Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Oxo-Replaced Polyoxometalates: There Is More than Oxygen.

ABSTRACT: The presence of oxo-ligands is one of the main required characteristics for polyoxometalates (POMs), although some oxygen ions in a metallic environment can be replaced by other nonmetals, while maintaining the POM structure. The replacement of oxo-ligands offers a valuable approach to tune the charge distribution and connected properties like reducibility and hydrolytic stability of POMs for the development of tailored compounds. By assessing the reported catalytic and biological applications and connecting them to POM structures, the present review provides a guideline for synthetic approaches and aims to stimulate further applications where the oxo-replaced compounds are superior to their oxo-analogues. Oxo-replacement in POMs deserves more attention as a valuable tool to form chemically activated precursors for the synthesis of novel structures or to upgrade established structures with extraordinary properties for challenging applications.

SUBMITTER: Breibeck J

PROVIDER: S-EPMC9732882 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Oxo-Replaced Polyoxometalates: There Is More than Oxygen.

Breibeck Joscha J Gumerova Nadiia I NI Rompel Annette A

ACS organic & inorganic Au 20220920 6

The presence of oxo-ligands is one of the main required characteristics for polyoxometalates (POMs), although some oxygen ions in a metallic environment can be replaced by other nonmetals, while maintaining the POM structure. The replacement of oxo-ligands offers a valuable approach to tune the charge distribution and connected properties like reducibility and hydrolytic stability of POMs for the development of tailored compounds. By assessing the reported catalytic and biological applications a ...[more]

PMID: 36510613

Similar Datasets

Polyoxometalates: more than a phasing tool in protein crystallography.

Project description:Protein crystallography is the most widely used method for determining the molecular structure of proteins and obtaining structural information on protein-ligand complexes at the atomic level. As the structure determines the functions and properties of a protein, crystallography is of immense importance for nearly all research fields related to biochemistry. However, protein crystallography suffers from some major drawbacks, whereby the unpredictability of the crystallization process represents the main bottleneck. Crystallization is still more or less a 'trial and error' based procedure, and therefore, very time and resource consuming. Many strategies have been developed in the past decades to improve or enable the crystallization of proteins, whereby the use of so-called additives, which are mostly small molecules that make proteins more amenable to crystallization, is one of the most convenient and successful methods. Most of the commonly used additives are, however, restricted to particular crystallization conditions or groups of proteins. Therefore, a more universal additive addressing a wider range of proteins and being applicable to a broad spectrum of crystallization conditions would represent a significant advance in the field of protein crystallography. In recent years, polyoxometalates (POMs) emerged as a promising group of crystallization additives due to their unique structures and properties. In this regard, the tellurium-centered Anderson-Evans polyoxotungstate [TeW6O24]6- (TEW) showed its high potential as crystallization additive. In this lecture text, the development of POMs as tools in protein crystallography are discussed with a special focus on the so far most successful cluster TEW.

| S-EPMC6294228 | biostudies-literature

Achieving deep desulfurization with inverse-micellar polyoxometalates and oxygen.

Project description:Designing green and efficient catalytic systems that can operate under mild conditions and utilize molecular oxygen as an oxidant for achieving deep desulfurization is highly desirable. In this study, an inverse-micellar polyoxometalate (POM) (NH4)5(CTA)6PMo4V8O40 (CTA = cetyltrimethylammonium), abbreviated as (CTA)PMo4V8, was designed and its activity in desulfurization was evaluated. Almost ∼100% of organic sulfur was removed in 8 h at 100 °C, using only flowing oxygen under atmospheric pressure. (CTA)PMo4V8 exhibited excellent activity in treating sulfur-containing compounds (dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (DMDBT), benzothiophene (BT) and thiophene) in real oils, i.e. diesel and FCC gasoline, affording clean oils with super-low sulfur content of 8.77 and 6.17 ppm, respectively. Furthermore, (CTA)PMo4V8 showed high activity in the oxidative desulfurization of real oils in the presence of oxygen and nitrogen (volume ratio 1 : 1). Such inverse-micellar POMs could be reused at least six times without significant loss of activity due to their high stability.

| S-EPMC8695393 | biostudies-literature

Boosting Oxygen Reduction Reaction Selectivity in Metal Nanoparticles with Polyoxometalates.

Project description:The lack of selectivity toward the oxygen reduction reaction (ORR) in metal nanoparticles can be linked to the generation of intermediates. This constitutes a crucial constraint on the performance of specific electrochemical devices, such as fuel cells and metal-air batteries. To boost selectivity of metal nanoparticles, a novel methodology that harnesses the unique electrocatalytic properties of polyoxometalates (POM) to scavenge undesired intermediates of the ORR (such as HO2 -) promoting selectivity is proposed. It involves the covalent functionalization of metal nanoparticle's surface with an electrochemically active capping layer containing a new sulfur-functionalized vanadium-based POM (AuNP@POM). To demonstrate this approach, preformed thiolate Au(111) nanoparticles with a relatively poor ORR selectivity are chosen. The dispersion of AuNP@POM on the surface of carbon nanofibers (CNF) enhances oxygen diffusion, and therefore the ORR activity. The resulting electrocatalyst (AuNP@POM/CNF) exhibits superior stability against impurities like methanol and a higher pH tolerance range compared to the standard commercial Pt/C. The work demonstrates for the first time, the use of a POM-based electrochemically active capping layer to switch on the selectivity of poorly selective gold nanoparticles, offering a promising avenue for the preparation of electrocatalyst materials with improved selectivity, performance, and stability for ORR-based devices.

| S-EPMC11672175 | biostudies-literature

REPLACED BY GSE136256

Project description:The data for this Series have been removed by request of the submitter. The submitter states that the data had compromised quality and the replicates were inconsistent due to the biological replicates.

