metal interactions
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2022 ◽  
Vol 5 (1) ◽  
Author(s):  
Bo Jin ◽  
Hai-Ru Li ◽  
Zhihong Wei ◽  
Miao Yan ◽  
Caixia Yuan ◽  
...  

AbstractNon-spherical distributions of ligand atoms in coordination complexes are generally unfavorable due to higher repulsion than for spherical distributions. To the best of our knowledge, non-spherical heptagonal bipyramidal nonacoordination is hitherto unreported, because of extremely high repulsion among seven equatorial ligand atoms. Herein, we report the computational prediction of such nonacoordination, which is constructed by the synergetic coordination of an equatorial hepta-dentate centripetal ligand (B7O7) and two axial mono-dentate ligands (-BO) in the gear-like mono-anionic complexes [OB-M©B7O7-BO]– (M = Fe, Ru, Os). The high repulsion among seven equatorial ligand B atoms has been compensated by the strong B–O bonding. These complexes are the dynamically stable (up to 1500 K) global energy minima with the HOMO-LUMO gaps of 7.15 to 7.42 eV and first vertical detachment energies of 6.14 to 6.66 eV (being very high for anions), suggesting their high probability for experimental realization in both gas-phase and condensed phases. The high stability stems geometrically from the surrounded outer-shell oxygen atoms and electronically from meeting the 18e rule as well as possessing the σ + π + δ triple aromaticity. Remarkably, the ligand-metal interactions are governed not by the familiar donation and backdonation interactions, but by the electrostatic interactions and electron-sharing bonding.


2021 ◽  
pp. 132144
Author(s):  
Vali Alizadeh ◽  
Ghodrat Mahmoudi ◽  
Marina A. Vinokurova ◽  
Kuzma M. Pokazeev ◽  
Kseniia A. Alekseeva ◽  
...  
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Author(s):  
Milena Dahlen ◽  
Niklas Reinfandt ◽  
Chengyu Jin ◽  
Michael T. Gamer ◽  
Karin Fink ◽  
...  

Author(s):  
Michael P. Thorgersen ◽  
Jingchuan Xue ◽  
Erica L.W. Majumder ◽  
Valentine V. Trotter ◽  
Xiaoxuan Ge ◽  
...  

To uncover metal toxicity targets and defense mechanisms of the facultative anaerobe Pantoea strain sp. MT58 (MT58), we used a multi-omic strategy combining two global techniques, random bar code transposon-site sequencing (RB-TnSeq) and activity-based metabolomics. MT58 is a metal-tolerant Oak Ridge Reservation (ORR) environmental isolate that was enriched in the presence of metals at concentrations measured in contaminated groundwater at an ORR nuclear waste site. The effects of three chemically-different metals found at elevated concentrations in the ORR contaminated environment were investigated: the cation Al 3+ , the oxyanion CrO 4 2- , and the oxycation UO 2 2+ . Both global techniques were applied using all three metals under both aerobic and anaerobic cultures to elucidate metal interactions mediated through the activity of metabolites and key genes/proteins. These revealed that Al 3+ binds intracellular arginine, CrO 4 2- enters the cell through sulfate transporters and oxidizes intracellular reduced thiols, and membrane-bound lipopolysaccharides protect the cell from UO 2 2+ toxicity. In addition, the Tol outer membrane system contributed to the protection of cellular integrity from the toxic effects of all three metals. Likewise, we found evidence of regulation of lipid content in membranes under metal stress. Individually, RB-TnSeq and metabolomics are powerful tools to explore the impact various stresses have on biological systems. Herein we show that together they can be used synergistically to identify the molecular actors and mechanisms of these pertubations to an organism furthering our understanding of how living systems interact with their environment. Importance Studying microbial interactions with their environment can lead to a deeper understanding of biological molecular mechanisms. In this manuscript, two global techniques, RB-TnSeq and activity metabolomics, were successfully used to probe the interactions between a metal resistant microorganism, Pantoea strain sp. MT58, and metals contaminating a site where the organism can be located. A number of novel metal to microbe interactions were uncovered including Al 3+ toxicity targeting arginine synthesis, which could lead to a deeper understanding of the impact Al 3+ contamination has on microbial communities as well as its impact on higher level organisms including plants for whom Al 3+ contamination is an issue. Using multi-omic approaches as the one described here is a way to further our understanding of microbial interactions and their impacts on the environment overall.


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