Bond and site selective dissociative electron attachment

Bond and site selective dissociative electron attachment (P 19073)

funded by FWF

Principal Investigator:	Paul Scheier
Duration:	01.06.2007 - 31.05.2012 (Approval date: 02.10.2006)
Scientific fields:	1242 Mass Spectrometry (40%) 1207 Bio Physics(1403,3203) (30%) 1235 Ion Physics (20%) 1249 Radiation Physics (3218) (10%)
Keywords:	Dissociative electron attachment; Unimolecular dissociation; Radiation damage; Kinetic energy release; Site selective reactions

Abstract:

Laboratory measurements are proposed to investigate dissociative electron attachment (DEA) to DNA bases and nitrotoluene and their derivatives. For most of the biologically relevant molecules studied so far, neutral H loss and the formation of H– are important DEA channels. Very recent studies on the H– loss from several organic molecules, including the phyrimidine bases uracil and thymine, demonstrate that by tuning the electron energy it is possible to selectively break a specific bond. Isotopically labeled molecules and methylated derivates enable experimentally the assignment of resonances to bond breaking at specific molecular sites. In the presently proposed studies it is planned to investigate site selectivity of neutral H and H– loss from the other DNA bases, i.e., adenine, cytosine and guanine. For NO2–, the most abundant fragment anion formed via DEA to various nitrotoluene molecules, site selectivity has been described in the literature, i.e., the energy and intensity of the resonances depend strongly on the position of the NO2 group relative to the methyl group. For several heavy fragment anions formed via DEA to various nitrotoluene molecules we discovered similar site selectivity. Again labeling with isotopes and functional groups is planned to assign the resonances in the attachment cross sections to bond rupture at a specific site. A pulsed hemispherical electron monochromator will be built. The interaction region between electrons and neutral target molecules will be field-free when electrons are present which is essential for high electron energy resolution. However, a strong extraction field in the time when the electron beam is off can be used to collect all ions with uniform efficiency, even if they are formed with a high kinetic energy. Furthermore, it is planned to utilize this pulsed ion source to measure the kinetic energy that is released in the DEA process. In the case of one atomic fragment, such as the H– formation, the kinetic energy of the anion determines the internal energy that remains in the heavy fragment. In extension to simple gas phase experiments it is planned to study free electron attachment to clusters of the molecules mentioned above or to molecules embedded in a well defined solvent layer. For this purpose two recently constructed neutral beam sources will be utilized, i.e., a helium cluster source and a spray source. Thereby the signature of site selective DEA channels on secondary reaction products resulting from intra-cluster anion molecule reactions will be studied. In the case of biomolecules clusters and complexes with water will bridge the gap between gas phase studies and the investigation of low-energy electron induced DNA strand breaks. Furthermore, free electron interactions with ultra-cold targets of water and biomolecules, formed via pick-up of superfluid He droplets, can give important insight into the formation, liberation and destruction of complex organic molecules in dense interstellar clouds.

Final Report (PDF)

Peer-reviewed publications:

2010
1. E. Alizadeh, K. Graupner, A. Mauracher, S. Haughey, A. Edtbauer, M. Probst, T. D. Märk, T. A. Field, P. Scheier, Electron attachment to 2-nitro-m-xylene. Int. J. Mass. Spectrom. 2-3/289 (2010) 128-137 doi:10.1016/j.ijms.2009.10.003
2. S. Denifl, H. D. Flosadottir, A. Edtbauer, O. Ingolfsson, T. D. Märk, P. Scheier, A detailed study on the decomposition pathways of the amino acid valine upon dissociative electron attachment. Eur. Phys. J. D 1/60 (2010) 37-44 doi:10.1140/epjd/e2010-00060-5
3. S. Denifl, V. Vizcaino, T. D. Märk, E. Illenberger, P. Scheier, High resolution electron attachment to CO2 clusters. Phys. Chem. Chem. Phys. 20/12 (2010) 5219-5224 doi:10.1039/b924526j
4. S. Denifl, F. Zappa, I. Mähr, A. Mauracher, M. Probst, J. Urban, P. Mach, A. Bacher, D. K. Bohme, O. Echt, T. D. Märk, P. Scheier, Ionization of doped helium nanodroplets. Complexes of C60 with water clusters. J. Chem. Phys. 23/132 (2010) 234307-11 doi:10.1063/1.3436721
5. A. Edtbauer, S. Denifl, V. Vizcaino, L. An der Lan, K. Russell, J. Taubitz, U. Wille, L. Feketeova, R. A. O'Hair, T. D. Märk, E. Illenberger, P. Scheier, Very Low Energy Electrons Transform the Cyclobutane-Pyrimidine Dimer into a Highly Reactive Intermediate. ChemPhysChem 3/11 (2010) 561-564 doi:10.1002/cphc.200900912
6. A. Edtbauer, P. Sulzer, A. Mauracher, C. Mitterdorfer, F. Ferreira da Silva, S. Denifl, T. D. Märk, M. Probst, Y. Nunes, P. Limao-Vieira, P. Scheier, Dissociative electron attachment to pentaerythritol tetranitrate. Significant fragmentation near 0 eV. J. Chem. Phys. 13/132 (2010) 134305-8 doi:10.1063/1.3386386
7. F. Ferreira da Silva, P. Bartl, S. Denifl, T. D. Märk, A. M. Ellis, P. Scheier, Formation of the Magic L-Serine Octamer in Helium Nanodroplets. ChemPhysChem 1/11 (2010) 90-92 doi:10.1002/cphc.200900826
8. F. Ferreira da Silva, S. Denifl, T. D. Märk, N. L. Doltsinis, A. M. Ellis, P. Scheier, Electron Attachment to Formamide Clusters in Helium Nanodroplets. J. Phys. Chem. A 4/114 (2010) 1633-1638 doi:10.1021/jp909890h
9. F. Ferreira da Silva, S. Denifl, T. D. Märk, A. M. Ellis, P. Scheier, Electron attachment to amino acid clusters in helium nanodroplets. Glycine, alanine, and serine. J. Chem. Phys. 21/132 (2010) 214306-6 doi:10.1063/1.3429743; selected for the Virtual Journal of Biological Physics Research 19 (2010) issue 12
10. M. Mahmoodi-Darian, S. X. Tian, S. Denifl, S. Matejcik, T. D. Märk, P. Scheier, Temperature dependence of dissociative electron attachment to 1-bromo-2-chlorobenzene and 1-bromo-3-chlorobenzene. Int. J. Mass. Spectrom. 1-3/293 (2010) 51-55 doi:10.1016/j.ijms.2010.04.004
11. A. Mauracher, S. Denifl, A. Edtbauer, M. Hager, M. Probst, O. Echt, T. D. Märk, P. Scheier, T. A. Field, K. Graupner, Metastable anions of dinitrobenzene. Resonances for electron attachment and kinetic energy release. J. Chem. Phys. 24/133 (2010) 244302-9 doi:10.1063/1.3514931
12. T. D. Märk, P. Scheier, Ionization dynamics. Unexpected electrons. Nat Phys 2/6 (2010) 82-83 doi:10.1038/nphys1526
13. H. Schöbel, P. Bartl, C. Leidlmair, M. Daxner, S. Zöttl, S. Denifl, T. D. Märk, P. Scheier, D. Spangberg, A. Mauracher, D. K. Bohme, Sequential Penning Ionization. Harvesting Energy with Ions. Phys. Rev. Lett. 24/105 (2010) 243402-4 doi:10.1103/PhysRevLett.105.243402
14. V. Vizcaino, S. Denifl, T. D. Märk, E. Illenberger, P. Scheier, Low energy (0-4 eV) electron impact to N2O clusters. Dissociative electron attachment, ion-molecule reactions, and vibrational Feshbach resonances. J. Chem. Phys. 15/133 (2010) 154512-6 doi:10.1063/1.3505143
