Bruno Martínez Haya Profesor Titular in Physical Chemistry    Department of Physical, Chemical and  Natural Systems Universidad Pablo de Olavide 41013 Seville, Spain. tel: +34-954-977562, fax: +34-954-349814 bmarhayupo.es
LASER SPECTROSCOPY MASS SPECTROMETRY GROUP Lines of Research (click on them for details): - Mass Spectrometry of Biomolecules and Polymers   - Laser Spectroscopy of Ionic Complexes   - Dynamics of Elementary and Photoinitiated Reactions - Statistical Mechanics of Molecular Fluids
Members of the Group Bruno Martínez Haya Profesor Titular bmarhayupo.es Ana Rodríguez Hortal    Postdoctoral researcher arodhorupo.es Paola Hurtado Castillo    Ph.D. research fellow  pmhurcasupo.es Francisco Gámez Márquez    Ph.D. research fellow  fgammarupo.es
MALDI-TOF and ESI-Ion Trap Mass Spectrometry of Biomolecules and Polymers
MALDI-TOF PROTEOMICS Our laboratory is equipped with an UltrafleXtreme MALDI-TOF/TOF and a HCT ESI-Ion Trap spectrometer from Bruker Daltonics. Both spectrometers can be coupled either on-line or off-line with a nano-LC chromatography system. MALDI-imaging of tissues and surfaces, providing chemical mapping with a resolution of tens of microns is also possible. We aim at providing solutions to problems in proteomics, lipidomics, genomics and metabolomics. For further information contact us by email or check the web page of the MALDI-TOF Proteomics facility
Development of MALDI-TOF methods Complementary to the (bio)analytical applications, we are strongly interested in developing novel MALDI methods. We have tested different sample preparation methods, based on solvent-free approaches, as well as on ionic liquid matrices. In addition, we are exploring the use of metal and semiconductor nanoparticles to assist the laser desorption/ionization of different types of analytes. We have been investigating different families of molecules, mainly biomolecules (peptides, oligosaccharides), synthetic polymers, triazinic pesticides and asphaltene extracts from crude oils. We collaborate in this field with our colleague Juan Antonio Anta, with Luis Bañares (Universidad Complutense de Madrid, Spain), Marta Castillejo (CSIC, Madrid, Spain), Klaus Dreisewerd (University of Münster, Germany), Oliver C. Mullins (Schlumberger-Doll Research, USA), and others.
Selected publications in the field of Laser spectroscopy and mass spectrometry: “Platinum Nanoparticles Prepared by Laser Ablation in Aqueous Solutions: Fabrication and Application to Laser Desorption Ionization” M. Cueto, M. Sanz,, M. Oujja, F. Gámez, Bruno Martínez-Haya, M. Castillejo, Journal of Physical Chemistry C, (2011) doi: 10.1021/jp207324h "One-step and two-step ultraviolet and infrared laser desorption ionization mass spectrometry of asphaltenes" P. Hurtado,  F. Gámez, B. Martínez-Haya, Energy & Fuels, 24 (2010) 6067-6073. "Nanoparticle TiO2 films prepared by pulsed laser deposition: laser desorption and cationization of model adsorbates" F. Gámez, A. Plaza-Reyes, P. Hurtado, E. Guillén, J.A. Anta, B. Martínez-Haya, S. Pérez, M. Sanz, M. Castillejo, J.G. Izquierdo, L. Bañares, Journal of Physical Chemistry C, 114 (2010) 17409-17415. "UV-vis-NIR laser desorption/ionization of synthetic polymers assisted by gold nanospheres, nanorods and nanostars" F. Gámez, P. Hurtado,  P.M. Castillo, C. Caro, A. R. Hortal, P. Zaderenko, B. Martínez-Haya, Plasmonics, 5 (2010) 125. "Solvent-free MALDI investigation of the cationization of linear polyethers with alkali metals" A. R. Hortal, P. Hurtado, B. Martínez-Haya, A. Arregui, L. Bañares, Journal of Physical Chemistry B, 112 (2008) 8530-8535. "Contrasting perspective on asphaltene molecular weight; this Comment vs. the Overview of A.A. Herod, K.D. Bartle, R. Kandiyoti" O.C. Mullins, B. Martínez-Haya, A.G. Marshall, Energy & Fuels, 22 (2008) 1765-1773. "Matrix-Assisted Laser Desorption Mass Spectrometry of gas-phase Peptide-Metal Complexes" A.R. Hortal, P. Hurtado, B. Martínez-Haya, Applied