Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

How Does Pseudo-Jahn-Teller Effect Induce the Photoprotective Potential of Curcumin?

ABSTRACT: In this paper, the molecular and electronic structure of curcumin is studied. High-symmetric gas-phase tautomers and their deprotonated forms in various symmetry groups are identified. The stability of lower-symmetry structures was explained by using the Pseudo-Jahn-Teller (PJT) effect. This effect leads to stable structures of different symmetries for the neutral enol and keto forms. The presented analysis demonstrated the potential significance of the PJT effect, which may modulate the setting of electronic and vibrational (vibronic) energy levels upon photodynamic processes. The PJT effect may rationalize the photoprotection action and activity of naturally occurring symmetric dyes.

SUBMITTER: Stellerova D

PROVIDER: S-EPMC10096455 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

How Does Pseudo-Jahn-Teller Effect Induce the Photoprotective Potential of Curcumin?

Štellerová Dagmar D Lukeš Vladimír V Breza Martin M

Molecules (Basel, Switzerland) 20230325 7

In this paper, the molecular and electronic structure of curcumin is studied. High-symmetric gas-phase tautomers and their deprotonated forms in various symmetry groups are identified. The stability of lower-symmetry structures was explained by using the Pseudo-Jahn-Teller (PJT) effect. This effect leads to stable structures of different symmetries for the neutral enol and keto forms. The presented analysis demonstrated the potential significance of the PJT effect, which may modulate the setting ...[more]

PMID: 37049707

Similar Datasets

Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues.

Project description:We revealed the origin of the structural features of a series of tetrasilacyclobutadiene analogues based on a detailed study of their electronic structure and the pseudo Jahn-Teller effect (PJTE). Starting with the D4h symmetry of the Si4R4 system with a square four-membered silicon ring as a reference geometry, and employing ab initio calculations of energy profiles along lower-symmetry nuclear displacements in the ground and several excited states, we show that the ground-state boat-like and chair-like equilibrium configurations are produced by the PJT interaction with appropriate excited sates. For Si4F4 a full two-mode b1g-b2g adiabatic potential energy surface is calculated showing explicitly the way of transformation from the unstable D4h geometry to the two equilibrium C2h configurations via the D2h saddle point. The PJTE origin of these structural features is confirmed also by estimates of the vibronic coupling parameters. For Si4R4 with large substituents the origin of their structure is revealed by analyzing the PJT interaction between the frontier molecular orbitals. The preferred chair-like structures of Si4R4 analogues with amido substituents, and heavier germanium-containing systems Ge4R4 (potential precursors for semiconducting materials) are predicted.

| S-EPMC4800417 | biostudies-literature

On the Potential Role of the (Pseudo-) Jahn-Teller Effect in the Membrane Transport Processes: Enniatin B and Beauvericin.

Project description:The molecular structure of mycotoxins enniatin B and beauvericin, which are used as ionophores, was studied using density functional theory in various symmetry groups and singly charged states. We have shown that the charge addition or removal causes significant structural changes. Unlike the neutral C3 molecules, the stability of the charged C1 structures was explained by the Jahn-Teller or Pseudo-Jahn-Teller effect. This finding agrees with the available experimental X-ray structures of their metal complexes where electron density transfer from the metal can be expected. Hence, the membrane permeability of metal sandwich-structure complexes possessing antimicrobial activities is modulated by the conformational changes.

| S-EPMC10488337 | biostudies-literature

Pseudo-Jahn-Teller Effect in Natural Compounds and Its Possible Role in Straintronics I: Hypericin and Its Analogs.

Project description:The distortions and instability of high-symmetry configurations of polyatomic systems in nondegenerate states are usually ascribed to the pseudo-Jahn-Teller effect (PJTE). The geometries of hypericin, isohypericin, and fringelite D were optimized within various symmetry groups. Group-theoretical treatment and (TD-)DFT calculations were used to identify the corresponding electronic states during the symmetry descent. The symmetry descent paths (up to the stable structures without imaginary vibrations) were determined using the corresponding imaginary vibrations as their kernel subgroups starting from the highest possible symmetry group. The vibronic interaction between the ground and excited electronic states relates to an increasing energy difference of both states during the symmetry decrease. This criterion was used to identify possible PJTE. We have shown that the PJTE in these naturally occurring compounds could explain only the symmetry descent paths C2v → C2 and C2v → Cs in hypericin, and the D2h → C2v, D2h → C2v → C2, and D2h → C2h ones in fringelite D. The electric dipole moments of hypericin and its analogs were determined prevailingly by the mutual orientations of the hydroxyl groups. The same held for the energies of frontier orbitals in these systems, but their changes during the symmetry descent were less significant.

