A comparative VUV absorption mass-spectroscopy study on protonated peptides of different size.

The ionization of gas-phase protonated peptides and proteins can induce molecular responses ranging from purely non-dissociative ionization to extensive multifragmentation of the system. In the case of soft X-ray photoionization, a monotonic transition between both regimes occurs in the mass range between 0.5 and 10 kDa. Despite the localized nature of the photoabsorption, excitation energy equilibrates before fragmentation sets in and the transition reflects the increase of the heat capacity with protein size. Here, we have investigated the influence of peptide size on vacuum ultraviolet (VUV) photoionization of protonated proteins, where photoexcitation and ionization are limited to valence electrons rather than inner shell electrons and the photoexcitation contribution is markedly lower. Gas phase protonated peptides with masses ranging from 0.6-2.8 kDa were trapped in a radiofrequency ion trap and exposed to synchrotron radiation. Time of flight mass spectrometry was employed for the investigation of the photoionization and photofragmentation processes. The relationship between peptide fragmentation and peptide size exhibits a similar trend as observed for soft X-ray absorption. Due to the lower excitation energies involved, however, dissociation is already quenched at smaller masses and peptide amino acid compositions, protonation states and ionization potentials lead to deviations from the general trend.

Near edge X-ray absorption mass spectrometry of gas phase proteins: the influence of protein size.

Multiply protonated peptides and proteins in the gas phase can respond to near edge X-ray absorption in three different ways: (i) non dissociative ionization and ionization accompanied by loss of small neutrals, both known to dominate for proteins with masses in the 10 kDa range. (ii) Formation of immonium ions, dominating for peptides in the 1 kDa range. (iii) Backbone scission leading to sequence ions which is typically weaker and has mainly been observed for peptides in the 1 kDa range. We have studied carbon 1s photoexcitation and photoionization for a series of peptides and proteins with masses covering the range from 0.5 kDa to more than 10 kDa. The gas phase protonated molecules were trapped in a radiofrequency ion trap and exposed to synchrotron radiation. Time of flight mass spectrometry was employed for investigation of the photoionization and photofragmentation processes. A smooth transition from the photofragmentation regime to the non-dissociative photoionization regime is observed. Mass spectra are most complex in the few kDa regime, where non-dissociative ionization, backbone scission and immonium ion formation coexist. The observed correlation between protein size and fragmentation, i.e. radiation damage, is of relevance for soft X-ray microscopy.

Near edge X-ray absorption mass spectrometry on coronene.

We have investigated the photoionization and photodissociation of free coronene cations C24H12 (+) upon soft X-ray photoabsorption in the carbon K-edge region by means of a time-of-flight mass spectrometry approach. Core excitation into an unoccupied molecular orbital (below threshold) and core ionization into the continuum both leave a C 1s vacancy, that is subsequently filled in an Auger-type process. The resulting coronene dications and trications are internally excited and cool down predominantly by means of hydrogen emission. Density functional theory was employed to determine the dissociation energies for subsequent neutral hydrogen loss. A statistical cascade model incorporating these dissociation energies agrees well with the experimentally observed dehydrogenation. For double ionization, i.e., formation of intermediate C24H12 (3+⋆)trications, the experimental data hint at loss of H(+) ions. This asymmetric fission channel is associated with hot intermediates, whereas colder intermediates predominantly decay via neutral H loss.

Deexcitation dynamics of superhydrogenated polycyclic aromatic hydrocarbon cations after soft-x-ray absorption.

We have investigated the response of superhydrogenated gas-phase coronene cations upon soft x-ray absorption. Carbon (1s)⟶π^{⋆} transitions were resonantly excited at hν=285 eV. The resulting core hole is then filled in an Auger decay process, with the excess energy being released in the form of an Auger electron. Predominantly highly excited dications are thus formed, which cool down by hydrogen emission. In superhydrogenated systems, the additional H atoms act as a buffer, quenching loss of native H atoms and molecular fragmentation. Dissociation and transition state energies for several H loss channels were computed by means of density functional theory. Using these energies as input into an Arrhenius-type cascade model, very good agreement with the experimental data is found. The results have important implications for the survival of polyaromatic hydrocarbons in the interstellar medium and reflect key aspects of graphene hydrogenation.

Absolute fragmentation cross sections in atom-molecule collisions: scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules.

We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH(+)) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH(+) + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C6H5). Thus nonstatistical fragmentation may be an effective initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.

Near-edge X-ray absorption mass spectrometry of a gas-phase peptide.