Physics A 93 (2008) 935-939 "Poly(ethylene glycol) cationization with alkali metals in matrix-assisted laser desorption ionization investigated with the solvent-free method" A.R. Hortal, P. Hurtado, B. Martínez-Haya, A. Arregui, L. Bañares, Applied Physics A 92 (2008) 859-863 "Fragmentation and gas phase aggregation processes in the laser desorption ionization of chlorodiamino-triazines" P. Hurtado, A.R. Hortal, M. Cruz-Guzmán, B. Martínez-Haya, European Journal of Mass Spectrometry13 (2007) 321-329. "MALDI detection of carbonaceous compounds in ionic liquid matrices" P. Hurtado, A.R. Hortal, B. Martínez-Haya, Rapid Communications in Mass Spectrometry 21 (2007) 3161-3164. "Molecular-weight distributions of coal and petroleum asphaltenes from laser desorption/ionization experiments" A.R.Hortal, P.Hurtado, B. Martínez-Haya, O.C. Mullins, Energy & Fuels 21 (2007) 2863-2868. "Laser desorption/ionization determination of molecular weight distributions of polyaromatic carbonaceous compounds and their aggregates"  B. Martínez-Haya, A.R. Hortal, P. Hurtado, M. Lobato, J.M. Pedrosa, Journal of Mass Spectrometry, 42 (2007) 701-713. "Characterization and Langmuir film properties of asphaltenes extracted from Arabian light crude oil" M. Lobato, J.M. Pedrosa, A.R. Hortal, B. Martínez-Haya, S. Lago,  Colloid & Surfaces A, 298 (2007) 72-79. "On the determination of molecular weight distributions of asphaltenes and their aggregates in laser desorption ionization experiments" A.R. Hortal, B. Martínez-Haya, M. Lobato, J.M. Pedrosa, S. Lago,  Journal of Mass Spectrometry, 41 (2006) 960-968
Laser Spectroscopy of Cationic Complexes of Biomolecular and Astrophysical interest
By combining MALDI and ESI to bring supramolecular ions to the gas phase, with molecular beam and laser spectroscopic techniques (resonant IR multiple photon dissociation, REMPI), we are currently investigating non-covalent aggregation and molecular recognition processes on model cationic systems. We have partivularly extensively investigated the conformational features of the inclusion complexes formed by crown ethers and cyclodextrins with alkali metal cations and protonated species, such as H3O^+, NH4^+, amines and aminoacids.  We are currently developing an ion-trapping system for the spectroscopic investigation of ionic complexes at low temperature. To interrogate the trapped ions, we have two Nd:YAG-pumped Dye laser systems which provide tunable pulsed laser radiation in the range 220-480nm, and an infrared OPO/OPA laser system producing tunable laser pulses within the 1.5-15 micron range. We collaborate in this field with Javier Aoiz (Universidad Complutense de Madrid, Spain), Stephan Schlemmer (University of Cologne, Germany), Jos Oomens (FOM, Holland), and others.
Selected publications in the field of Laser spectroscopy: "Vibrational study of isolated 18-crown-6 ether complexes with alkaline-earth metal cations" F. Gámez, P. Hurtado,  B. Martínez-Haya, G. Berden, J. Oomens, International Journal of Mass Spectrometry, 308 (2011) 217-224 "Crown Ether Complexes with H3O^+ and NH4^+: Proton Localization and Proton Bridge Formation" P. Hurtado,  F. Gámez, S. Hamad, B. Martínez-Haya, J.D. Steill, J. Oomens, Journal of Physical Chemistry A, 115 (2011) 7275-7282 "Gas phase complexes of cyclic and linear polyethers with alkali cations" P. Hurtado, A.R. Hortal, F. Gámez, S. Hamad, B. Martínez-Haya, Physical Chemistry Chemical Physics 12 (2010) 13752-13758. "Emergence of Symmetry and Chirality in Crown ether complexes with alkali metal cations" B. Martínez-Haya, P. Hurtado,  A.R. Hortal, S. Hamad, J.D. Steill, J. Oomens, Journal of Physical Chemistry A, 114 (2010)  7048-7054. "Spectroscopic investigation of the gas-phase conformations of 15-crown-5 ether complexes with K^+" B. Martínez-Haya, P. Hurtado,  A. R. Hortal, J.D. Steill, J. Oomens, P.J. Merkling, Journal of Physical Chemistry A, 113 (2009) 7748-7752. Selected for the issue cover.