2025-01-01 | GSE106132 | GEO

REPLACED by GSE232887

Project description:This dataset has been replaced by SuperSeries GSE232887.

2024-01-05 | GSE160127 | GEO

REPLACED BY GSE136256

Project description:REPLACED BY GSE136256

| PRJNA415907 | ENA

Electrochemical oxo-functionalization of cyclic alkanes and alkenes using nitrate and oxygen.

Project description:Direct functionalization of C(sp3)-H bonds allows rapid access to valuable products, starting from simple petrochemicals. However, the chemical transformation of non-activated methylene groups remains challenging for organic synthesis. Here, we report a general electrochemical method for the oxidation of C(sp3)-H and C(sp2)-H bonds, in which cyclic alkanes and (cyclic) olefins are converted into cycloaliphatic ketones as well as aliphatic (di)carboxylic acids. This resource-friendly method is based on nitrate salts in a dual role as anodic mediator and supporting electrolyte, which can be recovered and recycled. Reducing molecular oxygen as a cathodic counter reaction leads to efficient convergent use of both electrode reactions. By avoiding transition metals and chemical oxidizers, this protocol represents a sustainable oxo-functionalization method, leading to a valuable contribution for the sustainable conversion of petrochemical feedstocks into synthetically usable fine chemicals and commodities.

| S-EPMC10382549 | biostudies-literature

Probing the Viability of Oxo-Coupling Pathways in Iridium-Catalyzed Oxygen Evolution.

Project description:A series of Cp*IrIII dimers have been synthesized to elucidate the mechanistic viability of radical oxo-coupling pathways in iridium-catalyzed O2 evolution. The oxidative stability of the precursors toward nanoparticle formation and their oxygen evolution activity have been investigated and compared to suitable monomeric analogues. We found that precursors bearing monodentate NHC ligands degraded to form nanoparticles (NPs), and accordingly their O2 evolution rates were not significantly influenced by their nuclearity or distance between the two metals in the dimeric precursors. A doubly chelating bis-pyridine-pyrazolide ligand provided an oxidation-resistant ligand framework that allowed a more meaningful comparison of catalytic performance of dimers with their corresponding monomers. With sodium periodate (NaIO4) as the oxidant, the dimers provided significantly lower O2 evolution rates per [Ir] than the monomer, suggesting a negative interaction instead of cooperativity in the catalytic cycle. Electrochemical analysis of the dimers further substantiates the notion that no radical oxyl-coupling pathways are accessible. We thus conclude that the alternative path, nucleophilic attack of water on high-valent Ir-oxo species, may be the preferred mechanistic pathway of water oxidation with these catalysts, and bimolecular oxo-coupling is not a valid mechanistic alternative as in the related ruthenium chemistry, at least in the present system.

| S-EPMC3902142 | biostudies-literature

DELETED - Replaced by GSE280037

Project description:This Series has been replaced by GSE280037.

2024-10-12 | GSE263217 | GEO

Mechanistic insight into oxygen atom transfer reactions by mononuclear manganese(IV)-oxo adducts.

Project description:High-valent metal-oxo intermediates are well known to facilitate oxygen-atom transfer (OAT) reactions both in biological and synthetic systems. These reactions can occur by a single-step OAT mechanism or by a stepwise process initiated by rate-limiting electron transfer between the substrate and the metal-oxo unit. Several recent reports have demonstrated that changes in the metal reduction potential, caused by the addition of Brønsted or Lewis acids, cause a change in sulfoxidation mechanism of MnIV-oxo complexes from single-step OAT to the multistep process. In this work, we sought to determine if ca. 4000-fold rate variations observed for sulfoxidation reactions by a series of MnIV-oxo complexes supported by neutral, pentadentate ligands could arise from a change in sulfoxidation mechanism. We examined the basis for this rate variation by performing variable-temperature kinetic studies to determine activation parameters for the reactions of the MnIV-oxo complexes with thioanisole. These data reveal activation barriers predominantly controlled by activation enthalpy, with unexpectedly small contributions from the activation entropy. We also compared the reactivity of these MnIV-oxo complexes by a Hammett analysis using para-substituted thioanisole derivatives. Similar Hammett ρ values from this analysis suggest a common sulfoxidation mechanism for these complexes. Because the rates of oxidation of the para-substituted thioanisole derivatives by the MnIV-oxo adducts are much faster than that expected from the Marcus theory of outer-sphere electron-transfer, we conclude that these reactions proceed by a single-step OAT mechanism. Thus, large variations in sulfoxidation by this series of MnIV-oxo centers occur without a change in reaction mechanism.

| S-EPMC8075156 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data