Anion–π Interactions in Flavoproteins Involve a Substantial Charge‐Transfer Component

Yurenko, Yevgen P.; Bazzi, Sophia; Marek, Radek; Kozelka, Jiřı́

doi:10.1002/chem.201605307

Cited by 18 publications

(17 citation statements)

References 36 publications

(62 reference statements)

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“…Finally, it is customary to reference, that London dispersion forces is a crucial component of intramolecular dihydrogen bonding C−H⋅⋅⋅H−C in addition to charge delocalization contribution . The importance of the latter term in other untypical anion‐π interactions has been also recognized . To further reference, an excellent review on homopolar dihydrogen contacts in hydrogen storage materials is available in Ref.…”

Section: Resultsmentioning

confidence: 99%

Origin of Hydrocarbons Stability from a Computational Perspective: A Case Study of Ortho‐Xylene Isomers

et al. 2020

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It is shown herein that intuitive and text‐book steric‐clash based interpretation of the higher energy “in‐in” xylene isomer (as arising solely from the repulsive CH⋅⋅⋅HC contact) with respect to the corresponding global‐minimum “out‐out” configuration (where the clashing C−H bonds are tilted out) is misleading. It is demonstrated that the two hydrogen atoms engaged in the CH⋅⋅⋅HC contact in “in‐in” are involved in attractive interaction so they cannot explain the lower stability of this isomer. We have proven, based on the arsenal of modern bonding descriptors (EDDB, HOMA, NICS, FALDI, ETS‐NOCV, DAFH, FAMSEC, IQA), that in order to understand the relative stability of “in‐in” versus “out‐out” xylenes isomers one must consider the changes in the electronic structure encompassing the entire molecules as arising from the cooperative action of hyperconjugation, aromaticity and unintuitive London dispersion plus charge delocalization based intra‐molecular CH⋅⋅⋅HC interactions.

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Section: Resultsmentioning

confidence: 99%

Origin of Hydrocarbons Stability from a Computational Perspective: A Case Study of Ortho‐Xylene Isomers

et al. 2020

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“…The interaction energies computed using a triple‐zeta polarized Slater‐type basis set from the ADF library follow the same trends as the bond dissociation energies in Table . Analysis of the ZR‐EDA energy components unveils some general trends: 1) in all cationic complexes the orbital interaction is large, and for nonpolar graphane flakes it is the dominant energy component; and 2) among anionic systems, fluoride complexes benefit from the electrostatic term far more than their chloride and bromide counterparts, yet the orbital interaction is the main driving force for bond formation . ZR‐EDA reveals that the interplay between orbital interaction energy, electrostatics, and Pauli repulsion is responsible for the observed trends in the anion and cation affinities of G‐FF and G‐MeMe (see Supporting Information for description).…”

Section: Resultsmentioning

confidence: 94%

Anti‐Electrostatic CH–Ion Bonding in Decorated Graphanes

Novák

Marek

Foroutan‐Nejad

2017

Chemistry A European J

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State-of-the-art computations combined with Ziegler-Rauk energy decomposition analyses are employed to introduce a new class of anti-electrostatic ion-σ bonds with considerable stability and a substantial contribution from charge transfer and dispersion between ions and finite-size functionalized graphane flakes, G-XYs. G-XYs have diverse electric multipolar moments that are comparable with those of newly synthesized all-cis-hexa-halocyclohexanes. The strong, long-range electrostatic and Pauli repulsions between some G-XYs and certain ions induce a gas-phase energy barrier to the physisorption of ions on the surface of G-XYs. However, the repulsive interactions can be overbalanced by the strong orbital interactions operating in the formation of ion-σ complexes at short range, leading to covalent-type intermolecular bonds as strong as -34 kcal mol .

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“…Among all noncovalent interactions related to aromatic rings, anion-π interactions received the most attention in the last few years. Due to their significant role in aforementioned supramolecular chemistry [4][5][6][7], crystal engineering [8][9][10][11] and structural biology [12][13][14][15], these interactions became a subject of great interest. Anion-π, also referred to as anion-quadrupole, interactions are theorized to form between aromatic groups and anions.…”

Section: Introductionmentioning

confidence: 99%

“…Using the systematic search of protein structures followed by ab initio calculations, Deyà and co-workers showed that anion-π interactions are to be expected in flavin-dependent enzymes [18]. Anion-π interactions have been shown to stabilize flavoproteins and to regulate the redox potential of the flavin cofactor [15]. In addition, Moore and co-workers examined high-resolution structures of proteins and nucleic acids for the presence of " 6 "-type anion-π contacts, where the anion is placed directly above the centre of the six-membered ring [12].…”

Section: Introductionmentioning

confidence: 99%

Anion–π interactions in active centers of superoxide dismutases

Ribić

Stojanović

Zlatović

2018

International Journal of Biological Macromolecules

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We investigated 1060 possible anion-π interactions in a data set of 41 superoxide dismutase active centers. Our observations indicate that majority of the aromatic residues are capable to form anion-π interactions, mainly by long-range contacts, and that there is preference of Trp over other aromatic residues in these interactions. Furthermore, 68% of total predicted interactions in the dataset are multiple anion-π interactions. Anion-π interactions are distance and orientation dependent. We analyzed the energy contribution resulting from anion-π interactions using ab initio calculations. The results showed that, while most of their interaction energies lay in the range from -0 to -4kcalmol, those energies can be up to -9kcalmol and about 34% of interactions were found to be repulsive. Majority of the suggested anion-π interacting residues in ternary complexes are metal-assisted. Stabilization centers for these proteins showed that all the six residues found in predicted anion-π interactions are important in locating one or more of such centers. The anion-π interacting residues in these proteins were found to be highly conserved. We hope that these studies might contribute useful information regarding structural stability and its interaction in future designs of novel metalloproteins.

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Anion–π Interactions in Flavoproteins Involve a Substantial Charge‐Transfer Component

Cited by 18 publications

References 36 publications

Origin of Hydrocarbons Stability from a Computational Perspective: A Case Study of Ortho‐Xylene Isomers

Origin of Hydrocarbons Stability from a Computational Perspective: A Case Study of Ortho‐Xylene Isomers

Anti‐Electrostatic CH–Ion Bonding in Decorated Graphanes

Anion–π interactions in active centers of superoxide dismutases

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