Yoni Toker

UV excited-state photoresponse of biochromophore negative ions.

Members of the green fluorescent protein (GFP) family may undergo irreversible phototransformation upon irradiation with UV light. This provides clear evidence for the importance of the higher-energy photophysics of the chromophore, which remains essentially unexplored. By using time-resolved action and photoelectron spectroscopy together with high-level electronic structure theory, we directly probe and identify higher electronically excited singlet states of the isolated para- and meta-chromophore anions of GFP. These molecular resonances are found to serve as a doorway for very efficient electron detachment in the gas phase. Inside the protein, this band is found to be resonant with the quasicontinuum of a solvated electron, thus enhancing electron transfer from the GFP to the solvent. This suggests a photophysical pathway for photoconversion of the protein, where GFP resonant photooxidation in solution triggers radical redox reactions inside these proteins.

Unraveling the Intrinsic Color of Chlorophyll

The exact color of light absorbed by chlorophyll (Chl) pigments, the light-harvesters in photosynthesis, is tuned by the protein microenvironment, but without knowledge of the intrinsic color of Chl it remains unclear how large this effect is. Experimental first absorption energies of Chl a and b isolated in vacuo and tagged with quaternary ammonium cations are reported. The energies are largely insensitive to details of the tag structure, a finding supported by first-principles calculations using time-dependent density functional theory. Absorption is significantly blue-shifted compared to that of Chl-containing proteins (by 30-70 nm). A single red-shifting perturbation, such as axial ligation or the protein medium, is insufficient to account even for the smallest shift; the largest requires pigment-pigment interactions.

Formation and stability of hydrogenated PAHs in the gas phase

Aims. We report on experimental and computational studies of hydrogenation of polycyclic aromatic hydrocarbon (PAH) cations, HnPAHs, which are relevant to the interstellar medium. Methods. The yield of the hydrogenated PAH cations produced in a plasma-ion source and by electrospray ionization was measured. DFT calculations at the B3LYP/6-311+G(d, p) and B3LYP/6-31+G(d, p) level of theory were performed to investigate the hydrogenation pattern. Results. A clear pattern in the yield and binding energies of hydrogen is revealed. Hydrogenated closed shell molecules with an even number of attached hydrogen atoms are significantly more stable than molecules with an odd number of hydrogen atoms and show as a consequence to be more abundant in mass spectra of HnPAHs. The binding energy of a hydrogen atom to Hn−1PAH with an even n is ∼2 eV higher than for odd n. The exact distribution in n observed in the experimental mass spectra remains to be solved due to the unknown internal ion source conditions. Conclusions. The HnPAH cations have been produced under very different conditions, and the measured yield indicates high stability and likely high abundance in the interstellar medium.

Characterization of a new electrostatic storage ring for photofragmentation experiments

We describe the design of and the first commissioning experiments with a newly constructed electrostatic storage ring named SAPHIRA (Storage Ring in Aarhus for PHoton-Ion Reaction Analysis). With an intense beam of Cu(-) at 4 keV, the storage ring is characterized in terms of the stored ion beam decay rate, the longitudinal spreading of an injected ion bunch, as well as the direct measurements of the transverse spatial distributions under different conditions of storage. The ion storage stability in SAPHIRA was investigated systematically in a selected region of its electrical configuration space.

Lifetime measurements in an electrostatic ion beam trap using image charge monitoring

A technique for mass-selective lifetime measurements of keV ions in a linear electrostatic ion beam trap is presented. The technique is based on bunching the ions using a weak RF potential and non-destructive ion detection by a pick-up electrode. This method has no mass-limitation, possesses the advantage of inherent mass-selectivity, and offers a possibility of measuring simultaneously the lifetimes of different ion species with no need for prior mass-selection.

