Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency.

ABSTRACT: The spin-spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are largely investigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer, or multiple spin labeling in structural biology. Recently, 2,2,6,6-tetramethylpiperidinyloxyl and polymers functionalized with nitroxides have been described as successful redox mediators in several electrochemical applications; however, the study of spin-spin interaction effect in such an area is absent. This communication reports the preparation of a novel family of discrete polynitroxide molecules, with the same number of radical units but different arrangements to study the effect of intramolecular spin-spin interactions on their electrochemical potential and their use as oxidation redox mediators in a Li-oxygen battery. We find that the intensity of interactions, as measured by the d₁/d electron paramagnetic resonance parameter, progressively lowers the reduction potential. This allows us to tune the charging potential of the battery, optimizing its energy efficiency.

SUBMITTER: Badetti E

PROVIDER: S-EPMC8011802 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Intramolecular hydrophobic interactions are critical mediators of STAT5 dimerization.

Project description:STAT5 is an essential transcription factor in hematopoiesis, which is activated through tyrosine phosphorylation in response to cytokine stimulation. Constitutive activation of STAT5 is a hallmark of myeloid and lymphoblastic leukemia. Using homology modeling and molecular dynamics simulations, a model of the STAT5 phosphotyrosine-SH2 domain interface was generated providing first structural information on the activated STAT5 dimer including a sequence, for which no structural information is available for any of the STAT proteins. We identified a novel intramolecular interaction mediated through F706, adjacent to the phosphotyrosine motif, and a unique hydrophobic interface on the surface of the SH2 domain. Analysis of corresponding STAT5 mutants revealed that this interaction is dispensable for Epo receptor-mediated phosphorylation of STAT5 but essential for dimer formation and subsequent nuclear accumulation. Moreover, the herein presented model clarifies molecular mechanisms of recently discovered leukemic STAT5 mutants and will help to guide future drug development.

| S-EPMC5067585 | biostudies-literature

Redox mediators in visible light photocatalysis: photocatalytic radical thiol-ene additions.

Project description:Synthetically useful radical thiol-ene reactions can be initiated by visible light irradiation in the presence of transition metal polypyridyl photocatalysts. The success of this method relies upon the use of p-toluidine as an essential additive. Using these conditions, high-yielding thiol-ene reactions of cysteine-containing biomolecules can be accomplished using biocompatibile wavelengths of visible light, under aqueous conditions, and with the thiol component as the limiting reagent. We present evidence that p-toluidine serves as a redox mediator that is capable of catalyzing the otherwise inefficient photooxidation of thiols to the key thiyl radical intermediate. Thus, we show that co-catalytic oxidants can be important in the design of synthetic reactions involving visible light photoredox catalysis.

| S-EPMC3985841 | biostudies-literature

Redox-Addressable Single-Molecule Junctions Incorporating a Persistent Organic Radical.

Project description:Integrating radical (open-shell) species into non-cryogenic nanodevices is key to unlocking the potential of molecular electronics. While many efforts have been devoted to this issue, in the absence of a chemical/electrochemical potential the open-shell character is generally lost in contact with the metallic electrodes. Herein, single-molecule devices incorporating a 6-oxo-verdazyl persistent radical have been fabricated using break-junction techniques. The open-shell character is retained at room temperature, and electrochemical gating permits in situ reduction to a closed-shell anionic state in a single-molecule transistor configuration. Furthermore, electronically driven rectification arises from bias-dependent alignment of the open-shell resonances. The integration of radical character, transistor-like switching, and rectification in a single molecular component paves the way to further studies of the electronic, magnetic, and thermoelectric properties of open-shell species.

| S-EPMC9322687 | biostudies-literature

High-efficiency color-tunable ultralong room-temperature phosphorescence from organic-inorganic metal halides <i>via</i> synergistic inter/intramolecular interactions.

Project description:Materials exhibiting highly efficient, ultralong and multicolor-tunable room-temperature phosphorescence (RTP) are of practical importance for emerging applications. However, these are still very scarce and remain a formidable challenge. Herein, using precise structure design, several novel organic-inorganic metal-halide hybrids with efficient and ultralong RTP have been developed based on an identical organic cation (A). The original organic salt (ACl) exhibits red RTP properties with low phosphorescence efficiency. However, after embedding metals into the organic salt, the changed crystal structure endows the resultant metal-halide hybrids with excellent RTP properties. In particular, A2ZnCl4·H2O exhibits the highest RTP efficiency of up to 56.56% with a long lifetime of up to 159 ms. It is found that multiple inter/intramolecular interactions and the strong heavy-atom effect of the rigid metal-halide hybrids can suppress molecular motion and promote the ISC process, resulting in highly stable and localized triplet excitons followed by highly efficient RTP. More crucially, multicolor-tunable fluorescence and RTP achieved by tuning the metal and halogen endow these materials with wide application prospects in the fields of multilevel information encryption and dynamic optical data storage. The findings promote the development of phosphorescent metal-halide hybrids for potential high-tech applications.

| S-EPMC11220578 | biostudies-literature

The lightest organic radical cation for charge storage in redox flow batteries.