2009
1. S. Denifl, I. Mähr, F. Ferreira da Silva, F. Zappa, T. D. Märk, P. Scheier, Electron impact ionization studies with the amino acid valine in the gas phase and (hydrated) in helium droplets. Eur. Phys. J. D 1/51 (2009) 73-79 doi:10.1140/epjd/e2008-00092-4
2. S. Denifl, F. Zappa, I. Mähr, F. Ferreira da Silva, A. Aleem, A. Mauracher, M. Probst, J. Urban, P. Mach, A. Bacher, O. Echt, T. D. Märk, P. Scheier, Ion-Molecule Reactions in Helium Nanodroplets Doped with C60 and Water Clusters. Angew. Chem. Int. Ed. 47/48 (2009) 8940-8943 doi:10.1002/anie.200904381; german reprint in doi:10.1002/ange.200904381
3. A. Edtbauer, K. Russell, L. Feketeova, J. Taubitz, C. Mitterdorfer, S. Denifl, T. D. Märk, P. Scheier, U. Willi, Formation of pyrimidine dimer radical anions in the gas phase. Chem. Commun. 48/ (2009) 7291-7293 doi:10.1039/b920282j
4. N. Endstrasser, F. Zappa, A. Mauracher, A. Bacher, S. Feil, D. K. Böhme, P. Scheier, M. Probst, T. D. Märk, Absolute partial cross sections and kinetic energy analysis for the electron impact ionization of ethylene. Int. J. Mass. Spectrom. 1-3/280 (2009) 65-71 doi:10.1016/j.ijms.2008.08.004
5. F. Ferreira da Silva, P. Bartl, S. Denifl, O. Echt, T. D. Märk, P. Scheier, Argon clusters embedded in helium nanodroplets. Phys. Chem. Chem. Phys. 42/11 (2009) 9791-9797 doi:10.1039/b913175b
6. F. Ferreira da Silva, S. Jaksch, G. Martins, H. M. Dang, M. Dampc, S. Denifl, T. D. Märk, P. Limao-Vieira, J. Liu, S. Yang, A. M. Ellis, P. Scheier, Electron attachment and electron ionization of acetic acid clusters embedded in helium nanodroplets. Phys. Chem. Chem. Phys. 48/11 (2009) 11631-11637 doi:10.1039/b918210a
7. F. Ferreira da Silva, P. Waldburger, S. Jaksch, A. Mauracher, S. Denifl, O. Echt, T. D. Märk, P. Scheier, On the Size of Ions Solvated in Helium Clusters. Chem.-Eur. J. 29/15 (2009) 7101-7108 doi:10.1002/chem.200802554
8. S. Jaksch, F. Ferreira da Silva, S. Denifl, O. Echt, T. D. Märk, P. Scheier, Experimental Evidence for the Existence of an Electronically Excited State of the Proposed Dihydrogen Radical Cation He-H-H-He+. Chem.-Eur. J. 16/15 (2009) 4190-4194 doi:10.1002/chem.200802545
9. S. Jaksch, I. Mähr, S. Denifl, A. Bacher, O. Echt, T. D. Märk, P. Scheier, Electron attachment to doped helium droplets. C60-, (C60)2-, and C60D2O- anions. Eur. Phys. J. D 52 (2009) 91-94 doi:10.1140/epjd/e2008-00252-6
10. A. Mauracher, H. Schöbel, F. Ferreira da Silva, A. Edtbauer, C. Mitterdorfer, S. Denifl, T. D. Märk, E. Illenberger, P. Scheier, Electron attachment to trinitrotoluene (TNT) embedded in He droplets. complete freezing of dissociation intermediates in an extended range of electron energies. Phys. Chem. Chem. Phys. 37/11 (2009) 8240-8243 doi:10.1039/b908192e
11. H. Schöbel, M. Dampc, F. Ferreira da Silva, A. Mauracher, F. Zappa, S. Denifl, T. D. Märk, P. Scheier, Electron impact ionization of CCl4 and SF6 embedded in superfluid helium droplets. Int. J. Mass. Spectrom. 1-3/280 (2009) 26-31 doi:10.1016/j.ijms.2008.07.009
2008
1. S. Denifl, F. Zappa, I. Mähr, A. Mauracher, M. Probst, T.D. Märk, P. Scheier; Inelastic Electron Interaction with Chloroform Clusters Embedded in Helium Droplets. J. Am. Chem. Soc. 15/130 (2008) 5065-5071 doi:10.1021/ja075972m
2. K. Graupner, T.A. Field, A. Mauracher, P. Scheier, A. Bacher, S. Denifl, F. Zappa, T.D. Märk; Fragmentation of metastable SF6-* ions with microsecond lifetimes in competition with autodetachment. J. Chem. Phys. 10/128 (2008) 104304-8 doi:10.1063/1.2884346
