A Bioinspired Molybdenum Catalyst for Aqueous Perchlorate Reduction

Ren, Changxu; Yang, Peng; Sun, Jiaonan; Bi, Eric; Gao, Jinyu; Palmer, Jacob; Zhu, Mengqiang; Wu, Yiying; Liu, Jinyong

doi:10.1021/jacs.1c00595

Cited by 32 publications

(49 citation statements)

References 38 publications

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“…Different mechanisms such as CO-oxidation, light-harvesting complexes to sequester energy is very important for heterotrophs inside sabkha subjected to extreme saline environment, which impose extra costs for osmoregulation. This is also consistent with the noticeable presence of perchlorate reduction on the inside more than outside as well as more Chlorite reduction for these groups, which is an evidence for plausible microbe reaction on Martian brines and the reaction will emit oxygen, which will strongly contribute to facilitating the process of Mars colonization 66 , 67 .…”

Section: Discussionsupporting

confidence: 82%

Salt flat microbial diversity and dynamics across salinity gradient

Hazzouri

Sudalaimuthuasari

Saeed

et al. 2022

Sci Rep

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Sabkhas are hypersaline, mineral-rich, supratidal mudflats that harbor microbes that are adapted to high salt concentration. Sabkha microbial diversity is generally studied for their community composition, but less is known about their genetic structure and heterogeneity. In this study, we analyzed a coastal sabkha for its microbial composition using 16S rDNA and whole metagenome, as well as for its population genetic structure. Our 16S rDNA analysis show high alpha diversity in both inner and edge sabkha than outer sabkha. Beta diversity result showed similar kind of microbial composition between inner and edge sabkha, while outer sabkha samples show different microbial composition. At phylum level, Bacteroidetes (~ 22 to 34%), Euryarchaeota (~ 18 to ~ 30%), unclassified bacteria (~ 24 to ~ 35%), Actinobacteria (~ 0.01 to ~ 11%) and Cyanobacteria (less than 1%) are predominantly found in both inside and edge sabkha regions, whereas Proteobacteria (~ 92 to ~ 97%) and Parcubacteria (~ 1 to ~ 2%) are predominately found in outer sabkha. Our 225 metagenomes assembly from this study showed similar bacterial community profile as observed in 16S rDNA-based analysis. From the assembled genomes, we found important genes that are involved in biogeochemical cycles and secondary metabolite biosynthesis. We observed a dynamic, thriving ecosystem that engages in metabolic activity that shapes biogeochemical structure via carbon fixation, nitrogen, and sulfur cycling. Our results show varying degrees of horizontal gene transfers (HGT) and homologous recombination, which correlates with the observed high diversity for these populations. Moreover, our pairwise population differentiation (Fst) for the abundance of species across the salinity gradient of sabkhas identified genes with strong allelic differentiation, lower diversity and elevated nonsynonymous to synonymous ratio of variants, which suggest selective sweeps for those gene variants. We conclude that the process of HGT, combined with recombination and gene specific selection, constitute the driver of genetic variation in bacterial population along a salinity gradient in the unique sabkha ecosystem.

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Section: Discussionsupporting

confidence: 82%

Salt flat microbial diversity and dynamics across salinity gradient

Hazzouri

Sudalaimuthuasari

Saeed

et al. 2022

Sci Rep

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“…When it comes to molybdenum-containing systems, there is only a very early report of molybdate-catalyzed perchlorate reduction in the presence of stannous chloride in highly acidic solutions and a recent communication on a heterogeneous Mo-Pd/C catalyst. However, no bioinspired homogeneous catalyst capable of perchlorate reduction has been published so far. , …”

Section: Introductionmentioning

confidence: 99%

“…However, no bioinspired homogeneous catalyst capable of perchlorate reduction has been published so far. 20,21 Molybdenum(VI) complexes containing pyrimidine-and pyridine-2-thiolate ligands have lately been used as bioinspired oxygen atom transfer (OAT) catalysts by our group 22 and others. 23,24 Particularly, [MoO 2 (PymS) 2 ] (1, PymS = pyrimidine-2-thiolate) and [MoO 2 (6-MePyS) 2 ] (2, 6-MePyS = 6-methylpyridine-2-thiolate) turned out to be quite active catalysts for this kind of reaction (Figure 2).…”