Project description:In advanced electrical grids of the future, electrochemically rechargeable fluids of high energy density will capture the power generated from intermittent sources like solar and wind. To meet this outstanding technological demand there is a need to understand the fundamental limits and interplay of electrochemical potential, stability, and solubility in low-weight redox-active molecules. By generating a combinatorial set of 1,4-dimethoxybenzene derivatives with different arrangements of substituents, we discovered a minimalistic structure that combines exceptional long-term stability in its oxidized form and a record-breaking intrinsic capacity of 161?mAh/g. The nonaqueous redox flow battery has been demonstrated that uses this molecule as a catholyte material and operated stably for 100 charge/discharge cycles. The observed stability trends are rationalized by mechanistic considerations of the reaction pathways.

| S-EPMC4997354 | biostudies-literature

Boosting the efficiency of organic persistent room-temperature phosphorescence by intramolecular triplet-triplet energy transfer.

Project description:Persistent luminescence is a fascinating phenomenon with exceptional applications. However, the development of organic materials capable of persistent luminescence, such as organic persistent room-temperature phosphorescence, lags behind for their normally low efficiency. Moreover, enhancing the phosphorescence efficiency of organic luminophores often results in short lifetime, which sets an irreconcilable obstacle. Here we report a strategy to boost the efficiency of phosphorescence by intramolecular triplet-triplet energy transfer. Incorpotation of (bromo)dibenzofuran or (bromo)dibenzothiophene to carbazole has boosted the intersystem crossing and provided an intramolecular triplet-state bridge to offer a near quantitative exothermic triplet-triplet energy transfer to repopulate the lowest triplet-state of carbazole. All these factors work together to contribute the efficient phosphorescence. The generation and transfer of triplet excitons within a single molecule is revealed by low-temperature spectra, energy level and lifetime investigations. The strategy developed here will enable the development of efficient phosphorescent materials for potential high-tech applications.

| S-EPMC6453937 | biostudies-literature

Tunable intramolecular multicenter H-bonding interactions in first-row metal complexes bearing bidentate redox-active ligands.

Project description:In this research article, we report the synthesis and structural characterization of a family of first-row metal complexes bearing redox-active ligands with tunable H-bonding donors. We observed that these coordination complexes can adopt three different geometries and that they are stabilized by intramolecular multicenter H-bonding interactions, which are systematically modified by changing the metal ion (Co, Ni, Cu, Zn), the ligand scaffold (variations in the diamine and ureanyl substituents used) and the solvent of crystallization.

| S-EPMC8188844 | biostudies-literature

Unconventional Kondo effect in redox active single organic macrocyclic transistors.

Project description:Cyclo[6]- and cyclo[8]pyrrole, two aromatic expanded porphyrins, were studied in a single-molecule transistor (SMT) setup. The analyses of these compounds allowed us to observe an uncommon absence of an even-odd effect in the Kondo resonance in discrete, metal-free organic macrocyclic compounds. The findings from the SMT measurements of these cyclopyrroles were in accord with those from cyclic voltammetry (CV) studies and theoretical analyses. These findings provide support for the notion that SMT measurements could be useful as a tool for the characterization of similar types of aromatic macrocyclic compounds.

| S-EPMC3227745 | biostudies-literature

Intramolecular Hydrogen Atom Transfer in Aminyl Radical at Room Temperature with Large Kinetic Isotope Effect.

Project description:We report a large kinetic isotope effect at 298 K, kH/kD ? 150, associated with an intramolecular 1,5-hydrogen atom transfer (1,5-HAT) in the decay of a PEGylated carbazyl (aminyl) radical in solution. The experimental observations surprisingly combine the hallmarks of tunneling, including large KIEs and unusual activation parameters, with linear Arrhenius and Eyring plots over an exceptionally wide temperature range of 116 K.

| S-EPMC5528148 | biostudies-literature

Redox-Induced Gating of the Exchange Interactions in a Single Organic Diradical.

Project description:Embedding a magnetic electroactive molecule in a three-terminal junction allows for the fast and local electric field control of magnetic properties desirable in spintronic devices and quantum gates. Here, we provide an example of this control through the reversible and stable charging of a single all-organic neutral diradical molecule. By means of inelastic electron tunnel spectroscopy we show that the added electron occupies a molecular orbital distinct from those containing the two radical electrons, forming a spin system with three antiferromagnetically coupled spins. Changing the redox state of the molecule therefore switches on and off a parallel exchange path between the two radical spins through the added electron. This electrically controlled gating of the intramolecular magnetic interactions constitutes an essential ingredient of a single-molecule [Formula: see text] quantum gate.

| S-EPMC5492214 | 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