3. F. Zappa, M. Beikircher, A. Mauracher, S. Denifl, M. Probst, N. Injan, J. Limtrakul, A. Bacher, O. Echt, T.D. Märk, P. Scheier, T.A. Field, K. Graupner; Metastable Dissociation of Anions Formed by Electron Attachment. ChemPhysChem 4/9 (2008) 607-611 doi:10.1002/cphc.200700720
4. F. Zappa, S. Denifl, I. Mähr, A. Bacher, O. Echt, T.D. Märk, P. Scheier; Ultracold Water Cluster Anions. J. Am. Chem. Soc. 16/130 (2008) 5573-5578 doi:10.1021/ja075421w
2007
1. S. Denifl, A. Mauracher, P. Sulzer, A. Bacher, T.D. Märk, P. Scheier; Free electron attachment to the chloromethane CHCl3. Int. J. Mass. Spectrom. 2-3/265 (2007) 139-145 doi:10.1016/j.ijms.2007.01.021
2. S. Denifl, P. Sulzer, D. Huber, F. Zappa, M. Probst, T.D. Märk, P. Scheier, N. Injan, J. Limtrakul, R. Abouaf, H. Dunet; Influence of Functional Groups on the Site-Selective Dissociation of Adenine upon Low-Energy Electron Attachment. Angew. Chem. Int. Ed. 27/46 (2007) 5238-5241 doi:10.1002/anie.200700032; german reprint in doi:10.1002/ange.200700032
3. S. Feil, P. Sulzer, A. Mauracher, M. Beikircher, N. Wendt, A. Aleem, S. Denifl, F. Zappa, S. Matt-Leubner, A. Bacher, S. Matejcik, M. Probst, P. Scheier, T.D. Märk; Electron Impact Ionization/Dissociation of Molecules. Production of Energetic Radical Ions and Anions. J. Phys.: Conf. Ser. 86 (2007) 012003 doi:10.1088/1742-6596/86/1/012003 (Open Access)
4. H.D. Flosadottir, S. Denifl, F. Zappa, N. Wendt, A. Mauracher, A. Bacher, H. Jonsson, T.D. Märk, P. Scheier, O. Ingolfsson; Combined Experimental and Theoretical Study on the Nature and the Metastable Decay Pathways of the Amino Acid Ion Fragment [M-H]-. Angew. Chem. Int. Ed. 42/46 (2007) 8057-8059 doi:10.1002/anie.200703327; german reprint in doi:10.1002/ange.200703327
5. A. Mauracher, S. Denifl, A. Aleem, N. Wendt, F. Zappa, P. Cicman, M. Probst, T.D. Märk, P. Scheier, H.D. Flosadottir, O. Ingolfsson, E. Illenberger; Dissociative electron attachment to gas phase glycine. Exploring the decomposition pathways by mass separation of isobaric fragment anions. Phys. Chem. Chem. Phys. 42/9 (2007) 5680-5685 doi:10.1039/b709140k
6. I. Mähr, F. Zappa, S. Denifl, D. Kubala, O. Echt, T.D. Märk, P. Scheier; Multiply Charged Neon Clusters. Failure of the Liquid Drop Model?. Phys. Rev. Lett. 2/98 (2007) 023401-4 doi:10.1103/PhysRevLett.98.023401
7. P. Sulzer, A. Mauracher, S. Denifl, M. Probst, T.D. Märk, P. Scheier, E. Illenberger; Probing di-nitrobenzene by low energy electrons. Identification of isomers via resonances in dissociative electron attachment. Int. J. Mass. Spectrom. 1-3/266 (2007) 138-148 doi:10.1016/j.ijms.2007.07.018
8. P. Sulzer, A. Mauracher, S. Denifl, F. Zappa, S. Ptasinska, M. Beikircher, A. Bacher, N. Wendt, A. Aleem, F. Rondino, S. Matejcik, M. Probst, T.D. Märk, P. Scheier; Identification of Isomers of Nitrotoluene via Free Electron Attachment. Anal. Chem. 17/79 (2007) 6585-6591 doi:10.1021/ac070656b
9. P. Sulzer, A. Mauracher, S. Denifl, F. Zappa, S. Ptasinska, F. Rondino, P. Scheier, T.D. Märk; Dissociative electron attachment to nitroaromatic compounds – resonances as fingerprints for isomers. J. Phys.: Conf. Ser. 88 (2007) 012075 doi:10.1088/1742-6596/88/1/012075 (Open Access)
10. F. Zappa, S. Denifl, I. Mähr, J. Lecointre, F. Rondino, O. Echt, T.D. Märk, P. Scheier; Electron impact ionization of thymine clusters embedded in superfluid helium droplets. Eur. Phys. J. D 1-3/43 (2007) 117-120 doi:10.1140/epjd/e2007-00093-9