Orla Kelly

LIAD-fs scheme for studies of ultrafast laser interactions with gas phase biomolecules.

Laser induced acoustic desorption (LIAD) has been used for the first time to study the parent ion production and fragmentation mechanisms of a biological molecule in an intense femtosecond (fs) laser field. The photoacoustic shock wave generated in the analyte substrate (thin Ta foil) has been simulated using the hydrodynamic HYADES code, and the full LIAD process has been experimentally characterised as a function of the desorption UV-laser pulse parameters. Observed neutral plumes of densities >10(9) cm(-3) which are free from solvent or matrix contamination demonstrate the suitability and potential of the source for studying ultrafast dynamics in the gas phase using fs laser pulses. Results obtained with phenylalanine show that through manipulation of fundamental femtosecond laser parameters (such as pulse length, intensity and wavelength), energy deposition within the molecule can be controlled to allow enhancement of parent ion production or generation of characteristic fragmentation patterns. In particular by reducing the pulse length to a timescale equivalent to the fastest vibrational periods in the molecule, we demonstrate how fragmentation of the molecule can be minimised whilst maintaining a high ionisation efficiency.

A comb-sampling method for enhanced mass analysis in linear electrostatic ion traps

In this paper an algorithm for extracting spectral information from signals containing a series of narrow periodic impulses is presented. Such signals can typically be acquired by pickup detectors from the image-charge of ion bunches oscillating in a linear electrostatic ion trap, where frequency analysis provides a scheme for high-resolution mass spectrometry. To provide an improved technique for such frequency analysis, we introduce the CHIMERA algorithm (Comb-sampling for High-resolution IMpulse-train frequency ExtRAaction). This algorithm utilizes a comb function to generate frequency coefficients, rather than using sinusoids via a Fourier transform, since the comb provides a superior match to the data. This new technique is developed theoretically, applied to synthetic data, and then used to perform high resolution mass spectrometry on real data from an ion trap. If the ions are generated at a localized point in time and space, and the data is simultaneously acquired with multiple pickup rings, the method is shown to be a significant improvement on Fourier analysis. The mass spectra generated typically have an order of magnitude higher resolution compared with that obtained from fundamental Fourier frequencies, and are absent of large contributions from harmonic frequency components.

Determination of absolute ion yields from a MALDI source through calibration of an image-charge detector

MALDI (matrix-assisted laser desorption/ionization) is one of the most important techniques used to produce large biomolecular ions in the gas phase. Surprisingly, the exact ionization mechanism is still not well understood and absolute values for the ion yields are scarce. This is in part due to the unknown efficiencies of typical detectors, especially for heavy biomolecular ions. As an alternative, charged particles can be non-destructively detected using an image-charge detector where the output voltage signal is proportional to the total charge within the device. In this paper, we report an absolute calibration which provides the voltage output per detected electronic charge in our experimental arrangement. A minimum of 3 × 103 ions were required to distinguish the signal above background noise in a single pass through the device, which could be further reduced using filtering techniques. The calibration results have been applied to raw MALDI spectra to measure absolute ion yields of both matrix and analyte ions.

Short pulse laser-induced dissociation of vibrationally cold, trapped molecular ions

An electrostatic trapping scheme for use in the study of light-induced dissociation of molecular ions is outlined. We present a detailed description of the electrostatic reflection storage device and specifically demonstrate its use in the preparation of a vibrationally cold ensemble of deuterium hydride (HD+) ions. By interacting an intense femtosecond laser with this target and detecting neutral fragmentation products, we are able to elucidate previously inaccessible dissociation dynamics for fundamental diatomics in intense laser fields. In this context, we present new results of intense field dissociation of HD+ which are interpreted in terms of recent theoretical calculations.

Ultrafast science and development at the Artemis facility

The Artemis facility for ultrafast XUV science is constructed around a high average power carrier-envelope phasestabilised system, which is used to generate tuneable pulses across a wavelength range spanning the UV to the far infrared, few-cycle pulses at 800nm and short pulses of XUV radiation produced through high harmonic generation. The XUV pulses can be delivered to interaction stations for materials science and atomic and molecular physics and chemistry through two vacuum beamlines for broadband XUV or narrow-band tuneable XUV pulses. The novel XUV monochromator provides bandwidth selection and tunability while preserving the pulse duration to within 10 fs. Measurements of the XUV pulse duration using an XUV-pump IR-probe technique demonstrate that the XUV pulselength is below 30 fs for a 28 fs drive laser pulse. The materials science station, which contains a hemispherical electron analyser and five-axis manipulator cooled to 14K, is optimised for photoemission experiments with the XUV. The end-station for atomic and molecular physics and chemistry includes a velocity-map imaging detector and molecular beam source for gas-phase experiments. The facility is now fully operational and open to UK and European users for twenty weeks per year. Some of the key new scientific results obtained on the facility include: the extension of HHG imaging spectroscopy to the mid-infrared; a technique for enhancing the conversion efficiency of the XUV by combining two laser fields with non-harmonically related wavelengths; and observation of D3+ photodissociation in intense laser fields.

