural mimic of haloperoxidase enzymes. This species can persist for a certain period of time at room temperature and perform oxygen atom transfer and hydrogen atom abstraction to organic substrates.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Aya I. Hassaballah, Ahmed K. El-Ziaty, Ewies F. Ewies, Ehab M. Zayed, Gehad G. Mohamed
Summary: Mononuclear complexes of various metal ions and a pyrimidine ligand were synthesized and characterized. Thermal and spectroscopic analyses revealed their stability and structure. Computational studies provided insight into molecular mechanisms. The complexes exhibited antibacterial, antifungal, and anticancer activities.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jyoti, Natalia Fridman, Anil Kumar, Sudhir G. Warkar
Summary: A series of cobalt complexes with A2B type bis-pyridine ligands have been synthesized and characterized, where different electron withdrawing or donating substituents at the meso position have been studied for their effects on the properties of the complexes. The behavior of mono- and bis-pyridine ligation was investigated through UV-Visible spectroscopy, showing that the lower the electron density on the corrole macrocycle, the higher the tendency for axial ligand binding.
INORGANICA CHIMICA ACTA
(2021)
Article
Chemistry, Physical
Omar Berradj, Hadda Bougherra, Ahmed Adkhis, Tahar Amrouche, Nour Elyakine Amraoui, Dalila Hammoutene
Summary: Three new mixed-ligand complexes of [Co(Hdmg)(2)(Ura)X] type were synthesized and characterized. The thermal decomposition process was found to occur in three steps, with the complexes showing specific structural and bonding characteristics observed through IR and UV-visible spectroscopies. Antibacterial activity tests revealed that the combination of iodo and bromo complexes exhibited stronger inhibitory power compared to other combinations and free complexes.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Inorganic & Nuclear
Dattaprasad D. Narulkar, Azaj Ansari, Anil Kumar Vardhaman, Sarvesh S. Harmalkar, Giribabu Lingamallu, Vishal M. Dhavale, Muniyandi Sankaralingam, Sandip Das, Pankaj Kumar, Sunder N. Dhuri
Summary: A mononuclear manganese(III)-peroxo complex was synthesized and studied for its reactivity in aldehyde deformylation reaction, showing nucleophilic character. Various kinetic and chemical parameters of the reaction were measured and determined.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Sofia Tzani, Michael Pissas, Vassilis Psycharis, Dimitrios A. Pantazis, Yiannis Sanakis, Catherine P. Raptopoulou
Summary: Two complexes were obtained by the reaction of methyl-2-pyridyl ketone with FeCl3.6H(2)O in various solvents. The molecular structures and physical properties of the two complexes are different.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Luann R. D'souza, Sarvesh S. Harmalkar, Nikita N. Harmalkar, Raymond J. Butcher, Ankita S. Pal, Pratik A. Asogekar, Sunder N. Dhuri
Summary: In this report, the synthesis and characterization of five cobalt compounds are presented. The crystal structures, elemental composition, spectroscopic properties, magnetic properties, and thermal behavior of the compounds were analyzed using various techniques. The oxidizing properties of two of the compounds were evaluated through electron transfer reactions with ferrocene derivatives.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Multidisciplinary
Tesfay G. Ashebr, Leo La Droitte, Xiao-Lei Li, Chen Zhao, Jinjiang Wu, Quan Zhou, Olivier Cador, Boris Le Guennic, Jinkui Tang
Summary: Using an edaravone-based aryloxide ligand, four new mononuclear Dy(III) compounds were synthesized. The complexes exhibited a slow relaxation of the magnetization, and the magnetic properties were influenced by chemical modifications on the dominant crystal field interaction and the presence of different counterions.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Crystallography
Valentin L. Virgil, Anamaria Hanganu, Augustin M. Madalan
Summary: Chalcones are a type of α, β-unsaturated ketones with great structural diversity and various applications. In this study, a chalcone synthesized by condensation of 2-acetylpyridine with 2-naphthaldehyde was employed for the synthesis of two mononuclear complexes. The structures of the chalcone and complexes were characterized by single-crystal X-ray diffraction, revealing that the chalcone acts as a chelating bidentate ligand. The luminescent properties of the ligand and complexes were investigated in the solid state, and it was found that the emission of Eu(III) and Tb(III) ions are influenced by the excitation wavelength.
Review
Chemistry, Inorganic & Nuclear
Donghyun Jeong, Joan Selverstone Valentine, Jaeheung Cho
Summary: Metalloenzymes use transition metal ions as co-factors to bind with dioxygen, allowing it to be used in various biological processes. Metal-peroxo species have been proposed as key intermediates, and synthetic model chemistry has helped understand their mechanisms. This review focuses on nonheme first-row transition metal peroxo complexes with their physicochemical characterization, structural information, and chemical reactivities relevant to biological systems.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marianna Pioli, Cecilia Loffi, Paolo Pio Mazzeo, Alessia Bacchi, Paolo Pelagatti
Summary: Two different N-substituted naphthalimide ligands have been synthesized and reacted with a cationic organometallic fragment, showing different coordination behaviors. One ligand forms a sandwich complex with six coordination sites, while the other forms two isomeric complexes with different stabilities.
