Changing the Reactivity of Zero- and Mono-Valent Germanium with a Redox Non-Innocent Bis(silylenyl)carborane Ligand.
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ABSTRACT:
SUBMITTER: Yao S
PROVIDER: S-EPMC8252802 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Despite their potential role in enzymatic systems, there is a dearth of hydroxide-bridged high-valent oxidants. We recently reported the synthesis and characterization of NiIINiIII(μ-OH)2 (2) and Ni2 III(μ-OH)2 (3) species supported by a dicarboxamidate ligand (N,N'-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide). Herein, we explore the oxidative reactivity of these species using a series of para-substituted 2,6-di-tert-butyl-phenols (4-X-2,6-DTBP, X = -OCH3, -CH2CH3, -CH3, -C(CH3)3, -H, -Br, -CN, and -NO2) as a mechanistic probe. Interestingly, upon reaction of 3 with the substrates, the formation of a new transient species, 2', was observed. 2' is postulated to be a protic congener of 2. All three species were demonstrated to react with the substituted phenols through a hydrogen atom transfer reaction mechanism, which was elucidated further by analysis of the postreaction mixtures. Critically, 3 was demonstrated to react at far superior rates to 2 and 2', and oxidized substrates more efficiently than any bis-μ-oxo-Ni2 III reported to date. The kinetic superiority of 3 with respect to 2 and 2' was attributed to a stronger bond in the product of oxidation by 3 when compared to those calculated for 2 and 2'.
| S-EPMC8554787 | biostudies-literature
Project description:Quinoid-based ligands constitute the most common class of redox-active ligands used to construct electrically conductive and magnetic metal-organic frameworks (MOFs). Whereas this chemistry is intensively explored for transition-metal and lanthanide ions, any related actinide compound has not received attention. In particular, the MOF chemistry of actinide ions in the lower oxidation states is underexplored. We herein report the synthesis, and structural and physical property characterization of a uranium(IV) quinoid-based MOF, [U(Cl2dhbq)2(H2O)2]·4H2O (1, Cl2dhbq2- = deprotonated 2,5-dichloro-3,6-dihydroxybenzoquinone). 1 is a rare example of a U(IV)-based coordination solid and the first material to incorporate bona fide reducible bridging ligands. Despite the anticipated thermodynamic driving force, no indications of valence tautomerism are evident from magnetometry, near-IR spectroscopy, and X-band electron paramagnetic resonance measurements. These initial results suggest that reduction potentials alone are insufficient as guidelines for the prediction of the occurrence of electron transfer in uranium-quinoid-based materials.
| S-EPMC7045569 | biostudies-literature
Project description:Zero-valent iron (ZVI)- and zero-valent aluminium (ZVA)-activated persulfate (PS) oxidation procedure was applied to remove the industrial pollutants 3,5-dichlorophenol (3,5-DCP; 12.27 µM) and 2,4-dichloroaniline (2,4-DCA; 12.34 µM) from aqueous solutions. The effects of PS concentration and pH were investigated to optimize heterogeneous treatment systems. Negligible removals were obtained for both pollutants by individual applications of nanoparticles (1 g/L) and PS (1.00 mM). PS activation with ZVI resulted in 59% (1.00 mM PS; 1 g/L ZVI; pH 5.0; 120 min) and 100% (0.75 mM PS; 1 g/L ZVI; pH 5.0; 80 min) 3,5-DCP and 2,4-DCA removals, respectively. The ZVA/PS treatment system gave rise to only 31% 3,5-DCP (1.00 mM PS; 1 g/L ZVA; pH 3.0; 120 min) and 47% 2,4-DCA (0.25 mM PS; 1 g/L ZVA; pH 3.0; 120 min) removals. The pH decreases from 5.0 to 3.0 and from 3.0 to 1.5 enhanced contaminant removals for ZVI/PS and ZVA/PS treatments, respectively. Pollutant removal rates were in correlation with the consumption rates of the oxidants. Metal ion (Al, Fe) release increased in the presence of PS and with decreasing pH.