Femtosecond lasers for mass spectrometry: Proposed application to catalytic hydrogenation of butadiene

Mass spectra from the interaction of intense, femtosecond laser pulses with 1,3-butadiene, 1-butene, and n-butane have been obtained. The proportion of the fragment ions produced as a function of intensity, pulse length, and wavelength was investigated. Potential mass spectrometry applications, for example in the analysis of catalytic reaction products, are discussed.

Fragmentation of Neutral Amino Acids and Small Peptides by Intense, Femtosecond Laser Pulses

AbstractHigh power femtosecond laser pulses have unique properties that could lead to their application as ionization or activation sources in mass spectrometry. By concentrating many photons into pulse lengths approaching the timescales associated with atomic motion, very strong electric field strengths are generated, which can efficiently ionize and fragment molecules without the need for resonant absorption. However, the complex interaction between these pulses and biomolecular species is not well understood. To address this issue, we have studied the interaction of intense, femtosecond pulses with a number of amino acids and small peptides. Unlike previous studies, we have used neutral forms of these molecular targets, which allowed us to investigate dissociation of radical cations without the spectra being complicated by the action of mobile protons. We found fragmentation was dominated by fast, radical-initiated dissociation close to the charge site generated by the initial ionization or from subsequent ultrafast migration of this charge. Fragments with lower yields, which are useful for structural determinations, were also observed and attributed to radical migration caused by hydrogen atom transfer within the molecule. Figureᅟ

Effects of Charge Location on the Absorptions and Lifetimes of Protonated Tyrosine Peptides in Vacuo

Nearby charges affect the electronic energy levels of chromophores, with the extent of the effect being determined by the magnitude of the charge and degree of charge-chromophore separation. The molecular configuration dictates the charge-chromophore distance. Hence, in this study, we aim to assess how the location of the charge influences the absorption of a set of model protonated and diprotonated peptide ions, and whether spectral differences are large enough to be identified. The studied ions were the dipeptide YK, the tripeptide KYK (Y = tyrosine; K = lysine) and their complexes with 18-crown-6-ether (CE). The CE targets the ammonium group by forming internal ionic hydrogen bonds and limits the folding of the peptide. In the tripeptide, the distance between the chromophore and the backbone ammonium is enlarged relative to that in the dipeptide. Experiments were performed in an electrostatic ion storage ring using a tunable laser system, and action spectra based on lifetime measurements were obtained in the range from 210 to 310 nm. The spectra are all quite similar though there seems to be some changes in the absorption band between 210 and 250 nm, while in the lower energy band all ions had a maximum absorption at ~275 nm. Lifetimes after photoexcitation were found to shorten upon protonation and lengthen upon CE complexation, in accordance with the increased number of degrees of freedom and an increase in activation energies for dissociation as the mobile proton model is no longer operative.

Photodissociation of D-3(+) in an intense, femtosecond laser field

H+3 is the simplest triatomic molecule and plays an important role in laboratory and astrophysical plasmas. It is very stable both in terms of its electronic and nuclear degrees of freedom but is difficult to study in depth in the laboratory due to its ionic nature. In this communication, experimental results are presented for the strong field dissociation of the isotopic analogue D+3, using 30 fs, 800 nm laser pulses with intensities up to 1016 W cm−2. By employing a novel experimental set-up, ions were confined in an electrostatic ion trap so that dissociation of the molecule could be studied as it radiatively cools. It was determined that dissociation could only be observed for molecules in ro-vibrational states relatively close to the dissociation limit, while more tightly bound states demonstrated remarkable stability in even the strongest fields.

Ionisation and Fragmentation of Small Biomolecules with Femtosecond LaserPulses

We report on femtosecond laser studies of small biomolecules, produced in the gas phase via laser induced acoustic desorption. In studies of the aromatic amino acid phenylalanine, we have found that the wavelength of the femtosecond pulse can be used to manipulate molecular fragmentation. These preliminary experiments indicate that this technique provides a promising scheme for investigations of ultrafast dynamics in complex molecules. Future studies should enable temporally resolved observations, by employing ultrafast pump-probe techniques.