INORGANICA CHIMICA ACTA
(2021)
Article
Biochemistry & Molecular Biology
Kalai Selvan Karumban, Rajnikant Raut, Parth Gupta, Arabinda Muley, Bishnubasu Giri, Sadananda Kumbhakar, Ashish Misra, Somnath Maji
Summary: Mononuclear cobalt(II) complexes were synthesized and characterized, showing strong DNA binding ability and efficient DNA cleavage. These complexes also induced apoptosis in human cancer cells.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Marta A. Fik-Jaskolka, Izabela Pospieszna-Markiewicz, Giovanni N. Roviello, Maciej Kubicki, Wanda Radecka-Paryzek, Violetta Patroniak
Summary: The LaPA complex stabilizes the hybrid-type G4 structure of Te126 in a K+ solution, showing biological potential. Additionally, LaPA induces structural changes in Te126 in a K+-deprived solution, suggesting potential conformational changes in non-G4 telomeric DNA.
INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Hannah M. Rhoda, Alexander J. Heyer, Benjamin E. R. Snyder, Dieter Plessers, Max L. Bols, Robert A. Schoonheydt, Bert F. Sels, Edward Solomon
Summary: Second-sphere interactions play a crucial role in the high activity and selectivity of transition-metal-exchanged zeolites, despite the differences in active-site structures compared to metalloenzymes.
Article
Chemistry, Physical
Edward Solomon, Anex Jose
Summary: This paper provides an overview of the unique spectroscopic features of metal sites in biology, reflecting novel geometric and electronic structures imposed by the protein; it introduces the example of the blue copper active site and its significance in biological electron transfer; it also demonstrates the role of the protein in the geometric and electronic structure of the active site.
FARADAY DISCUSSIONS
(2022)
Article
Biochemistry & Molecular Biology
Yang Ha, Sara A. Dille, Augustin Braun, Kyle Colston, Britt Hedman, Keith O. Hodgson, Partha Basu, Edward I. Solomon
Summary: This study investigates the bonding descriptions and geometric structures of oxidized dithiolene complexes bound to low-valent late transition metal ions, such as Zn-II, Cu-I, and Cu-II, using a combination of S K-edge X-ray absorption spectroscopy and density functional theory calculations. The study quantifies the competition between ligand-ligand repulsion and changes in electronic structures in determining the final geometric structures of the complexes.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2022)
Correction
Instruments & Instrumentation
Diego A. Huyke, Ashwin Ramachandran, Oscar Ramirez-Neri, Jose A. Guerrero-Cruz, Leland B. Gee, Augustin Braun, Dimosthenis Sokaras, Brenda Garcia-Estrada, Edward I. Solomon, Britt Hedman, Mario U. Delgado-Jaime, Daniel P. DePonte, Thomas Kroll, Juan G. Santiago
JOURNAL OF SYNCHROTRON RADIATION
(2022)
Article
Multidisciplinary Sciences
Ioannis Kipouros, Agnieszka Stanczak, Jake W. Ginsbach, Prokopis C. Andrikopoulos, Lubomir Rulsek, Edward I. Solomon
Summary: Melanins are important biopolymer pigments that provide photoprotection, and their biosynthesis involves the catalytic role of tyrosinase (Ty). This study combines spectroscopic, kinetic, and computational methods to investigate the mechanism of the rate-limiting step in melanin biosynthesis. The results provide insights into the O-2 activation and reactivity by the active sites of coupled binuclear copper, with implications in biocatalysis.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Review
Biochemistry & Molecular Biology
Ioannis Kipouros, Edward I. Solomon
Summary: Tyrosinase, a member of the CBC protein family, has been studied extensively. Recent research has revealed the structure of a catalytic ternary intermediate and proposed a revised mechanism for monophenol monooxygenation. These findings are significant for understanding structure-function relationships in CBC enzymes and the activation of O-2 in bioinorganic active sites.
Article
Chemistry, Inorganic & Nuclear
Wesley J. Transue, Rae Ana Snyder, Jonathan D. Caranto, Donald M. Kurtz Jr, Edward I. Solomon
Summary: This paper describes a particle swarm optimization (PSO) algorithm for fitting ground-state spin Hamiltonian parameters from variable-temperature/variable-field magnetic circular dichroism (MCD) data. The PSO algorithm is used to determine the ground state of two catalytic intermediates from a flavodiiron protein with nitric oxide reductase activity. The fits of the spin Hamiltonians provide important geometric and electronic insight into these species.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Dieter Plessers, Alexander J. Heyer, Hannah M. Rhoda, Max L. Bols, Edward I. Solomon, Robert A. Schoonheydt, Bert F. Sels
Summary: The industrial implementation of a direct methane-to-methanol process would bring about environmental and economic benefits. Copper zeolites can effectively catalyze this reaction at lower temperatures, especially mordenite zeolites which enable high methanol production. By changing the co-cation, a new method for simplifying the material is introduced, allowing for better analysis, which has implications for the study and tuning of heterogeneous catalysts in general.