| S-EPMC8164209 | biostudies-literature
Project description:BackgroundIonic and molecular carriers of dissolved (filter-passing) zero-valent sulfur (S0) in anaerobic natural waters include polysulfides, Sn2-, molecular S8(aq), organic macromolecules and certain higher valent thioanions. Because S0 is rapidly transferred among these various carriers, its biogeochemical roles in such processes as dehalogenation of organic compounds, chelation of trace metals, and anaerobic microbial metabolism are not determined solely by one ionic or molecular species. Here, S0 is treated collectively as a virtual thermodynamic component, and computational as well as graphical methods for quantifying its activity (aS0) in natural waters are presented. From aS0, concentrations of the ionic and molecular carriers of S0 can be calculated easily.ResultsConcentration ratios of any two polysulfide ions define aS0 (Method I). Unfortunately these concentrations are often too low in nature for accurate quantification with current methods. Measurements of total divalent sulfur (ΣS-II), zero-valent sulfur (ΣS0) and pH provide a more widely applicable approach (Method II). Systematic errors in ΣS0 measurements are the main limit to accuracy of this method at the present time. Alternative methods based on greigite solubility and potentiometry are discussed. A critical comparison of Methods I and II reveals inconsistencies at low ΣS0/ΣS-II that imply errors in the thermodynamic data for HS2- and S2-. For samples having low ΣS0/ΣS-II, an interim remedy is recommended: letting pKa2 = 6.3 for all HSn- ions.ConclusionsNewly assembled data for aS0 in a selection of anaerobic natural waters indicate that S0 is always metastable in the surveyed samples with respect to disproportionation to sulfide and sulfate. In all the surveyed environments, sulfur-rich minerals, such as greigite, covellite and orpiment, are stable in preference to their sulfur-poor cohorts, mackinawite, chalcocite and realgar. The aS0 values in the dataset span conditions favoring Hg-polysulfide complexes vs. Hg-sulfide complexes, implying that aS0 could affect Hg-methylation rates in nature. No support is found for the common assumption that aS0 = 1 in reducing natural waters. This paper calls attention to an urgent need for improved measurement methods, especially for total zero-valent sulfur, as well as new determinations of ionization constants for all HSn- species.
| S-EPMC4631721 | biostudies-literature
Project description:Zero-valent iron nanoparticles (nano-ZVIs) have been widely studied for in situ remediation of groundwater and other environmental matrices. Nano-ZVI particle mobility and reactivity are still the main impediments in achieving efficient in situ groundwater remediation. Compared to the nano-ZVI "coating" strategy, nano-ZVI stabilization on supporting material allows direct contact with the contaminant, reduces the electron path from the nano-ZVI to the target contaminant and increases nano-ZVI reactivity. Herein, we report the synthesis of nano-ZVI stabilized by cellulose nanocrystal (CNC) rigid nanomaterials (CNC-nano-ZVI; Fe/CNC = 1 w/w) with two different CNC functional surfaces (-OH and -COOH) using a classic sodium borohydride synthesis pathway. The final nanocomposites were thoroughly characterized and the reactivity of CNC-nano-ZVIs was assessed by their methyl orange (MO) dye degradation potential. The mobility of nanocomposites was determined in (sand/glass bead) porous media by utilizing a series of flowthrough transport column experiments. The synthesized CNC-nano-ZVI provided a stable colloidal suspension and demonstrated high mobility in porous media with an attachment efficiency (α) value of less than 0.23. In addition, reactivity toward MO increased up to 25% compared to bare ZVI. The use of CNC as a delivery vehicle shows promising potential to further improve the capability and applicability of nano-ZVI for in situ groundwater remediation and can spur advancements in CNC-based nanocomposites for their application in environmental remediation.
| S-EPMC5929147 | biostudies-literature
Project description:Here, we established a successive Fe0-enhanced microbe system to remove azo dye (a typical organic pollutant) by Shewanella decolorationis S12 (S. decolorationis S12, an effective azo dye degradation bacterium) and examined the gene expression time course (10, 30, 60, and 120 min) in whole genome transcriptional level. Comparing with the treatment without ZVI, approximately 8% genes affiliated with 10 different gene expression profiles in S. decolorationis S12 were significantly changed in 120 min during the ZVI-enhanced microbial azo reduction. Intriguingly, MarR transcriptional factor might play a vital role in regulating ZVI-enhanced azo reduction in the aspect of energy production, iron homeostasis, and detoxification. Further investigation showed that induced [Ni-Fe] H2ase genes (hyaABCDEF) and azoreductase genes (mtrABC-omcA) contributed to ZVI-enhanced energy production, while reduced iron uptake (hmuVCB and feoAB), induced sulfate assimilation (cysPTWA) and cysteine biosynthesis (cysM) related genes were essential to iron homeostasis and detoxification. This study disentangles underlying mechanisms of ZVI-enhanced azo reduction in S. decolorationis S12 and lays a foundation for further optimization of integrated ZVI-microbial system for efficient organic pollution treatment.
