Browsing by Author "Jaque, Pablo"
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- Item5-HT2 Receptor Subfamily and the Halogen Bond Promise(2021) Fierro, Angelica; Matthies, Douglas J.; Cassels, Bruce K.; Jaque, Pablo; Zapata-Torres, GeraldThe binding of C-4-halogenated 1-(4-X-2,5-dimethoxyphenyl)-2-aminopropane (DOX) serotonin agonist psychedelics at all three 5-HT2 receptor subtypes is up to two orders of magnitude stronger for X = Cl, Br, or I (but not F) than when C-4 bears a hydrogen atom and more than expected from their hydrophobicities. Our docking and molecular dynamics simulations agree with the fact that increasing the polarizability of halogens results in halogen-oxygen distances to specific backbone C=O groups, and C-X center dot center dot center dot O angles, in ranges expected for halogen bonds (XBs), which could contribute to the high affinities observed. Good linear correlations are found for each receptor type, indicating that the binding pocketl-igand affinity is enhanced as the XB interaction becomes stronger (i.e., I approximate to Br > Cl > F). It is also striking to note how the linear equations unveil that the receptor's response on the strength of the XB interaction is quite similar among 5-HT2A and 5-HT2C, whereas the 5-HT2B's sensitivity is less. The calculated dipole polarizabilities in the binding pocket of the receptors reflect the experimental affinity values, indicating that less-polarizable and harder binding sites are more prone to XB formation.
- ItemCan electrophilicity act as a measure of the redox potential of first-row transition metal ions?(WILEY-V C H VERLAG GMBH, 2007) Moens, Jan; Roos, Goedele; Jaque, Pablo; De Proft, Frank; Geerlings, PaulPrevious contributions concerning the computational approach to redox chemistry have made use of thermodynamic cycles and Car-Parrinello molecular dynamics simulations to obtain accurate redox potential values, whereas this article adopts a conceptual density functional theory (DFT) approach. Conceptual DFT descriptors have found widespread use in the study of thermodynamic and kinetic aspects of a variety of organic and inorganic reactions. However, redox reactions have not received much attention until now. In this contribution, we prove the usefulness of global and local electrophilicity descriptors for the prediction of the redox characteristics of first row transition metal ions (from Sc3+vertical bar Sc2+ to Cu3+vertical bar Cu2+) and introduce a scaled definition of the electrophilicity based on the number of electrons an electrophile ideally accepts. This scaled electrophilicity concept acts as a good quantitative estimate of the redox potential. We also identify the first solvation sphere together with the metal ion as the primary active region during the electron uptake process, whereas the second solvation sphere functions as a non-reactive continuum region.
- ItemCCDC 1051038: Experimental Crystal Structure Determination(2015) Perez, Patricia; Yepes, Diana; Jaque, Pablo; Chamorro, Eduardo; Domingo, Luis R; Rojas, Rene S; Toro Labbe, Alejandro Miguel
- ItemCCDC 1051039: Experimental Crystal Structure Determination(2015) Perez, Patricia; Yepes, Diana; Jaque, Pablo; Chamorro, Eduardo; Domingo, Luis R; Rojas, Rene S; Toro Labbe, Alejandro Miguel
- ItemCCDC 1051040: Experimental Crystal Structure Determination(2015) Perez, Patricia; Yepes, Diana; Jaque, Pablo; Chamorro, Eduardo; Domingo, Luis R; Rojas, Rene S; Toro Labbe, Alejandro Miguel
- ItemThe study of redox reactions on the basis of conceptual DFT principles: EEM and vertical quantities(AMER CHEMICAL SOC, 2008) Moens, Jan; Jaque, Pablo; De Proft, Frank; Geerlings, PaulIn this article, two new approaches are introduced which describe redox reactions through descriptors defined within the field of conceptual density functional theory (DFT). One approach starts with the grand canonical ensemble DFT from which a formula is derived for the chemical potential of the electrode in terms of intrinsic properties of oxidized and reduced states of the electroactive species. Second, starting from a Born-Haber scheme, the redox potential is solely expressed in terms of the vertical electron affinity and ionization potential of oxidized and reduced species, respectively. A large collection of 44 organic and inorganic systems are studied in different solvents including implicit and explicit solvation models. Both strategies seem well capable of reproducing experimental values of redox potentials.