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confidence: 99%

Nature-Inspired Homogeneous Catalytic Perchlorate Reduction Using Molybdenum Complexes

et al. 2021

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Inspired by the reactivity of (per)chlorate reducing molybdoenzymes and encouraged by the lack of molybdenum-containing functional models thereof, two molybdenum(VI) complexes of the type [MoO 2 L 2 ] (L = pyrimidine-2-thiolate or 6methylpyridine-2-thiolate) were found to be active homogeneous catalysts for the reduction of ClO 4 − to ClO 3 − in CH 2 Cl 2 using PPh 3 as sacrificial oxygen acceptor. The subsequent stepwise reduction of ClO 3 − to Cl − is facilitated by our catalysts, but it can also proceed with only PPh 3 without the aid of a catalyst. We followed the decrease in perchlorate concentration in the catalytic solutions not only indirectly by oxidation of PPh 3 to OPPh 3 via 1 H NMR spectroscopy but also directly by determining the perchlorate concentration at certain time points over 24 h with high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICPMS/MS). These experiments revealed the pyrimidine-2-thiolate system to be more efficient. The reduction of ClO 4 − to ClO 3 − with [MoOL 2 ], which is generated after the reaction of [MoO 2 L 2 ] with PPh 3 , was computed to be highly exergonic with low kinetic barriers for both catalysts. Thus, the rate-determining step of the overall catalytic reaction is the initial oxygen atom transfer from [MoO 2 L 2 ] to PPh 3 .

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“…Addressing perchlorate reduction, the Mösch-Zanetti group put a lot of effort into investigating homogenous catalysts with rhenium as metal center using the hoz ligand system (Figure 11c) initially developed by Abu-Omar et al and further applied different tetradentate iminophenolate ligands together with molybdenum, which resulted in the first bioinspired homogenous molybdenum catalysts supported by PymS and PyS ligands (Figure 11d), respectively [25,26,130,135]. Additionally, reports in the literature exist of molybdenum-based heterogeneous catalysts on Pd/C platforms for aqueous (per)chlorate reduction; however, this falls beyond the scope of this review [136][137][138].…”

Section: Non-dithiolene Complexesmentioning

confidence: 99%

Inspired by Nature—Functional Analogues of Molybdenum and Tungsten-Dependent Oxidoreductases

et al. 2022

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Throughout the previous ten years many scientists took inspiration from natural molybdenum and tungsten-dependent oxidoreductases to build functional active site analogues. These studies not only led to an ever more detailed mechanistic understanding of the biological template, but also paved the way to atypical selectivity and activity, such as catalytic hydrogen evolution. This review is aimed at representing the last decade’s progress in the research of and with molybdenum and tungsten functional model compounds. The portrayed systems, organized according to their ability to facilitate typical and artificial enzyme reactions, comprise complexes with non-innocent dithiolene ligands, resembling molybdopterin, as well as entirely non-natural nitrogen, oxygen, and/or sulfur bearing chelating donor ligands. All model compounds receive individual attention, highlighting the specific novelty that each provides for our understanding of the enzymatic mechanisms, such as oxygen atom transfer and proton-coupled electron transfer, or that each presents for exploiting new and useful catalytic capability. Overall, a shift in the application of these model compounds towards uncommon reactions is noted, the latter are comprehensively discussed.

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A Bioinspired Molybdenum Catalyst for Aqueous Perchlorate Reduction

Cited by 32 publications

References 38 publications

Salt flat microbial diversity and dynamics across salinity gradient

Salt flat microbial diversity and dynamics across salinity gradient

Nature-Inspired Homogeneous Catalytic Perchlorate Reduction Using Molybdenum Complexes

Inspired by Nature—Functional Analogues of Molybdenum and Tungsten-Dependent Oxidoreductases

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