Article
Chemistry, Inorganic & Nuclear
Molly M. Lockart, Kyle C. Edwards, John B. Vincent, Brad S. Pierce
Summary: The study detected an EPR signal for Mn(III) bound to transferrin, suggesting the six-coordinate nature of the Mn(III) centers in an elongated tetragonal environment. Incorporation of Mn(III) within the Tf active site did not significantly alter the coordination number or active site geometry compared to native Fe(III)(2)-Tf. The parallel mode EPR signal for Mn(III)(2)-Tf could be valuable for future studies on the physiological relevance of Mn(III)(2)-Tf.
Article
Chemistry, Multidisciplinary
Santina S. Cruz, Vadim Tanygin, Benjamin J. Lear
Summary: Using electron spin resonance spectroscopy, it has been demonstrated that morphological asymmetries in small spheroidal metallic nanoparticles significantly affect the electronic behavior of states near the metal's Fermi energy. The study found that morphological effects were more important than size distributions in explaining the asymmetry in electronic behavior, and this was consistent across various particles made from different metals. Additionally, the study also showed that morphological changes can tune the electronic properties of even small particles, as evidenced by the modeling used to explain asymmetries in both electron spin resonance spectra and plasmon spectra.
Article
Biochemistry & Molecular Biology
Anthony John Pastore, Alvaro Montoya, Manasi Kamat, Kari B. Basso, James S. Italia, Abhishek Chatterjee, Maria Drosou, Dimitrios A. Pantazis, Alexander Angerhofer
Summary: Oxalate decarboxylase is an acid stress response enzyme that converts oxalic acid into formate and carbon dioxide. The enzyme relies on binuclear Mn and long-range electron transfer facilitated by pi-stacked tryptophan dimers. Substituting one of the tryptophan residues with 5-hydroxytryptophan hinders electron transfer and suppresses enzymatic activity.
Article
Materials Science, Multidisciplinary
A. M. Panich, A. Shames, A. E. Aleksenskii, E. B. Yudina, A. Ya Vul'
Summary: In this study, a novel nanomaterial called detonation nanodiamond (DND) with manganese ions grafted to its surface was successfully prepared and investigated for its potential as an MRI contrast agent. The chemical binding of Mn2+ ions to the nanodiamond surface was confirmed, with interactions accelerating spin-lattice relaxation. Comparison with Gd-grafted DND suggests that Mn-DND has promising applications in MRI contrast imaging.
DIAMOND AND RELATED MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Qi Chen, Olugbenga Adeniran, Zhen-Fei Liu, Zhongyue Zhang, Kunio Awaga
Summary: In this study, the electrochemical process of a two-dimensional pi-d conjugated metal-organic framework (MOF) was monitored using magnetometric techniques. The results revealed the presence of a graphite-like charge storage mechanism, which explained the high charge storage capacity of the MOF.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Q. Chen, Olugbenga Adeniran, Zhen-Fei Liu, Zhongyue Zhang, Kunio Awaga
Summary: This study utilized magnetometric techniques to monitor the electrochemical process of two-dimensional metal-organic frameworks and discovered a graphite-like charge storage mechanism that explains their high charge storage capacity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qi Chen, Olugbenga Adeniran, Zhen-Fei Liu, Zhongyue Zhang, Kunio Awaga
Summary: This study investigates the charge storage mechanism of quasi-2D ir-d conjugated Cu-THQ MOF through magnetometric techniques and density functional theory calculations. It reveals the presence of a graphite-like charge storage mechanism, which can explain the high charge storage capacity of Cu-THQ and can be applied to other ir-d conjugated MOFs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Analytical
Hideo Utsumi, Toshiki Masumizu, Ryoma Kobayashi, Tomoko Tahira, Fuminori Hyodo, Tatsuya Shimizu, Tatsuya Naganuma, Kazunori Anzai
Summary: Free radicals are key substances in organisms but can also cause oxidative diseases. Dynamic nuclear polarization- magnetic resonance imaging is a noninvasive imaging method that can be used for in vivo free radical imaging.
ANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Toshinobu Nakajo, Jun Kumagai, Shinpei Kusaka, Akihiro Hori, Yuh Hijikata, Jenny Pirillo, Yunsheng Ma, Ryotaro Matsuda
Summary: Triplet carbenes (TCs) are highly reactive species with unique electronic states, making it challenging to balance reactivity and stability. By confining TCs in the nanospace of a metal-organic framework (MOF), it is possible to enhance their thermal stability while maintaining reactivity, allowing for the stabilization of highly reactive species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Crystallography
Valentin G. Grachev, Galina Malovichko
Summary: Intrinsic and extrinsic defects, especially paramagnetic ions of transition metals and rare-earth elements, have a significant impact on the properties of lithium niobate (LN) and tantalate (LT), determining their suitability for various applications. Discussions on the structures of defects in LN/LT have been ongoing for decades, with experimental methods facilitating progress in determining the structures of impurity centers. Symmetry and charge compensation considerations restrict the number of possible structures, and comparison of measured angular dependences of ENDOR frequencies with calculated ones allows for the accurate determination of the exact location of paramagnetic impurities. Self-compensation of excessive charges in stoichiometric LN/LT leads to the appearance of interstitial Li+ in the structural vacancy near paramagnetic ions Me3+(Nb5+).
Article
Chemistry, Multidisciplinary
Alexandre Genoux, Magnus Pauly, Conor L. Rooney, Chungseok Choi, Bo Shang, Scott McGuigan, Majed S. Fataftah, Yves Kayser, Simon C. B. Suhr, Serena Debeer, Hailiang Wang, Paul A. Maggard, Patrick L. Holland
Summary: Carbon nitride materials with stoichiometric iron sites having the same environment were synthesized and characterized. The material showed tetrahedral high-spin iron(II) sites throughout and exhibited excellent electrocatalytic activity for nitrate reduction to ammonia.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Anthony J. Campanella, Manh-Thuong Nguyen, Jun Zhang, Thacien Ngendahimana, William E. Antholine, Gareth R. Eaton, Sandra S. Eaton, Vassiliki-Alexandra Glezakou, Joseph M. Zadrozny
Summary: This work investigates how variations in ligand structures affect the EPR spectroscopic properties of five Cr(III) complexes, indicating that the spectral broadening is correlated to rigidity in the inner coordination sphere and reflected in ligand-dependent distribution of Cr-N bond distances.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Krzysztof Kruczala, Susann Neubert, Kapil Dhaka, Dariusz Mitoraj, Petra Janosikova, Christiane Adler, Igor Krivtsov, Julia Patzsch, Jonathan Bloh, Johannes Biskupek, Ute Kaiser, Rosalie K. Hocking, Maytal Caspary Toroker, Radim Beranek
Summary: There is limited knowledge of the mechanism of photocatalytic enhancement in SAC-modified photocatalysts. This study reports highly active photocatalysts for the aerobic degradation of pollutants based on TiO2 modified with various SACs. The results provide valuable insights into the mechanistic diversity of different SACs and identify essential design guidelines for the future development of SAC-based photocatalysts with enhanced performance.
Article
Chemistry, Applied
Chaoyi Xue, Yong Li, Wei Quan, Peng Deng, Zhiyong He, Fang Qin, Zhaojun Wang, Jie Chen, Maomao Zeng
Summary: The synchronous mitigative effects of Alpinia officinarum Hance and curcumin on the generation of methylimidazole and acrylamide in cookies were investigated. Mechanisms related to quenching free radicals, reducing lipid oxidation and eliminating carbonyl intermediates were explored. The results showed that both Alpinia officinarum Hance and curcumin reduced the formation of methylimidazole and acrylamide in a dose-dependent manner, possibly by quenching free radicals.
