Electron-capture—Induced dissociation of protoporphyrin IX ions

Bernigaud, V.; Drenck, Kasper; Huber, B. A.; Hvelplund, P.; Jabot, Tristan; Kadhane, U.; Kirketerp, Maj-Britt Suhr; Liu, Bo; Lykkegaard, Morten Køcks; Manil, B.; Nielsen, Steen Brøndsted

doi:10.1016/j.jasms.2008.01.002

Cited by 11 publications

(7 citation statements)

References 33 publications

(31 reference statements)

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“…The fragment distributions in Fig. 3 and those reported in Refs [33][34][35] are markedly different from those observed in other experiments. 12,17,19 Fragments from the loss of the phenyl groups were seen following 30 keV O 3+ and 70 eV electron impact on neutral FeTPPCl.…”

Section: Resultscontrasting

confidence: 74%

“…3 are similar to those measured earlier for collisions between (TPP +H) + and He at 278 eV center-of-mass energy 33 and for collisions with protonated protoporphyrin IX and Fe(III)-heme. 34,35 There, [33][34][35] peaks corresponding to the loss of one or several heavy atoms were clearly observed but their origins were not discussed. The fragment distributions in Fig.…”

Section: Resultsmentioning

confidence: 99%

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Knockout driven fragmentation of porphyrins

Giacomozzi

Gatchell

Ruette

et al. 2017

Phys. Chem. Chem. Phys.

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We have studied collisions between tetraphenylporphyrin cations and He or Ne at center-of-mass energies in the range 50-110 eV. The experimental results were interpreted in view of density functional theory calculations of dissociation energies and classical molecular dynamics simulations of how the molecules respond to the He/Ne impact. We demonstrate that prompt atom knockout strongly contributes to the total destruction cross sections. Such impulse driven processes typically yield highly reactive fragments and are expected to be important for collisions with any molecular system in this collision energy range, but have earlier been very difficult to isolate for biomolecules.

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Section: Resultscontrasting

confidence: 74%

Section: Resultsmentioning

confidence: 99%

Knockout driven fragmentation of porphyrins

Giacomozzi

Gatchell

Ruette

et al. 2017

Phys. Chem. Chem. Phys.

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“…108 for DnOP, has an overlap region between the two partners of B; this suggested that the LUMO is not antibonding between the O and the C of the alkene group. Such bonding characteristic of a LUMO has been previously described [28]. In the case DEHP, the overlap of the LUMO was not observed because of the relative orientation of the two partners of the complex.…”

Section: Modeling Radical Cation Molecule Complexsupporting

confidence: 73%

Density Functional Theory and Mass Spectrometry of Phthalate Fragmentations Mechanisms: Modeling Hyperconjugated Carbocation and Radical Cation Complexes with Neutral Molecules

Jeilani

Cardelino

Ibeanusi

2011

J. Am. Soc. Mass Spectrom.

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This is the first ab initio study of the energetics of the fragmentation mechanisms of phthalate, by mass spectrometry, leading to protonated phthalic anhydride (m/z 149). Phthalates fragment by two major pathways; namely, the McLafferty+1 rearrangement and the loss of alkoxy. Both pathways involve a carbonyl oxygen attack to the ortho-carbonyl carbon leading to structures with tetrahedral carbon intermediates that eventually give m/z 149. These pathways were studied by collision induced dissociation (CID) using triple quadrupole mass spectrometry. The proposed McLafferty+1 pathway proceeds through a distonic M•+ , leading to the loss of an allylic-stabilized alkene radical. The McLafferty rearrangement step proceeds through a six-membered ring transition state with a small activation energy ranging 0.4-6.2 kcal/mol; the transfer of a second H from the distonic ion of the rearrangement step proceeds through a radical cation molecule complex. Based on quantum chemical modeling of the cation molecule complexes, two kinds of cation molecule complexes were identified as radical cation molecule complex and hyperconjugated cation molecule complex. This distinction is based on the cation and simplifies future modeling of similar complexes. Optimization of important fragments in these pathways showed cyclized and hydrogen-bonded structures to be favored. An exception was the optimized structure of the protonated phthalic anhydride (m/z 149) that showed a structure with an open anhydride ring.

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“…Previous mass-spectrometric studies on electrosprayed metal protoporphyrin IX ions employed collision-induced dissociation (CID), [24][25][26][27] electron-capture-induced dissociation (ECD) 28 and laser-induced dissociation (LID) 18,25,26,[29][30][31][32] following absorption at the Soret and Q bands to investigate their dissociation processes. Moreover, it has been shown for gas-phase heme + that photoexcitation in the UV/vis region can be followed by dissociation via two kinetically competing channels on a microsecond to millisecond timescale.…”

Section: Introductionmentioning

confidence: 99%