Elementary and Photoinitated Reaction Dynamics
This is mostly old work that I initiated with my Ph.D. project (1992-96), supervised by Prof. J.P. Toennies at the Max-Planck Institut für Strömungsforschung (Max-Planck Institute for Fluid Dynamics) in the city of Göttingen (Germany) . The different topics addressed have been the following ones: - High resolution crossed molecular beam investigation of the elementary reaction F + H2. Determination of absolute differential state-to-state cross sections for the HF products. Dependence on initial rotation of the hydrogen molecule. These are the Göttingen experiments. - Laser Multiphoton Ionization (REMPI-TOF and velocity-map ion-imaging) study of the photodissociation of organosulfides and other methylated molecules (e.g., ICH3, CH3SCH3, CH3S2CH3), and the rotational relaxation of molecules (N2, CO, H2)  in supersonic expansions. Experiments performed during my postdoctoral stay (1997-1999) in the lab of Javier Aoiz at the Physical Chemistry Department of the Universidad Complutense de Madrid, and as Royal Society visiting scientist in the lab of Mark Brouard (Oxford, England). - Quantum and quasiclassical theoretical Reaction Dynamics investigations. Determination of scalar observables, such as state-to-state differential and integral cross sections or rate constants, and vectorial properties (polarization dependent cross sections) characterising the stereodynamics of the reaction. The chemical systems investigated are three-atom and four-atom bechmark gas-phase reactions. These are a few examples:   H+H2 , F+H2 , O+H2 and, more recently, Cl+O3.
Selected publications in the field of Elementary Reaction Dynamics: "Theoretical study of the dynamics of Cl+O3 reaction I. Ab initio potential energy surface and quasiclassical trajectory results" J.F. Castillo, F.J. Aoiz, B. Martnez-Haya Physcial Chemistry Chemical Physics,13 (2011) 8537-8548 "Quasiclassical determination of reaction probabilities as a function of the total angular momentum" F.J. Aoiz, V.Sáez-Rábanos, B.Martínez-Haya, T.González-Lezana, Journal Chemical Physics, 123 (2005)  094101. "Photodissociation and Multiphoton Dissociative Ionisation Processes in CH3S2CH3 at 193 nm Studied using Velocity-map Imaging" B. Martínez-Haya, M.J. Bass, M. Brouard, C. Vallance, I. Torres, J. Barr. Journal of Chemical Physics, 120 (2004)  p.11042 "Angular momentum alignment of Cl(^2P3/2) in the 308 nm photolysis of Cl2 determined using Fourier moment velocity-map imaging" M.J. Bass,  M. Brouard, A.P. Clark, C. Vallance and B. Martínez-Haya, Physical Chemistry Chemical Physics, 5 (2003) p. 856 "The photodissociation of CH3SCH3 and CD3SCD3 at 220--231nm investigated by velocity map ion imaging" B. Martínez-Haya, P. Quintana, L. Bañares , P. Samartzis, D.J. Smith,  T.N. Kitsopoulos, Journal of Chemical Physics, 114 (2001)  p. 4450. "The Low Temperature Rotational Relaxation of N2 studied with Resonance Enhanced Multiphoton Ionization" F.J. Aoiz, T. Díez Rojo, V.J. Herrero, B. Martínez-Haya, M. Menéndez, P. Quintana, L. Ramonat, I. Tanarro and E. Verdasco, Journal of Physical Chemistry, 103 (1999) p.823 "Rotational State Resolved Differential Cross Sections for the Reaction F+D2>DF+D at Collision Energies 140-240 meV" M.Faubel, B.Martínez-Haya, L.Y. Rusin, U. Tappe, J.P.Toennies, F.J.Aoiz and L.Bañares. Journal of Physical Chemistry, 102 (1998) p.8695. "State-to-state differential cross sections for the reaction F+D2 at 90meV: a crossed molecular beam experiment and a quantum mechanical study" M. Baer, M. Faubel, B. Martínez-Haya, L.Y. Rusin, U. Tappe y J.P. Toennies. Journal of Chemichal Physics, 108 (1998) p.9694 "Elastic and Rotationally Inelastic Scattering of Fluorine Atoms by Deuterium Molecules at 112meV Collision Energy" M. Ayabakan, M. Faubel, B. Martínez-Haya, L.Y. Rusin, M.B. Sevryuk, U. Tappe, J.P. Toennies. Chemical Physics 229 (1998) 21 "Quantum mechanical and Quasi-classical Simulations of Molecular Beam Experiments for the F+H2>HF+H Reaction on two ab initio potential energy surfaces" J.F. Castillo, B. Hartke, H.J. Werner, F.J. Aoiz, L. Bañares and B. Martínez-Haya. Journal of Chemical Physics, 109 (1998) 7224. "Experimental Absolute Cross Sections for the Reaction F+D2 at Collision Energies 90-240meV" M. Faubel, B.Martínez-Haya, L.Y.Rusin, U.Tappe, J.P.Toennies. Journal of Physical Chemistry, 101 (1997) 6415 "The H+D2 Reaction in the Vicinity of the Conical Intersection" E. Wrede, L. Schnieder, K.H. Welge, F.J. Aoiz, L. Bañares, V.J. Herrero, B. Martínez-Haya and V. Sáez Rábanos Journal of Chemical Physics, 106 (1997) 7862