We have studied the dissociation of the gas-phase protonated peptide leucine enkephalin [YGGFL+H](+) upon X-ray absorption in the region of the C K-edge. The yield of photodissociation products was recorded as a function of photon energy. The total photoabsorption yield is qualitatively similar to near-edge X-ray absorption fine structure (NEXAFS) spectra recorded from condensed phase peptides and proteins. Fragment specificity reveals distinct quantitative differences between spectra obtained for different masses. Fragmentation channels can be assigned to specific electronic transitions some of which are site specific. For instance, C 1s → π(★) excitations in the leucine enkephalin aromatic side chains lead to relatively little fragmentation, whereas such excitations along the peptide backbone induce strong fragmentation.

Length effects in VUV photofragmentation of protonated peptides.

We have studied photoionization of protonated synthetic peptides YG(n)F (n = 0, 1, 3, 5, 10). Photon energies ranging from 8 to 30 eV were used. For YG(n)F peptides up to n = 5 small fragment ions related to the sidechains of the aromatic terminal amino acids Y and F dominate the fragmentation patterns. The associated yields scale with total photoabsorption cross section, demonstrating efficient hole migration towards the terminal amino acids upon photoionization of the peptide backbone. For n = 10 the side-chain loss channel is quenched and a series of large dications appear.

Photodissociation of protonated leucine-enkephalin in the VUV range of 8-40 eV.

Until now, photodissociation studies on free complex protonated peptides were limited to the UV wavelength range accessible by intense lasers. We have studied photodissociation of gas-phase protonated leucine-enkephalin cations for vacuum ultraviolet (VUV) photons energies ranging from 8 to 40 eV. We report time-of-flight mass spectra of the photofragments and various photofragment-yields as a function of photon energy. For sub-ionization energies our results are in line with existing studies on UV photodissociation of leucine-enkephalin. For photon energies exceeding 10 eV we could identify a new dissociation scheme in which photoabsorption leads to a fast loss of the tyrosine side chain. This loss process leads to the formation of a residual peptide that is remarkably cold internally.

Fragmentation of alpha- and beta-alanine molecules by ions at Bragg-peak energies.

The interaction of keV He(+), He(2+), and O(5+) ions with isolated alpha and beta isomers of the amino acid alanine was studied by means of high resolution coincidence time-of-flight mass spectrometry. We observed a strong isomer dependence of characteristic fragmentation channels which manifests in strongly altered branching ratios. Despite the ultrashort initial perturbation by the incoming ion, evidence for molecular rearrangement leading to the formation of H(3)(+) was found. The measured kinetic energies of ionic alanine fragments can be sufficient to induce secondary damage to DNA in a biological environment.

Response of polyatomic molecules to ultrastrong laser- and ion-induced fields.

The exposure of molecules to short, ultrastrong electric fields leads to multiple ionization and a subsequent Coulomb explosion. We present a comparative study where uracil molecules are exposed to fields generated by high-power laser pulses (tau approximately 75 fs, I > 10(16) W/cm2) or swift highly charged ions (0.5 MeV Xe25+) representing a half-cycle pulse of less than 10 fs duration. Molecular dynamics and structural information contained in the fragmentation pathways can be assessed separately. Despite the similar field strengths large differences in fragment kinetic energies are found which are related to field shape and duration with the aid of molecular dynamics simulations.

Charge driven fragmentation of nucleobases.

We studied multiple ionization of single nucleobases by means of slow highly charged ions (Xe(q+), q=5-25). The products of the subsequent fragmentation were studied using high resolution coincidence time-of-flight spectrometry. We observed a strong dependence of the fragment kinetic energies on the initial charge state of the intermediate parent ions as well as on the initial chemical environment of the respective fragment ions within the parent molecule. The data allow us to shed light on the charge distribution within the molecule as well as on the fragmentation dynamics of these intermediate size systems.

Charge localization in collision-induced multiple ionization of van der Waals clusters with highly charged ions.

Charge localization in multiple ionization and fragmentation of small argon clusters is reported. The processes are initiated by interaction of the neutral cluster with highly charged Xe(q+) (5< or =q< or =25). Products are detected by means of multicoincidence time-of-flight methods. A strong dependence of the fragmentation pattern on the Xe charge state q is observed. In particular, we find evidence for formation of multiply charged atomic Ar(r+) fragment ions up to r = 7. Such high charge states have neither been observed in fission of multiply charged van der Waals clusters nor in ion-induced fragmentation of fullerenes or metal clusters. This hints at fundamentally different excitation and fragmentation dynamics.

Z oscillations in ion-induced fullerene fragmentation

Multiply charged ion-induced fragmentation and ionization of C60 is governed by electronic and nuclear stopping of the projectile as well as charge exchange. We have studied the collision dynamics as a function of the projectile atomic number Z ( 2