Article
Chemistry, Inorganic & Nuclear
Zofia Janas, Julia Jezierska, Andrew Ozarowski, Alina Bienko, Tadeusz Lis, Adam Jezierski, Marta Krawczyk
Summary: A family of oxidovanadium(IV) compounds with various linear diaminebis(phenolate) ligands and non-oxidovanadium(III) compounds have been synthesized and characterized, showing weak ferromagnetic metal-metal exchange interactions. Different coordination modes between the ligands and vanadium center were observed through X-ray crystallography.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Elena Atrian-Blasco, Lucie de Cremoux, Xudong Lin, Rufus Mitchell-Heggs, Laurent Sabater, Sebastien Blanchard, Christelle Hureau
Summary: Two Keggin polyoxometalates were tested as copper ligands to counteract the effects of Cu-II(Amyloid-beta) interaction. They demonstrated the ability to remove Cu-II from Cu-II(Amyloid-beta), inhibit Cu-II(Amyloid-beta)-induced reactive oxygen species formation, and restore the apo-like self-assembly of Cu-II(Amyloid-beta).
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Micaela Richezzi, Joaquin Ferreyra, Juan Puzzolo, Lisandro Milesi, Claudia M. Palopoli, Diego M. Moreno, Christelle Hureau, Sandra R. Signorella
Summary: The reactivity of Cu(II) complex toward O-2(center dot-) and H2O2 was investigated. The complex showed fast reaction rates with O-2(center dot-) and H2O2, forming stable Cu(II)-hydroperoxide. The Cu(II)-hydroperoxide was found to mediate the oxidation of phenols.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
[Anonymous]
Summary: This article introduces the versatility of a copper complex and its reactions with hydrogen peroxide and superoxide, as well as the catalytic oxidation activity towards phenol.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Plant Sciences
Pilla Sankara Krishna, Stuart Daniel Woodcock, Sebastian Pfeilmeier, Stephen Bornemann, Cyril Zipfel, Jacob George Malone
Summary: Polysaccharides play important roles in helping Pseudomonas syringae pv. tomato overcome environmental challenges during plant infection, with their expression tightly regulated by various environmental signals. Functional redundancy and combinatorial phenotypes are key features of how polysaccharides function in this process.
JOURNAL OF EXPERIMENTAL BOTANY
(2022)
Article
Chemistry, Multidisciplinary
Svetlana Eliseeva, Tu N. Nguyen, Jeff W. Kampf, Evan R. Trivedi, Vincent L. Pecoraro, Stephane Petoud
Summary: This study reports a new family of Zn(16)Ln(HA)(16) metallacrowns with outstanding luminescence properties in the near-infrared (NIR) and suitability for cell imaging. The authors synthesized MCs with two new hydroximate ligands and found that they efficiently sensitize the NIR emissions of Yb-III, Er-III, and Nd-III. The photophysical properties and quantum yields of the MCs were analyzed, providing valuable information for creating MCs suitable for NIR optical imaging.
Article
Biochemistry & Molecular Biology
Vasilii Graur, Yurii Chumakov, Olga Garbuz, Christelle Hureau, Victor Tsapkov, Aurelian Gulea
Summary: A series of metal complexes were synthesized and characterized in this study. The synthesized compounds showed different inhibitory effects and selectivity on the proliferation of cancer cells and normal cells, with zinc and copper complexes exhibiting high antibacterial activity. Additionally, the study found that the biological activity of the compounds could be predicted using theoretical calculations.
BIOINORGANIC CHEMISTRY AND APPLICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Tyler B. J. Pinter, Catherine S. Ervin, Aniruddha Deb, James E. Penner-Hahn, Vincent L. Pecoraro
Summary: The protein ORF1p of long interspersed nuclear elements-1 (L1) can bind copper ions in a pH-dependent manner, potentially affecting its structure and biological activity.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Karl J. Koebke, Tyler B. J. Pinter, Winston C. Pitts, Vincent L. Pecoraro
Summary: This review highlights the progress and milestone achievements in the field of de novo metalloprotein design in the past decade, with a focus on heme binding proteins, catalytic sites, and electron transfer sites. The significant contributions to our understanding of these subfields or de novo metalloprotein design are categorized and discussed in the context of history and science. Suggestions for future research directions are also provided.
