Adrià Gil Mestres


    Ongoing Projects

  • Computational design of bioactive organometallic complexes for catalytic processes involving nucleotides: Medical applications

  • mcm01

    Since the incorporation of cisplatin in chemotherapy treatments for cancer, the interest in the application of transition metal systems in medicine has grown rapidly. One step beyond was the incorporation of phenanthroline (phen) in metal complexes, these systems showing significant antitumoral activity. Within the interactions of coordination complexes with DNA, intercalation is an important binding mode and the intercalative capacity of molecules is influenced by the planarity of ligand, type of donor atom, and metal coordination geometry. Several drug delivery systems have been devised to increase selectivity in chemotherapy. Recent studies show that phen and its derivatives bind directly to the G-quadruplexes inhibiting telomerase activity. Pt and Zn complexes with phen and some π-extended derivatives have been prepared and showed to stabilize G-quadruplexes, hence exhibiting cytotoxicity towards tumor cells lines. Given the interest in using these systems for a range of medical applications, the knowledge of their interactions with DNA becomes important. Thus the main objectives of this project are the comprehension and rationalization of the interaction of phen coordination complexes in processes involving DNA strands (regular and G-quadruplex) by means of computational techniques.

    This line of research has collaborations with:

    Vicenç Branchadell, Universitat Autònoma de Barcelona
    Manuel Melle-Franco, Universidade do Minho (Braga)
    Antonio Monari, SRSMC Université de Lorraine – Nancy et CNRS

  • Promotion of phosphoester hydrolysis by Mo(VI) complexes and polyoxometalates. Computational design of artificial phosphoesterases

  • mcm01

    In absence of any catalyst or enzyme, phosphoeter hydrolysis may be extremely slow under normal conditions. The study of the acceleration of the phosphoester bond cleavage mechanism results interesting for the degradation treatment of organophoshate pesticides, and also for the application of some drugs with antitumor activity better than cisplatin. Molybdenum seems a promising metal and derivatives such as metal complexes and polyoxometalates (POMs) have been found good promoters of such hydrolysis. Since Mo is an essential trace element for organisms, plays a crucial role as cofactor for enzymes, and is transported and excreted as [MoO4]2-, its low toxicity and its effects on metabolism should make possible the use of Mo coordination complexes and POMs as artificial phosphoesterases. Nevertheless, the application of POMs in medicine has some drawbacks because of their unstability in water at physiological pH and their toxicity. Thus many efforts focused on the modification of their shape, composition, polarity, redox potential, surface charge distribution, and acidity in order to find new POMs with higher physiological stability, higher biological activity and lower toxicity. Thus, this project aims at the comprehension and rationalization of the interaction of metal complexes and POMs in processes involving the phosphodiester bond hydrolysis mechanism, by means of computational techniques.

    This line of research has collaborations with:

    Marta Abrantes, Instituto Superior Técnico (Lisboa)

  • Simulation of Mössbauer spectroscopy parameters for complexes containing Fe(II)

  • mcm01

    Mössbauer spectroscopy probes tiny changes in the energy levels of an atomic nucleus in response to its environment. However, the use of this technique is limited to some of the elements of the periodic table. In the case of transition metals, Fe is one of these active elements and Mössbauer spectra have become part of the characterization of ferrocenes and other complexes containing iron. The development of computational methodologies in recent years has led to more accurate ways of calculating characteristic Mössbauer parameters such as the isomer shift or the quadrupole splitting. In this line of research, we try to calculate such parameters for several systems containing Fe(II) or Fe(III) by means of computational chemistry in order to explain and give some insight to the experimental evidence.

    This line of research has collaborations with:

    Karl Kirchner, Institut für Angewandte Synthesechemie – Technische Universität Wien
    Maria de Deus Carvalho and Liliana Ferreira, CQB – Universidade de Lisboa

  • Determination of the structure of pyrochlores in Portuguese Azulejos (tiles)

  • mcm01

    Azulejo panels decorating many buildings and public spaces are one of the most important touristic attractions when visiting Portugal. In fact, azulejos are considered the most important historic Portuguese decorative art, having been used without interruption for more than five centuries. Despite the importance of the azulejo heritage, relatively few scientific studies concerning their materials have been published. This line of research aims at the use of computational chemistry to complement other analytical techniques in the identification of the pigments and pigment mixtures based on pyrochlores that are used to produce the colors of azulejos.

    This line of research has collaborations with:

    Solange Muralha, Universidade Nova de Lisboa

  • Theoretical studies of reaction mechanisms arising from electron induced decomposition of biomolecules probed in potassium collision processes

  • mcm01

    This line of research aims at the study of reaction mechanisms involving the cleavage of (bio)molecules that takes place in potassium collision processes. Radical anions are experimentally produced by means of electron transfer from potassium atoms to the (bio)chemical samples. Because of the nature of the experimental technique, we take into account all the possible pathways that can be obtained in an energy window up to 5 eV and try to give some insight on the nature of the peaks recorded in the mass spectra. Taking into account the experimental and theoretical information, we deduce the energy profiles and propose the mechanisms for these processes.

