Soft X-ray harmonic comb from relativistic electron spikes

We demonstrate a new high-order harmonic generation mechanism reaching the "water window" spectral region in experiments with multiterawatt femtosecond lasers irradiating gas jets. A few hundred harmonic orders are resolved, giving mu J/sr pulses. Harmonics are collectively emitted by an oscillating electron spike formed at the joint of the boundaries of a cavity and bow wave created by a relativistically self-focusing laser in underdense plasma. The spike sharpness and stability are explained by catastrophe theory. The mechanism is corroborated by particle-in-cell simulations.

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 review on the use of corneal implants for the treatment of presbyopia

In recent years there has seen an increased interest in refractive surgery for the correction of presbyopia. This can be attributed to a number of factors such as the increased demand from patients to have perfect vision without the need for glasses, spurred on by the success of high street refractive laser surgery. Also the World Health Organisation (WHO) estimated in 2005 that over a 1.04 billion people worldwide are affected by presbyopia (Holden et al. 2008). This vast number of people is valued as a potential market and is a huge enticement to the ophthalmic industry to try and develop devices and products to treat this condition. Recent advances in technology have renewed interest in the implantation of corneal inlays for surgical treatment of presbyopia. Dexl et al. (2011) suggest that the reason for this is the further development of biomaterial technology, advances in femtosecond laser and the need for a reversible presbyopic treatment.

Harmonic generation and wave mixing in nonlinear metamaterials and photonic crystals (Invited paper)

The basic concepts and phenomenology of wave mixing and harmonic generation are reviewed in context of the recent advances in the enhanced nonlinear activity in metamaterials and photonic crystals. The effects of dispersion, field confinement and phase synchronism are illustrated by the examples of the on-purpose designed artificial nonlinear structures. (c) 2012 Wiley Periodicals, Inc. Int J RF and Microwave CAE 22:469482, 2012.

High order harmonics from relativistic electron spikes

A new regime of relativistic high-order harmonic generation has been discovered (Pirozhkov 2012 Phys. Rev. Lett. 108 135004). Multi-terawatt relativistic-irradiance (>1018 W cm−2) femtosecond (~30–50 fs) lasers focused to underdense (few × 1019 cm−3) plasma formed in gas jet targets produce comb-like spectra with hundreds of even and odd harmonic orders reaching the photon energy of 360 eV, including the 'water window' spectral range. Harmonics are generated either by linearly or circularly polarized pulses from the J-KAREN (KPSI, JAEA) and Astra Gemini (CLF, RAL, UK) lasers. The photon number scalability has been demonstrated with a 120 TW laser, producing 40 μJ sr−1 per harmonic at 120 eV. The experimental results are explained using particle-in-cell simulations and catastrophe theory. A new mechanism of harmonic generation by sharp, structurally stable, oscillating electron spikes at the joint of the boundaries of the wake and bow waves excited by a laser pulse is introduced. In this paper, detailed descriptions of the experiments, simulations and model are provided and new features are shown, including data obtained with a two-channel spectrograph, harmonic generation by circularly polarized laser pulses and angular distribution.

Resonantly Enhanced Multi-Photon Ionization Spectrum of the Neutral Green Fluorescent Protein Chromophore

The photophysics of the green fluorescent protein is governed by the electronic structure of the chromophore at the heart of its β-barrel protein structure. We present the first two-color, resonance-enhanced, multiphoton ionization spectrum of the isolated neutral chromophore in vacuo with supporting electronic structure calculations. We find the absorption maximum to be 3.65 ± 0.05 eV (340 ± 5 nm), which is blue-shifted by 0.5 eV (55 nm) from the absorption maximum of the protein in its neutral form. Our results show that interactions between the chromophore and the protein have a significant influence on the electronic structure of the neutral chromophore during photoabsorption and provide a benchmark for the rational design of novel chromophores as fluorescent markers or photomanipulators.