Article
Chemistry, Multidisciplinary
Bohee Kim, Magdalene T. T. Brueggemeyer, Wesley J. J. Transue, Younwoo Park, Jaeheung Cho, Maxime A. A. Siegler, Edward I. I. Solomon, Kenneth D. D. Karlin
Summary: Lytic polysaccharide monooxygenases are important in converting biomass to biofuel, and recent studies show that their peroxygenase activity using H2O2 as an oxidant is more important than their monooxygenase functionality. New insights into this activity have been described, including ligand-substrate hydroxylation and Fenton-type chemistry reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jeffrey T. T. Babicz Jr, Melanie S. Rogers, Dory E. DeWeese, Kyle D. Sutherlin, Rahul Banerjee, Lars H. Bottger, Yoshitaka Yoda, Nobumoto Nagasawa, Makina Saito, Shinji Kitao, Masayuki Kurokuzu, Yasuhiro Kobayashi, Kenji Tamasaku, Makoto Seto, John D. Lipscomb, Edward I. Solomon
Summary: The extradiol dioxygenases and intradiol dioxygenases play a crucial role in the carbon cycle by catalyzing oxidative aromatic ring cleavage. This study investigates the mechanisms behind their regiospecificity in cleavage, using EDO and IDO enzymes as models. The results reveal the structural and electronic properties of key intermediates and propose a viable mechanism for intradiol cleavage.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Augustin Braun, Leland B. Gee, Michael W. Mara, Ethan A. Hill, Thomas Kroll, Dennis Nordlund, Dimosthenis Sokaras, Pieter Glatzel, Britt Hedman, Keith O. Hodgson, A. S. Borovik, Michael L. Baker, Edward I. Solomon
Summary: Fe K-edge XAS is widely used for studying high-valent iron intermediates in catalysts. The 4p-mixing into the 3d orbitals complicates the analysis, but understanding it correctly enables deeper insights into the structure and reactivity. This study reveals that the loss of inversion in the equatorial plane leads to 4p mixing into the 3dx2-y2,xy orbitals, providing structural insights for distinguishing 6- vs 5-coordinate active sites. Furthermore, the study investigates the electronic structure of Fe(IV)=O active sites and their reactivity selectivity through O K-edge XAS.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Casey Van Stappen, Huiguang Dai, Anex Jose, Shiliang Tian, Edward I. Solomon, Yi Lu
Summary: This research investigates the influence of the primary and secondary coordination sphere on CuII-catalyzed S-nitrosylation. The study reveals that kinetic competency is correlated with Cu-S bond strength, Cu spin localization, and relative S(p(s)) vs S(p(p)) contributions to the ground state.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hyeongtaek Lim, Magdalene T. Brueggemeyer, Wesley J. Transue, Katlyn K. Meier, Stephen M. Jones, Thomas Kroll, Dimosthenis Sokaras, Bradley Kelemen, Britt Hedman, Keith O. Hodgson, Edward I. Solomon
Summary: This study investigates the electronic structure of the d(10) Cu(I) active site in LPMO using Kβ X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the required 3d/p mixing for intensity in the Kβ valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kβ XES data are correlated to density functional theory (DFT) calculations to define the bonding, particularly the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H2O2 O-O bond and understand the activation of the geometric and electronic structure of the Cu(I)-LPMO site for rapid reactivity with H2O2.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Asmita Singha, Alina Sekretareva, Lizhi Tao, Hyeongtaek Lim, Yang Ha, Augustin Braun, Stephen M. Jones, Britt Hedman, Keith O. Hodgson, R. David Britt, Daniel J. Kosman, Edward I. Solomon
Summary: In multicopper oxidases (MCOs), the T1 Cu accepts electrons from the substrate and transfers them to the TNC, reducing O-2 to H2O. The literature fails to explain the wide range of T1 potentials in MCOs, ranging from 340 to 780 mV. This study focuses on the difference in potential of the T1 center in Fet3p and Trametes versicolor laccase (TvL) that have the same ligand set, and reveals that second-sphere H-bonding interactions and carboxylate residues significantly lower the T1 potential.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ioannis Kipouros, Agnieszka Stanczak, Martin Culka, Erik Andris, Timothy R. Machonkin, Lubomir Rulisek, Edward Solomon
Summary: This study reveals the H-bonding interactions between active-site waters and the mu-eta(2):eta(2)-peroxide of oxy-tyrosinase, and defines their effects on the Cu(ii)(2)O-2 electronic structure and O-2 activation using spectroscopic and computational methods.
CHEMICAL COMMUNICATIONS
(2022)