    This line of research has collaborations with:

    Filipe Ferreira da Silva and Paulo Limão-Vieira, CEFITEC – Universidade Nova de Lisboa.

    Academic training

  • PhD in Theoretical and Computacional Chemistry, Universitat Autònoma de Barcelona - 2006

  • Master in Theoretical and Computational Chemistry, Universitat Autònoma de Barcelona - 2003

  • Certificate for pedagogical aptitude (C. A. P), Institut de ciències de l’Educació (I. C. E.), Universitat Rovira i Virgili (Tarragona) - 1999

  • Chemistry degree, Universitat Rovira i Virgili (Tarragona) - 1999

  • Scientific/professional positions

  • Postdoctoral position. Centro de Química e Bioquímica. Facultade de Ciências. Universidade de Lisboa, 2013 - Present

  • Postdoctoral position and teaching assistant. Institute de Chimie des Milieux et Matériaux de Poitiers (IC2MP), UMR 7285 CNRS. Université de Poitiers, 2012

  • Postdoctoral position. Institut Català d'Investigació Química (ICIQ), 2010 - 2012

  • Postdoctoral position. Laboratoire de Catalyse en Chimie Organique, UMR 6503 CNRS. Université de Poitiers, 2010

  • Postdoctoral position. Cluster of Excellence Engineering of Advanced Materials / Computer Chemie Centrum, Friedrich-Alexander-Universität Erlangen-Nürnberg, 2009

  • Postdoctoral position. Laboratoire de Catalyse en Chimie Organique, UMR 6503 CNRS. Université de Poitiers, 2008

  • Postdoctoral position. Laboratoire de Chimie. école Normale Supérieure de Lyon, 2007 - 2008

  • Teaching assistant. Unitat de Química Física. Departament de Química. Facultat de ciències. Universitat Autònoma de Barcelona, 2001 - 2005

  • Support and training research grant. Grup d'Estructura i Reactivitat Química. Unitat de Química Física. Departament de Química. Facultat de ciències. Universitat Autònoma de Barcelona, 2001 - 2002

  • Support and training research grant. Grup de Química Quàntica. Departament de Química Física i Química Inorgànica. Facultat de Química. Universitat Rovira i Virgili, (Tarragona), 1999 - 2000

  • Publications

  • 22.Holzhacker, C.; Stöger, B.; Carvalho, M. D.; Ferreira, L. P; Pittenauer, E.; Allmaier, G.; Veiros, L. F.; Realista, S.; Gil, A.; Calhorda, M. J.; Müller, D.; Kirchner, K.* Synthesis and Reactivity of Taddol-Based Chiral Fe(II) PNP Pincer Complexes –Solution Equilibria between k2P,N- and k3P,N,P-Bound PNP Pincer LigandsDalton Trans 2015, 44, 13071

  • 21.Gil, A.*; Melle-Franco, M.; Branchadell, V.; Calhorda, M. J.* How the Intercalation of Phenanthroline Affects the Structure, Energetics and Bond Properties of DNA Base Pairs. Theoretical Study Applied to Adenine-Thymine and Guanine-Cytosine TetramersJ. Chem. Theory Comput. 2015, 11, 2714

  • 20.Valencia, H.; Gil, A.*; Frapper, G.* Trends in the Hydrogen Activation and Storage by Adsorbed 3D Transition Metal Atoms onto Graphene and Nanotube Surfaces: A DFT Study and Molecular Orbital AnalysisJ. Phys. Chem. C 2015, 119, 5506

  • 19.Holzhacker, C.; Calhorda, M. J.; Gil, A.; Carvalho, M. D.; Ferreira, L. P.; Mereiter, K.; Stöger, B.; Pittenauer, E.; Allmaier, G.; Kirchner, K.* Four- and five-coordinate high-spin iron (II) complexes bearing bidentate soft/hard SN ligands based on 2-aminopyridine. Polyhedron 2014, 81, 45 11

  • 18.Holzhacker, C.; Calhorda, M. J.; Gil, A.; Carvalho, M. D.; Ferreira, L. P.; Godinho, M.; Stöger, B.; Mereiter, K.; Weil, M.; Müller, D.; Weinberger, P.; Pittenauer, E.; Allmaier, G.; Kirchner, K. Six-Coordinate High Spin Iron(II) Complexes with Bidentate PN Ligands based on 2-Aminopyridine – New Fe(II) Spin Crossover Systems. Dalton Trans., 2014, 43, 11152