Photodissociation pathways and lifetimes of protonated peptides and their dimers

Photodissociation lifetimes and fragment channels of gas-phase, protonated YA(n) (n = 1,2) peptides and their dimers were measured with 266 nm photons. The protonated monomers were found to have a fast dissociation channel with an exponential lifetime of ~200 ns while the protonated dimers show an additional slow dissociation component with a lifetime of ~2 μs. Laser power dependence measurements enabled us to ascribe the fast channel in the monomer and the slow channel in the dimer to a one-photon process, whereas the fast dimer channel is from a two-photon process. The slow (1 photon) dissociation channel in the dimer was found to result in cleavage of the H-bonds after energy transfer through these H-bonds. In general, the dissociation of these protonated peptides is non-prompt and the decay time was found to increase with the size of the peptides. Quantum RRKM calculations of the microcanonical rate constants also confirmed a statistical nature of the photodissociation processes in the dipeptide monomers and dimers. The classical RRKM expression gives a rate constant as an analytical function of the number of active vibrational modes in the system, estimated separately on the basis of the equipartition theorem. It demonstrates encouraging results in predicting fragmentation lifetimes of protonated peptides. Finally, we present the first experimental evidence for a photo-induced conversion of tyrosine-containing peptides into monocyclic aromatic hydrocarbon along with a formamide molecule both found in space.

On the Exciton Coupling between Two Chlorophyll Pigments in the Absence of a Protein Environment: Intrinsic Effects Revealed by Theory and Experiment.

Exciton coupling between two or more chlorophyll (Chl) pigments is a key mechanism associated with the color tuning of photosynthetic proteins but it is difficult to disentangle this effect from shifts that are due to the protein microenvironment. Herein, we report the formation of the simplest coupled system, the Chl a dimer, tagged with a quaternary ammonium ion by electrospray ionization. Based on action spectroscopic studies in vacuo, the dimer complexes were found to absorb 50-70 meV to the red of the monomers under the same conditions. First-principles calculations predict shifts that somewhat depend on the relative orientation of the two Chl units, namely 50 and 30 meV for structures where the Chl rings are stacked and unstacked, respectively. Our work demonstrates that Chl association alone can produce a large portion of the color shift observed in photosynthetic macromolecular assemblies.

Isotope Labeling Study of Retinal Chromophore Fragmentation

Previous studies have shown that the gas-phase fragmentation of the retinal chromophore after S0-S1 photoexcitation results in a prominent fragment of mass 248 which cannot be explained by the cleavage of any single bond along the polyene chain. It was therefore theorized that the fragmentation mechanism involves a series of isomerizations and cyclization processes, and two mechanisms for these processes were suggested. Here we used isotope labeling MS-MS to provide conclusive support for the fragmentation mechanism suggested by Coughlan et al. (J. Phys. Chem. Lett. 2014, 5, 3195).

Sidebands from longitudinal bunch oscillations in an electrostatic ion beam trap

Sidebands are observed in the Fourier transform of the pickup signal of an RF-bunched beam oscillating in an electrostatic ion beam trap. We show that the sidebands are dominated by a collective longitudinal oscillation of the center of the bunch around the synchronous ion as the bunch travels within the storage device. We present evidence for a linear dependence of the sideband frequency and for a seemingly chaotic behavior of the amplitude of the sideband peaks on the number of stored ions.

Electrostatic ion beam trap

The conventional way of trapping ions is based on the uses of RF or magnetic fields, like in Paul or Penning traps. In such traps the ions are stored with approximately zero kinetic energy. In many applications a well-defined ion beam is needed especially in collision experiment, where the initial direction of a beam is critical for reaction product measurements and a well defined field free region is required at the collision place. In the last few years we have developed a new type of electrostatic ion trap for ion beams of a few keV per charge, with no mass limit. The ions are injected through a stack of electrodes, which are used as an electrostatic mirror. The ions are confined in a region of few tens of centimeters by two electrostatic mirrors, located on opposite sides. The stability criterion of such a trap can be demonstrated to be similar to the one existing for optical resonator. The dynamics of such trapped ion beam was studied for various potentials on the electrostatic mirrors. Two modes of operation were found. In the first mode a self bunching effect was observed where the ion-ion Coulomb interaction generates a single bunch with constant length along the whole trapping time. This mode of operation can be used for Fourier mass spectrometry. A second mode, where the Coulomb interaction enhances the correlation between the ion position and momentum, enables phase space manipulation of the stored ion beam.