Statistical Mechanics of Simple Fluids
Statistical Mechanics (Monte Carlo and Molecular Dynamics computer simulations, Integral Equation techniques)  investigation of simple rigid models of anisotropic molecular fluids with different dispersive and electrostatic intermolecular interactions. In collaboration with my colleague Alejandro Cuetos. We have been looking into the Liquid Crystal phases (isotropic, nematic, smectic, hexatic, columnar) of fluids of prolate and oblate molecules dressed with different types of Kihara-type interaction. We have developed a novel orientation-dependent interaction model for these molecular fluids, which combines distinct properties of the well known Kihara and Gay-Berne pair potentials.
Selected publications in the field of Statistical Mechanics of Simple Fluids: "Phase Behavior of Hard Colloidal Platelets using Free Energy Calculations"  M. Marechal,  A. Cuetos, B. Martínez-Haya, M. Dijkstra Journal of Chemical Physics, 134 (2011) 094501 "Nematic stability of discotic molecules with orientation-dependent interactions" B. Martínez-Haya, A. Cuetos Physical Review E, 81 (2010) 020701 1-4 "Columnar Phases of discotics with orientation-dependent interactions"  B. Martínez-Haya, A. Cuetos Journal of Chemical Physics, 131 (2009) 074901 1-8 "Simulation study of discotic molecules in the vicinity of the isotropic-liquid crystal transition"  B. Martínez-Haya, A. Cuetos Molecular Simulation, 35 (2009) 1077-1083. "Columnar phases of Discotic Spherocylinders" A. Cuetos, B. Martínez-Haya, Journal of Chemical Physics, 129 (2008) 214706 1-7 "Stability of Nematic and Smectic phases in rod-like mesogens with orientation-dependent attractive interactions" B. Martínez-Haya, A. Cuetos, Journal of Physical Chemistry B, 111 (2007) 8150-8157 "Use of Parsons-Lee and Onsager theories to predict nematic and demixing behavior in binary mixtures of hard rods and spheres" A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull. Physical Review E, 75 (2007) 061701 1-12 "Effect of Macromolecular Crowding on the conformation of confined Chain Polymers" B. Martínez-Haya and M.C. Gordillo, Macromolecular Theory and Simulations, 14 (2005) p. 421 "Parsons-Lee and Monte Carlo study of soft repulsive nematogens"  A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull. Journal of Physical Chemistry B, 109 (2005) p.13729 "A Novel Orientation-dependent Potential Model for Prolate Mesogens"  A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull. Journal of Chemical Physics, 122 (2005)  024908 "Crowding Effects in Binary Mixtures of Rod-like and Spherical Particles"  S. Lago, A. Cuetos,  B. Martínez-Haya, L.F. Rull. Journal of Molecular Recognition, 17 (2004) p.417. "Liquid Crystal Behavior of the Kihara Fluid"  A. Cuetos,  B. Martínez-Haya, S. Lago, L.F. Rull, Physical Review E, 68 (2003) 0011704. "Monte Carlo Study of Liquid Crystal Phases of Hard and Soft Spherocylinders"  A. Cuetos,  B. Martínez-Haya, L.F. Rull, S. Lago. Journal of Chemical Physics, 117 (2002) p.2034. Erratum, ibid. 117 (2002) p.11405. "Gibbs-Ensemble Simulation of the Vapor-liquid Equilibrium of Square Well Spherocylinders" B. Martínez-Haya, L.F. Rull, A. Cuetos, S. Lago. Molecular Physics 99  (2001) p.509 "Analytical Solution to a Non-separable Interaction Model for a One-dimensional Fluid of Anisotropic Molecules near a Hard Wall" B. Martínez-Haya, J.M. Pastor, J.A. Cuesta. Physical Review E, 59 (1999) 1957