  • 17.Tiferet, E.; Gil, A.; Bo, C.; Shvareva, T. Y.; Nyman, M.; Navrotsky, A. The Energy Landscape of Uranyl Peroxide Species. Chem.-Eur. J., 2014, 20, 3646

  • 16.Kopilevich, S.; Gil, A.; Garcia-Ratés, M.; Bonet Avalos, J.; Bo, C.; Müller, A.; Weinstock, I. A. Catalysis in a Porous Molecular Capsule: Activation by Regulated Access to Sixty Metal Centers Spanning a Truncated Icosahedron. J. Am. Chem. Soc., 2012, 134, 13082

  • 15.Gil, A.; Karhánek, D.; Miró, P.; Antonio, M. R.; Nyman, M.; Bo, C. A journey inside U28 nanocapsule. Chem.-Eur. J., 2012, 18, 8340

  • 14.Deguil, J.; Pineau, L.; Snyder, E. C. R.; Dupont, S.; Beney, L.; Gil, A.; Frapper, G.; Ferreira, T. Modulation of lipid-induced ER stress by fatty acid shape. Traffic, 2011, 12(3) 349

  • 13.Delatouche, R.; Mondon, M.; Gil, A.; Frapper, G.; Bachmann, C.; Bertrand, P. Novel triazolyl derivatives for acidic release of amines. Tetrahedron, 2011, 67(2), 401

  • 12.Miró, P.; Pierrefixe, S.; Gicquel, M.; Gil, A.; Bo, C. On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters. J. Am. Chem. Soc., 2010, 132(50) 17787

  • 11.Valencia, H.; Gil, A.; Frapper, G. Trends in the Adsorption of 3d Transition Metal Atoms onto Graphene and Nanotube Surfaces: A DFT Study and Molecular Orbital Analysis. J. Phys. Chem. C, 2010, 114(33), 14141

  • 10.Gil, A.; Branchadell, V.; Bertran, J.; Oliva, A. An analysis of the Different Behavior of DNA and RNA through the Study of the Mutual Relationship between Stacking and Hydrogen Bonding. J. Phys. Chem. B, 2009, 113, 4907

  • 9.Gil, A.; Sodupe, M.; Bertran, J. Influence of ionisation on the conformational preferences of peptide models. Ramachandran surfaces of N-formyl-glycine amide and N-formyl-alanine amide radical cations. J. Comput. Chem., 2009, 30(12), 1771

  • 8.Gil, A.; Simon, S.; Sodupe. M.; Bertran. J. How the site of ionisation influences side-chain fragmentation in histidine radical cations. Chem. Phys. Lett., 2008, 451, 276

  • 7.Gil, A.; Simon, S.; Rodríguez-Santiago, L.; Bertran, J.; Sodupe, M. Influence of the side chain in the structure and fragmentation of amino acid radical cations. J. Chem. Theory Comput., 2007, 3, 2210

  • 6.Gil, A.; Simon, S.; Sodupe, M.; Bertran, J. Gas-phase proton-transport self-catalysed isomerisation of glutamine radical cation. The important role of the side-chain. Theor. Chem. Acc., 2007, 118, 589

  • Gil, A.; Branchadell, V.; Bertran, J.; Oliva, A. The CH/π Interactions in DNA and Proteins. A Theoretical Study. J. Phys. Chem. B, 2007, 111, 9372

  • 5.Horrillo-Martínez, P.; Hultzsch, K. C.; Gil, A.; Branchadell, V. Base-Catalyzed Anti-Markovnikov Hydroamination of Vinylarenes – Scope, Limitations and Computational Studies. Eur. J. Org. Chem., 2007, 3311

  • 4.Gil, A.; Bertran, J.; Sodupe, M. Effects of ionization on N-glycylglycine peptide: Influence of intramolecular hydrogen bonds. J. Chem. Phys., 2006, 124, 154306

  • 3.Simon, S.; Gil, A.; Sodupe, M.; Bertran, J. Structure and fragmentation of glycine, alanine, serine and cysteine radical cations. A theoretical study. J. Mol. Struct. (THEOCHEM), 2005, 727, 191

  • 2.Gil, A.; Sodupe, M.; Bertran, J. Unusual hydrogen bonds in [AH3-H3O]+ radical cations (A = C, Si, Ge, Sn and Pb). Single-electron hydrogen bond, proton-hydride hydrogen bond and formation of [H2AOH2-H2]+ complexes. Chem. Phys. Lett., 2004, 395, 27

  • 1.Gil, A.; Sodupe, M.; Bertran, J. Gas Phase Dissociation Energies of Saturated AHn+ Radical Cations and AHn Neutrals (A = Li-F, Na-Cl): Dehydrogenation, Deprotonation, and Formation of AHn-2+ - H2 Complexes. J. Am. Chem. Soc., 2003, 125(24), 7461