How does microhydration impact on structure, spectroscopy and formation of disulfide radical anions? An ab initio investigation on dimethyldisulfide

Geronimo, Inacrist; Chéron, Nicolas; Fleurat‐Lessard, Paul; Dumont, Élise

doi:10.1016/j.cplett.2009.09.079

Cited by 8 publications

(14 citation statements)

References 33 publications

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“…The drastic ring strain indeed leads to a mixing of MOs, as discussed by Maity on disulfide radical cations 31 ], the slope in eq 2 implies that considerable blue or red shifts can be achieved, since hemibonded systems are highly malleable. 10,32 For convenience, one can propose a rule of thumb to estimate them, with a deviation of 46 nm per 0.1 Å knowing that λ max ref = 436 nm for d = 2.79 Å. At this stage, we have evidenced a clear geometrical dependence on a constrained prototypical disulfide RA.…”

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confidence: 83%

Intersulfur Distance Is a Key Factor in Tuning Disulfide Radical Anion Vertical UV−Visible Absorption

Dumont

Laurent

Assfeld

2010

J. Phys. Chem. Lett.

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International audienceMaximum absorption wavelengths λmax for σ* ← σ vertical transition of peptidic disulfide radical anions of increasing complexity were investigated by means of time-dependent density functional theory. Values among a representative set of 17 two-cysteinyl peptides range between 385 and 624 nm (TD-BH&HLYP/DZP++//MP2/DZP++:HF/6-31G* level of theory). This considerable spread contrasts with the usually admitted value of ca. 400−450 nm typically ascribed to two-center three-electron bonds. It is traced back to the large range of equilibrium intersulfur distances d, with values comprised between 2.73 and 3.19 Å. More quantitatively, blue- and red-shifts follow a near-linear regime (slope of 46 nm per 0.1 Å). They can be mapped onto a relaxed scan of l,l-cystine taken as a prototypical system λmaxref = 436 nm, 2.79 Å. This result could assist future radioprotectants rational design, with disulfide-linking arcs of controlled geometry. Meanwhile, the presence of a secondary structure motif such as an α-helix does not affect the UV−vis transition

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mentioning

confidence: 83%

Intersulfur Distance Is a Key Factor in Tuning Disulfide Radical Anion Vertical UV−Visible Absorption

Dumont

Laurent

Assfeld

2010

J. Phys. Chem. Lett.

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“…Such an analysis involves three relevant descriptors: adiabatic electron affinity (AEA), inter-sulfur distance d SS , and longest wavelength of maximal absorption k max . However, we established a nearly linear dependence between the two latter properties [31,6], and only AEA and d SS are considered in this Letter.…”

Section: Introductionmentioning

confidence: 93%

Performances of recently-proposed functionals for describing disulfide radical anions and similar systems

Dumont

Laurent

Assfeld

et al. 2011

Chemical Physics Letters

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“…It is important to consider that a balance between solute–water and w–w interactions determines the structure of a hydrated organic complex. In this regard, Geronimo et al have recently introduced a ratio to measure semi–quantitatively the competitive formation of solute–water and inter-water H-bonds network in hydrogen-bonded hydrated complexes defined as scriptH = normalΔ E − normalΔ E normals − normalw + E def − normalc + E def − normalw normalΔ E where E def–c and E def–w are deformation energies (one per subclusters), which correspond to the energy difference between the frozen geometry within the microhydrated complexes and the absolute geometry minimum for each monomer. The E def–w for each complex is the sum of the individual deformation energy of the n water in it.…”

Section: Methods and Calculation Detailsmentioning

confidence: 99%

Preferential Formation of the Different Hydrogen Bonds and Their Effects in Tetrahydrofuran and Tetrahydropyran Microhydrated Complexes

Vallejos

Peruchena

2012

J. Phys. Chem. A

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The role of cycloether-water (c-w) and water-water (w-w) hydrogen bonds (H-bonds) on the stability of the tetrahydrofuran THF/(H(2)O)(n) and the tetrahydropyran THP/(H(2)O)(n) complexes with n = 1-4 was investigated herein using the density functional and ab initio methods and the atoms in molecules theory. Geometry optimizations for these complexes were carried out with various possible initial guess structures. It was revealed that the major contributions of the mono and dihydrated complexes came from c-w H-bonds. A competition between c-w and w-w H-bonds contribution was observed for trihydrated complexes. For most of tetrahydrated complexes, the inter-water H-bonds provided the greatest contribution, whereas the c-w contributions were small but not negligible. It was confirmed that to produce a hydrophobic hydration of cycloethers, the C-H···O(w) H-bond should be associated with a network of H-bonds that connects both portions of the solute, through the formation of a bifunctional H-bond. A linear correlation is obtained for the sum of electron density at the bond critical points (ρ(b)) with the interaction energy (ΔE) and with the solute-solvent interaction energy (ΔE(s-w)) of the microhydrated complexes. In addition, a new way to estimate the energetic contribution as well as the preferential formation of the different H-bonds based completely on ρ(b) was found. Even more, it allows to differentiate the contribution from c-w interactions in both hydrophilic and hydrophobic contributions, it is therefore a useful tool for studying the hydration of large biomolecules. The analysis of the modifications in the atomic and group properties brought about by successive addition of H(2)O molecules allowed to pinpoint the atoms or molecular groups that undergo the greatest changes in electron population and energetic stabilization. It was identified that the remarkable stabilization of the water oxygen atoms is crucial for the stabilization of the complexes.

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How does microhydration impact on structure, spectroscopy and formation of disulfide radical anions? An ab initio investigation on dimethyldisulfide

Cited by 8 publications

References 33 publications

Intersulfur Distance Is a Key Factor in Tuning Disulfide Radical Anion Vertical UV−Visible Absorption

Intersulfur Distance Is a Key Factor in Tuning Disulfide Radical Anion Vertical UV−Visible Absorption

Performances of recently-proposed functionals for describing disulfide radical anions and similar systems

Preferential Formation of the Different Hydrogen Bonds and Their Effects in Tetrahydrofuran and Tetrahydropyran Microhydrated Complexes

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