Rafael Abela

Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex

X-ray absorption spectroscopy is a powerful probe of molecular structure, but it has previously been too slow to track the earliest dynamics after photoexcitation. We investigated the ultrafast formation of the lowest quintet state of aqueous iron(II) tris(bipyridine) upon excitation of the singlet metal-to-ligand-charge-transfer (1MLCT) state by femtosecond optical pump/x-ray probe techniques based on x-ray absorption near-edge structure (XANES). By recording the intensity of a characteristic XANES feature as a function of laser pump/x-ray probe time delay, we find that the quintet state is populated in about 150 femtoseconds. The quintet state is further evidenced by its full XANES spectrum recorded at a 300-femtosecond time delay. These results resolve a long-standing issue about the population mechanism of quintet states in iron(II)-based complexes, which we identify as a simple 1MLCT→3MLCT→5T cascade from the initially excited state. The time scale of the 3MLCT→5T relaxation corresponds to the period of the iron-nitrogen stretch vibration.

Iodide accumulation provides kelp with an inorganic antioxidant impacting atmospheric chemistry

Brown algae of the Laminariales (kelps) are the strongest accumulators of iodine among living organisms. They represent a major pump in the global biogeochemical cycle of iodine and, in particular, the major source of iodocarbons in the coastal atmosphere. Nevertheless, the chemical state and biological significance of accumulated iodine have remained unknown to this date. Using x-ray absorption spectroscopy, we show that the accumulated form is iodide, which readily scavenges a variety of reactive oxygen species (ROS). We propose here that its biological role is that of an inorganic antioxidant, the first to be described in a living system. Upon oxidative stress, iodide is effluxed. On the thallus surface and in the apoplast, iodide detoxifies both aqueous oxidants and ozone, the latter resulting in the release of high levels of molecular iodine and the consequent formation of hygroscopic iodine oxides leading to particles, which are precursors to cloud condensation nuclei. In a complementary set of experiments using a heterologous system, iodide was found to effectively scavenge ROS in human blood cells.

Hierarchical microimaging for multiscale analysis of large vascular networks

There is a wide range of diseases and normal physiological processes that are associated with alterations of the vascular system in organs. Ex vivo imaging of large vascular networks became feasible with recent developments in microcomputed tomography (microCT). Current methods permit to visualize only limited numbers of physically excised regions of interests (ROIs) from larger samples. We developed a method based on modified vascular corrosion casting (VCC), scanning electron microscopy (SEM), and desktop and synchrotron radiation microCT (SRmicroCT) technologies to image vasculature at increasing levels of resolution, also referred to as hierarchical imaging. This novel approach allows nondestructive 3D visualization and quantification of large microvascular networks, while retaining a precise anatomical context for ROIs scanned at very high resolution. Scans of entire mouse brain VCCs were performed at 16-microm resolution with a desktop microCT system. Custom-made navigation software with a ROI selection tool enabled the identification of anatomical brain structures and precise placement of multiple ROIs. These were then scanned at 1.4-microm voxel size using SRmicroCT and a local tomography setup. A framework was developed for fast sample positioning, precise selection of ROIs, and sequential high-throughput scanning of a large numbers of brain VCCs. Despite the use of local tomography, exceptional image quality was achieved with SRmicroCT. This method enables qualitative and quantitative assessment of vasculature at unprecedented resolution and volume with relatively high throughput, opening new possibilities to study vessel architecture and vascular alterations in models of disease.

Implementation of a fast method for high resolution phase contrast tomography

We report the implementation of a method which can yield the 3D distribution of the phase (refractive index) of a weakly absorbing object from a single tomographic data set. In order to reduce the residual absorption artifact (due to the fact that only one data set is used) the original algorithm presented by A. V. Bronnikov is amended by adding in the filter a factor found by using a semi empirical approach. The quality of the reconstruction is largely sufficient for optimal segmentation and further postprocessing even though the filter correction is based on assumption of constant absorption. This one step approach allows keeping radiation dose to the minimum. Spatial resolution is comparable to the conventional absorption based technique. The performance of the method is validated by using an established phase contrast technique.