Near-monochromatic high-harmonic radiation from relativistic laser-plasma interactions with blazed grating surfaces

Intense, femtosecond laser interactions with blazed grating targets are studied through experiment and particle-in-cell (PIC) simulations. The high harmonic spectrum produced by the laser is angularly dispersed by the grating leading to near-monochromatic spectra emitted at different angles, each dominated by a single harmonic and its integer-multiples. The spectrum emitted in the direction of the third-harmonic diffraction order is measured to contain distinct peaks at the 9th and 12th harmonics which agree well with two-dimensional PIC simulations using the same grating geometry. This confirms that surface smoothing effects do not dominate the far-field distributions for surface features with sizes on the order of the grating grooves whilst also showing this to be a viable method of producing near-monochromatic, short-pulsed extreme-ultraviolet radiation.

A table-top laser-based source of short, collimated, ultra-relativistic positron beams

An ultra-relativistic electron beam passing through a thick, high-Z solid target triggers an electromagnetic cascade, whereby a large number of high energy photons and electron-positron pairs are produced. By exploiting this physical process, we present here the first experimental evidence of the generation of ultra-short, highly collimated and ultra-relativistic positron beams following the interaction of a laser-wake field accelerated electron beam with high-Z solid targets. Clear evidence has also been obtained of the generation of GeV electron-positron jets with variable composition depending on the solid target material and thickness. The percentage of positrons in the overall leptonic beam has been observed to vary from a few per cent up to almost fifty per cent, implying a quasi-neutral electron-positron beam. We anticipate that these beams will be of direct relevance to the laboratory study of astrophysical leptonic jets and their interaction with the interstellar medium.

Coherent spectral enhancement of carrier-envelope-phase stable continua with dual-gas high harmonic generation

Attosecond science is enabled by the ability to convert femtosecond near-infrared laser light into coherent harmonics in the extreme ultraviolet spectral range. While attosecond sources have been utilized in experiments that have not demanded high intensities, substantially higher photon flux would provide a natural link to the next significant experimental breakthrough. Numerical simulations of dual-gas high harmonic generation indicate that the output in the cutoff spectral region can be selectively enhanced without disturbing the single-atom gating mechanism. Here, we summarize the results of these simulations and present first experimental findings to support these predictions. (c) 2012 Optical Society of America

Detection Limits of Organic Compounds Achievable with Intense, Short-Pulse Lasers

Many organic molecules have strong absorption bands which can be accessed by ultraviolet short pulse lasers to produce efficient ionization. This resonant multiphoton ionization scheme has already been exploited as an ionization source in time-of-flight mass spectrometers used for environmental trace analysis. In the present work we quantify the ultimate potential of this technique by measuring absolute ion yields produced from the interaction of 267 nm femtosecond laser pulses with the organic molecules indole and toluene, and gases Xe, N2 and O2. Using multiphoton ionization cross sections extracted from these results, we show that the laser pulse parameters required for real-time detection of aromatic molecules at concentrations of one part per trillion in air and a limit of detection of a few attomoles are achievable with presently available commercial laser systems. The potential applications for the analysis of human breath, blood and tissue samples are discussed.

Ultrafast charge dynamics in an amino acid induced by attosecond pulses

In the past few years, attosecond techniques have been implemented for the investigation of ultrafast dynamics in molecules. The generation of isolated attosecond pulses characterized by a relatively high photon flux has opened up new possibilities in the study of molecular dynamics. In this paper, we report on experimental and theoretical results of ultrafast charge dynamics in a biochemically relevant molecule, namely, the amino acid phenylalanine. The data represent the first experimental demonstration of the generation and observation of a charge migration process in a complexmolecule, where electron dynamics precede nuclear motion. The application of attosecond technology to the investigation of electron dynamics in biologically relevant molecules represents a multidisciplinary work, which can open new research frontiers: those in which few-femtosecond and even subfemtosecond electron processes determine the fate of biomolecules. It can also open new perspectives for the development of new technologies, for example, in molecular electronics, where electron processes on an ultrafast temporal scale are essential to trigger and control the electron current on the scale of the molecule.

LIAD-fs: A novel method for studies of ultrafast processes in gas phase neutral biomolecules

A new experimental technique for femtosecond (fs) pulse studies of gas phase biomolecules is reported. Using Laser-Induced Acoustic Desorption (LIAD) to produce a plume of neutral molecules, a time-delayed fs pulse is employed for ionisation/fragmentation, with subsequent products extracted and mass analysed electrostatically. By varying critical laser pulse parameters, this technique can be used to implement control over molecular fragmentation for a range of small biomolecules, with specific studies of amino acids demonstrated.