Article
Chemistry, Inorganic & Nuclear
Elvin V. Salerno, Collin M. Foley, Vittoria Marzaroli, Bernadette L. Schneider, Max D. Sharin, Jeff W. Kampf, Luciano Marchio, Matthias Zeller, Regis Guillot, Talal Mallah, Matteo Tegoni, Vincent L. Pecoraro, Curtis M. Zaleski
Summary: Seven dimeric metallacrowns based on Ln[12-MCM(III)N(shi)-4] have been synthesized and characterized. Magnetic properties of the dysprosium-manganese dimers were measured. The choice of dicarboxylate affects the binding position of the countercations. All three Dy2Mn8 dimers show an out-of-phase magnetic susceptibility signal associated with magnetization relaxation.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Elvin Salerno, Albano N. Carneiro Neto, Svetlana Eliseeva, Miguel A. Hernandez-Rodriguez, Jacob C. Lutter, Timothee Lathion, Jeff W. Kampf, Stephane Petoud, Luis D. Carlos, Vincent L. Pecoraro
Summary: This study examines the impact of ligands' energy levels on the thermal dependence of lanthanide emission and successfully creates new molecular nanothermometers. The results show that the difference in energy levels between the triplet state and the excited state of lanthanides is a key factor controlling the thermal dependence of emission intensity. Moreover, the energy gap between ligand-centered states also affects the thermal behavior.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tu N. Nguyen, Svetlana V. Eliseeva, Ivana Martinic, Peggy L. Carver, Timothee Lathion, Stephane Petoud, Vincent L. Pecoraro
Summary: By combining pyrazine- and quinoxaline-based hydroximate building blocks ligands, we created water-soluble mixed-ligand metallacrowns (MCs) with extended absorption to the visible range. The Yb-III analogue showed improved photophysical properties in the near-infrared (NIR) range in cell culture media, making it suitable for NIR optical imaging in living HeLa cells.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Matteo Melegari, Vittoria Marzaroli, Rosy Polisicchio, Davide Seletti, Luciano Marchio, Vincent L. Pecoraro, Matteo Tegoni
Summary: The solution structure of lanthanide metallacrowns was studied using H-1 NMR and DFT models. NMR data and DFT models provided information on dynamic equilibrium processes in solution that could not be observed from X-ray data alone. The NMR spectra and structural analysis of Ln(III)Na(I)(OBz)(4)[12-MCGaIII(N)Shi-4] complexes revealed significant structural changes from the solid state to solution phase, especially in the orientation of the phenyl groups of the benzoate ions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Micaela Richezzi, Sharon Signorella, Claudia Palopoli, Nora Pellegri, Christelle Hureau, Sandra R. Signorella
Summary: The flexibility of the ligand plays a crucial role in tuning the reactivity of Mn SOD mimics, and immobilization techniques can enhance the stability and activity of the catalyst.
Review
Chemistry, Multidisciplinary
Enrico Falcone, Christelle Hureau
Summary: This study reports on a concept that explains the formation of reactive oxygen species by copper ions bound to the amyloid-β peptide involved in Alzheimer's disease. The concept is based on a refined and extended in-between state mechanism that was first described a decade ago for pure electron transfer.
CHEMICAL SOCIETY REVIEWS
(2023)
Review
Chemistry, Multidisciplinary
Karl J. Koebke, Tyler B. J. Pinter, Winston C. Pitts, Vincent L. Pecoraro
Summary: This review summarizes the progress and milestone achievements in the field of de novo metalloprotein design in the past decade, with a special focus on new designs within common subfields of bioinorganic study. The reports discussed provide important contributions to our understanding of these subfields and de novo metalloprotein design. The review also offers general suggestions for future directions to advance our understanding and accelerate discovery.