| S-EPMC11643763 | biostudies-literature

First-Principles Path Integral Monte Carlo Studies of the Pseudo Jahn-Teller Effect in the Aromatic Cyclo[10]carbon.

Project description:There has been renewed interest in carbon nanoscale structures. Experimental measurements at 4.7 K and subsequent first-principles-based vibrational diffusion Monte Carlo simulations at 0 K recently showed that the aromatic cyclo[10]carbon prefers a D5h pentagon-like structure to a regular D10h decagon. This symmetry breaking is due to the second-order Jahn-Teller effect (JTE) and has been amply described in the literature for the cumulenic cyclo[4m + 2]carbon clusters. Yet temperature dependence of the JTE in cyclo[4m + 2]carbon clusters in general and the cyclo[10]carbon in particular has not been studied systematically. In this work, we employ path integral Monte Carlo simulations on a first-principles-derived permutationally invariant potential energy surface (PES) to examine the JTE in cyclo[10]carbon as a function of temperature. The PES was trained on a set of τHCTH/cc-pVQZ energies sampled up to ∼7.7 eV above the D5h global minimum and locally adjusted to a high-level benchmark (reported by others) of the 812 cm-1 electronic energy difference between the D5h global minimum and the D10h transition state. The calculations show a strong JTE at lower temperatures with a dominant D5h composition at 100 K and a gradually diminishing JTE at higher temperatures with a washed-out pentagonal structure above 300 K.

| S-EPMC11891903 | biostudies-literature

Spin-orbit entanglement driven by the Jahn-Teller effect.

Project description:Spin-orbit entanglement in 4d and 5d transition metal systems can enhance electronic correlations, leading to nontrivial ground states and the emergence of exotic excitations. There is also an interest to investigate spin-orbit entanglement in 3d compounds, though this is challenging due to their smaller spin-orbit coupling. Here we demonstrate that the Jahn-Teller effect in Mn3+ reduces the energy gap between high- and low- spin-orbital states that lead to enhanced spin-orbit entanglement. Our results show a rare example of synergistic effects of Jahn-Teller and spin-orbit interactions and provide a way to entangle different degrees of freedom in d-metal oxides, which may allow paths to explore the interplay of orbital, lattice and spins in 3d correlated systems.

| S-EPMC11461866 | biostudies-literature

An orbital strategy for regulating the Jahn-Teller effect.

Project description:The Jahn-Teller effect (JTE) arising from lattice-electron coupling is a fascinating phenomenon that profoundly affects important physical properties in a number of transition-metal compounds. Controlling JT distortions and their corresponding electronic structures is highly desirable to tailor the functionalities of materials. Here, we propose a local coordinate strategy to regulate the JTE through quantifying occupancy in the [Formula: see text] and [Formula: see text] orbitals of Mn and scrutinizing the symmetries of the ligand oxygen atoms in MnO6 octahedra in LiMn2O4 and Li0.5Mn2O4. The effectiveness of such a strategy has been demonstrated by constructing P2-type NaLi x Mn1 - x O2 oxides with different Li/Mn ordering schemes. In addition, this strategy is also tenable for most 3d transition-metal compounds in spinel and perovskite frameworks, indicating the universality of local coordinate strategy and the tunability of the lattice-orbital coupling in transition-metal oxides. This work demonstrates a useful strategy to regulate JT distortion and provides useful guidelines for future design of functional materials with specific physical properties.

| S-EPMC11339606 | biostudies-literature

Spin-orbital Jahn-Teller bipolarons.