2021-10-01 | GSE160493 | GEO
Project description:We report a new DSR pathway that directly generates zero-valent sulfur (ZVS) in phylogenetically diverse SRB.
2023-04-27 | E-MTAB-12239 | biostudies-arrayexpress
Project description:Zero-valent iron nanoparticles (nano-Fe0) in aqueous solution rapidly inactivated Escherichia coli. A strong bactericidal effect of nano-Fe0 was found under deaerated conditions, with a linear correlation between log inactivation and nano-Fe0 dose (0.82 log inactivation/mg/L nano-Fe0 x h). The inactivation of E. coli under air saturation required much higher nano-Fe0 doses due to the corrosion and surface oxidation of nano-Fe0 by dissolved oxygen. Significant physical disruption of the cell membranes was observed in E. coli exposed to nano-Fe0, which may have caused the inactivation or enhanced the biocidal effects of dissolved iron. The reaction of Fe(II) with intracellular oxygen or hydrogen peroxide also may have induced oxidative stress by producing reactive oxygen species. The bactericidal effect of nano-Fe0 was a unique property of nano-Fe0, which was not observed in other types of iron-based compounds.
| S-EPMC2536719 | biostudies-literature
Project description:Here we exploit the simple, ultra-stable, modular architecture of consensus-designed tetratricopeptide repeat proteins (CTPRs) to create a platform capable of displaying both single as well as multiple functions and with diverse programmable geometrical arrangements by grafting non-helical short linear binding motifs (SLiMs) onto the loops between adjacent repeats. As proof of concept, we built synthetic CTPRs to bind and inhibit the human tankyrase proteins (hTNKS), which play a key role in Wnt signaling and are upregulated in cancer. A series of mono-valent and multi-valent hTNKS binders was assembled. To fully exploit the modular scaffold and to further diversify the multi-valent geometry, we engineered the binding modules with two different formats, one monomeric and the other trimeric. We show that the designed proteins are stable, correctly folded and capable of binding to and inhibiting the cellular activity of hTNKS leading to downregulation of the Wnt pathway. Multivalency in both the CTPR protein arrays and the hTNKS target results in the formation of large macromolecular assemblies, which can be visualized both in vitro and in the cell. When delivered into the cell by nanoparticle encapsulation, the multivalent CTPR proteins displayed exceptional activity. They are able to inhibit Wnt signaling where small molecule inhibitors have failed to date. Our results point to the tremendous potential of the CTPR platform to exploit a range of SLiMs and assemble synthetic binding molecules with built-in multivalent capabilities and precise, pre-programmed geometries.
| S-EPMC7885266 | biostudies-literature
Project description:In contrast to molecular CO and CO2, their heavier mono- and dichalcogenide homologues, EX and EX2 (E = Si, Ge, Sn, Pb; X = O, S, Se, Te), are important support materials (e.g., SiO2) and/or semiconductors (e.g., SiS2) and exist typically as insoluble crystalline or amorphous polymers under normal conditions. Herein, we report the first successful synthesis and characterisation of an extraordinary series of isolable monomeric GeX and GeX2 complexes (X = S, Se, Te), representing novel classes of compounds and heavier congeners of CO and CO2. This could be achieved by solvent-dependent oxidation reactions of the new zero-valent germanium ('germylone')-GaCl3 precursor adduct (bis-NHC)Ge0?GaCl31 (bis-NHC = H2C[{NC(H)[double bond, length as m-dash]C(H)N(Dipp)}C:]2, Dipp = 2,6-iPr2C6H3) with elemental chalcogens, affording the donor-acceptor stabilised monomeric germanium(iv) dichalcogenide (bis-NHC)GeIV([double bond, length as m-dash]X)[double bond, length as m-dash]X?GaCl3 (X = S, 2; X = Se, 3) and germanium(ii) monochalcogenide complexes (bis-NHC)GeII[double bond, length as m-dash]X?GaCl3 (X = Se, 4; X = Te, 5), respectively. Moreover, the reactivity of 4 and 5 towards elemental sulphur, selenium, and tellurium has been investigated. In THF, the germanium(ii) monoselenide complex 4 reacts with activated elemental selenium to afford the desired germanium(iv) diselenide complex 3. Unexpectedly, both reactions of 4 and 5 with elemental sulphur, however, lead to the formation of germanium(iv) disulfide complex 2 under liberation of elemental Se and Te as a result of further oxidation of the germanium centre and replacement of the Se and Te atoms by sulphur atoms. All novel compounds 1-5 have been fully characterised, including single-crystal X-ray diffraction analyses, and studied by DFT calculations.
| S-EPMC6021755 | biostudies-literature