Gamma-ray emission in near critical density plasmas at laser intensities of 1021 W/cm2

We study synchrotron radiation emission from laser interaction with near critical density (NCD) plasmas at intensities of 1021 W∕cm2 using three-dimensional particle-in-cell simulations. It is found that the electron dynamics depend on the laser shaping process in NCD plasmas, and thus the angular distribution of the emitted photons changes as the laser pulse evolves in space and time. The final properties of the resulting synchrotron radiation, such as its overall energy, the critical photon energy, and the radiation angular distribution, are strongly affected by the laser polarization and plasma density. By using a 420 TW∕50 fs laser pulse at the optimal plasma density (∼1nc ), about 108 photons/0.1% bandwidth are produced at multi-MeV photon energies, providing a route to ultraintense, femtosecond gamma ray pulses.

Time-resolved four-wave-mixing spectroscopy for inner-valence transitions

Noncollinear four-wave-mixing (FWM) techniques at near-infrared (NIR), visible, and ultraviolet frequencies have been widely used to map vibrational and electronic couplings, typically in complex molecules. However, correlations between spatially localized inner-valence transitions among different sites of a molecule in the extreme ultraviolet (XUV) spectral range have not been observed yet. As an experimental step toward this goal, we perform time-resolved FWM spectroscopy with femtosecond NIR and attosecond XUV pulses. The first two pulses (XUV-NIR) coincide in time and act as coherent excitation fields, while the third pulse (NIR) acts as a probe. As a first application, we show how coupling dynamics between odd- and even-parity, inner-valence excited states of neon can be revealed using a two-dimensional spectral representation. Experimentally obtained results are found to be in good agreement with ab initio time-dependent R-matrix calculations providing the full description of multielectron interactions, as well as few-level model simulations. Future applications of this method also include site-specific probing of electronic processes in molecules.

Phthalocyanines : interaction with carbon structures and as PDT agents

This dissertation describes the synthesis and characterization of different phthalocyanine (Pc) derivatives, as well as some porphyrins (Pors), for supramolecular interaction with different carbon nanostructures, to evaluate their potential application in electronic nanodevices. Likewise, it is also reported the preparation and biological evaluation of interesting phthalocyanine conjugates for cancer photodynamic therapy (PDT) and microorganisms photodynamic inactivation (PDI). The phthalonitrile precursors were prepared from commercial phthalonitriles by nucleophilic substitution of -NO2, -Cl, or -F groups, present in the phthalonitrile core, by thiol or pyridyl units. After the synthesis of these phthalonitriles, the corresponding Pcs were prepared by ciclotetramerization using a metallic salt as template at high temperatures. A second strategy involved the postfunctionalization of hexadecafluorophthalocyaninato zinc(II) through the adequate substituents of mercaptopyridine or cyclodextrin units on the macrocycle periphery. The different compounds were structurally characterized by diverse spectroscopic techniques, namely 1H, 13C and 19F nuclear magnetic resonance spectroscopies (attending the elemental composition of each structure); absorption and emission spectroscopy, and mass spectrometry. For the specific photophysical studies were also used electrochemical characterization, femtosecond and raman spectroscopy, transmission electron and atomic force microscopy. It was highlighted the noncovalent derivatisation of carbon nanostructures, mainly single wall carbon nanotubes (SWNT) and graphene nanosheets with the prepared Pc conjugates to study the photophysical properties of these supramolecular nanoassemblies. Also, from pyridyl-Pors and ruthenium phthalocyanines (RuPcs) were performed Por-RuPcs arrays via coordination chemistry. The results obtained of the novel supramolecular assemblies showed interesting electron donor-acceptor interactions and might be considered attractive candidates for nanotechnological devices. On the other hand, the amphiphilic phthalocyanine-cyclodextrin (Pc-CD) conjugates were tested in biological trials to assess their ability to inhibit UMUC- 3 human bladder cancer cells. The results obtained demonstrated that these photoactive conjugates are highly phototoxic against human bladder cancer cells and could be applied as promising PDT drugs.