Project description:Polarons and spin-orbit (SO) coupling are distinct quantum effects that play a critical role in charge transport and spin-orbitronics. Polarons originate from strong electron-phonon interaction and are ubiquitous in polarizable materials featuring electron localization, in particular 3d transition metal oxides (TMOs). On the other hand, the relativistic coupling between the spin and orbital angular momentum is notable in lattices with heavy atoms and develops in 5d TMOs, where electrons are spatially delocalized. Here we combine ab initio calculations and magnetic measurements to show that these two seemingly mutually exclusive interactions are entangled in the electron-doped SO-coupled Mott insulator Ba2Na1-xCaxOsO6 (0 < x < 1), unveiling the formation of spin-orbital bipolarons. Polaron charge trapping, favoured by the Jahn-Teller lattice activity, converts the Os 5d1 spin-orbital Jeff = 3/2 levels, characteristic of the parent compound Ba2NaOsO6 (BNOO), into a bipolaron 5d2 Jeff = 2 manifold, leading to the coexistence of different J-effective states in a single-phase material. The gradual increase of bipolarons with increasing doping creates robust in-gap states that prevents the transition to a metal phase even at ultrahigh doping, thus preserving the Mott gap across the entire doping range from d1 BNOO to d2 Ba2CaOsO6 (BCOO).

| S-EPMC11258125 | biostudies-literature

Dynamic Jahn-Teller effect in the strong spin-orbit coupling regime.

Project description:Exotic quantum phases, arising from a complex interplay of charge, spin, lattice and orbital degrees of freedom, are of immense interest to a wide research community. A well-known example of such an entangled behavior is the Jahn-Teller effect, where the lifting of orbital degeneracy proceeds through lattice distortions. Here we demonstrate that a highly-symmetrical 5d1 double perovskite Ba2MgReO6, comprising a 3D array of isolated ReO6 octahedra, represents a rare example of a dynamic Jahn-Teller system in the strong spin-orbit coupling regime. Thermodynamic and resonant inelastic x-ray scattering experiments, supported by quantum chemistry calculations, undoubtedly show that the Jahn-Teller instability leads to a ground-state doublet, resolving a long-standing puzzle in this family of compounds. The dynamic state of ReO6 octahedra persists down to the lowest temperatures, where a multipolar order sets in, allowing for investigations of the interplay between a dynamic JT effect and strongly correlated electron behavior.

| S-EPMC11450152 | biostudies-literature

Jahn-Teller effects in Au25(SR)18.

Project description:The relationship between oxidation state, structure, and magnetism in many molecules is well described by first-order Jahn-Teller distortions. This relationship is not yet well defined for ligated nanoclusters and nanoparticles, especially the nano-technologically relevant gold-thiolate protected metal clusters. Here we interrogate the relationships between structure, magnetism, and oxidation state for the three stable oxidation states, -1, 0 and +1 of the thiolate protected nanocluster Au25(SR)18. We present the single crystal X-ray structures of the previously undetermined charge state Au25(SR)18+1, as well as a higher quality single crystal structure of the neutral compound Au25(SR)180. Structural data combined with SQUID magnetometry and DFT theory enable a complete description of the optical and magnetic properties of Au25(SR)18 in the three oxidation states. In aggregate the data suggests a first-order Jahn-Teller distortion in this compound. The high quality single crystal X-ray structure enables an analysis of the ligand-ligand and ligand-cluster packing interactions that underlie single-crystal formation in thiolate protected metal clusters.

| S-EPMC5965251 | biostudies-literature

Jahn-Teller distortion driven magnetic polarons in magnetite.

Project description:The first known magnetic mineral, magnetite, has unusual properties, which have fascinated mankind for centuries; it undergoes the Verwey transition around 120 K with an abrupt change in structure and electrical conductivity. The mechanism of the Verwey transition, however, remains contentious. Here we use resonant inelastic X-ray scattering over a wide temperature range across the Verwey transition to identify and separate out the magnetic excitations derived from nominal Fe2+ and Fe3+ states. Comparison of the experimental results with crystal-field multiplet calculations shows that the spin-orbital dd excitons of the Fe2+ sites arise from a tetragonal Jahn-Teller active polaronic distortion of the Fe2+O6 octahedra. These low-energy excitations, which get weakened for temperatures above 350 K but persist at least up to 550 K, are distinct from optical excitations and are best explained as magnetic polarons.

| S-EPMC5493765 | 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