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Authordc.contributor.authorMartínez Cifuentes, Maximiliano 
Authordc.contributor.authorWeiss López, Boris es_CL
Authordc.contributor.authorSantos, Leonardo S. es_CL
Authordc.contributor.authorAraya Maturana, Ramiro es_CL
Cita de ítemdc.identifier.citationMolecules 2014, 19, 9354-9368en_US
Identifierdc.identifier.otherDOI: 10.3390/molecules19079354
General notedc.descriptionArtículo de publicación ISIen_US
Abstractdc.description.abstractIntramolecular hydrogen bonds (IHBs) play a central role in the molecular structure, chemical reactivity and interactions of biologically active molecules. Here, we study the IHBs of seven related o-carbonyl hydroquinones and one structurally-related aromatic lactone, some of which have shown anticancer and antioxidant activity. Experimental NMR data were correlated with theoretical calculations at the DFT and ab initio levels. Natural bond orbital (NBO) and molecular electrostatic potential (MEP) calculations were used to study the electronic characteristics of these IHB. As expected, our results show that NBO calculations are better than MEP to describe the strength of the IHBs. NBO energies (ΔEij (2)) show that the main contributions to energy stabilization correspond to LPσ* interactions for IHBs, O1 …O2-H2 and the delocalization LPπ* for O2-C2 = Cα(β). For the O1 …O2-H2 interaction, the values of ΔEij (2) can be attributed to the difference in the overlap ability between orbitals i and j (Fij), instead of the energy difference between them. The large energy for the LP O2π* C2 = Cα(β) interaction in the compounds 9-Hydroxy-5-oxo-4,8, 8-trimethyl-l,9(8H)-anthracenecarbolactone (VIII) and 9,10-dihydroxy- 4,4-dimethylanthracen-1(4H)-one (VII) (55.49 and 60.70 kcal/mol, respectively) when compared with the remaining molecules (all less than 50 kcal/mol), suggests that the IHBs in VIII and VII are strongly resonance assisted.en_US
Patrocinadordc.description.sponsorshipWe are grateful to FONDECYT grants 1140753, FONDECYT/POSTDOCTORADO 3140286 (M.M-C) and ACT grant 1107.en_US
Type of licensedc.rightsAttribution-NonCommercial-NoDerivs 3.0 Chile*
Link to Licensedc.rights.uri*
Títulodc.titleIntramolecular hydrogen bond in biologically active o-carbonyl hydroquinonesen_US
Document typedc.typeArtículo de revistaen_US

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Except where otherwise noted, this item's license is described as Attribution-NonCommercial-NoDerivs 3.0 Chile