A high-repetition rate scheme for synchrotron-based picosecond laser pump/x-ray probe experiments on chemical and biological systems in solution

We present the extension of time-resolved optical pump/x-ray absorption spectroscopy (XAS) probe experiments towards data collection at MHz repetition rates. The use of a high-power picosecond laser operating at an integer fraction of the repetition rate of the storage ring allows exploitation of up to two orders of magnitude more x-ray photons than in previous schemes based on the use of kHz lasers. Consequently, we demonstrate an order of magnitude increase in the signal-to-noise of time-resolved XAS of molecular systems in solution. This makes it possible to investigate highly dilute samples at concentrations approaching physiological conditions for biological systems. The simplicity and compactness of the scheme allows for straightforward implementation at any synchrotron beamline and for a wide range of x-ray probe techniques, such as time-resolved diffraction or x-ray emission studies.

Coherent science at the SwissFEL x-ray laser

The Paul Scherrer Institute is planning the construction of a hard-x-ray free-electron laser, the SwissFEL, by 2016, which will produce intense, ultrashort pulses of transversely coherent radiation in the wavelength range 0.1?7?nm, with future extensions to cover the range 0.08?30?nm. Special design considerations include (a) a compact construction, compatible with the status of a national facility, (b) a uniform 100?Hz repetition rate, well suited to sample manipulations and detector readout, (c) flexible wavelength tuning by the electron beam energy and undulator gaps, (d) soft x-rays at approximately 1?nm wavelength, with circular polarization and Fourier-transform-limited pulses, (e)?hard x-rays of pulse duration 5?20?fs and (f) an independent source of high-energy, half-cycle terahertz pump pulses. The science case for the Swiss FEL project, which emphasizes the dynamics of condensed matter systems and the damage-free imaging of nanostructures, includes novel considerations that make optimal use of these features.

Structural Determination of a Photochemically Active Diplatinum Molecule by Time‐Resolved EXAFS Spectroscopy

Metallica: A large contraction of the Pt-Pt bond in the triplet excited state of the photoreactive [Pt(2)(P(2)O(5)H(2))(4)](4-) ion is determined by time-resolved X-ray absorption spectroscopy (see picture). The strengthening of the Pt-Pt interaction is accompanied by a weakening of the ligand coordination bonds, resulting in an elongation of the platinum-ligand bond that is determined for the first time.

A setup for ultrafast time-resolved x-ray absorption spectroscopy

We present a setup which allows the measurement of time-resolved x-ray absorption spectra with picosecond temporal resolution on liquid samples at the Advanced Light Source at Lawrence Berkeley National Laboratories. The temporal resolution is limited by the pulse width of the synchrotron source. We characterize the different sources of noise that limit the experiment and present a single-pulse detection scheme.

Exploiting EXAFS and XANES for time-resolved molecular structures in liquids

Abstract Time-resolved X-ray absorption fine structure (XAFS) spectroscopy with picosecond temporal resolution is a new method to observe electronic and geometric structures of short-lived reaction intermediates. It combines an intense femtosecond laser source synchronized to the X-ray pulses delivered by a synchrotron Swiss light source (SLS). We present key experiments on charge transfer reactions as well as spin-crossover processes in coordination chemistry compounds next to solvation dynamics studies of photogenerated atomic radicals. These examples emphasize the observables at hand using ultrafast XAFS techniques, which include the density of states, full and even partial changes in oxidation state, and internuclear distances with milli-Angström accuracy. An outlook towards femtosecond studies and biologically relevant systems stresses the high potential of XAFS methods using new femtosecond X-ray sources like free electron lasers (XFELs).

Towards structural dynamics in condensed chemical systems exploiting ultrafast time-resolved x-ray absorption spectroscopy

The authors present the case for exploiting time-resolved x-ray absorption to study structural dynamics in the liq. phase. With this aim in mind and considering the large differences between absorption coeffs. in the optical and the x-ray domains as well as the x-ray absorption cross sections due to unexcited species, the authors have estd. the anticipated signal-to-noise ratio (S/N) under realistic conditions with femtosecond laser pump pulses and synchrotron radiation x-ray probe pulses. As a model system, the authors examine I- photodetachment in H2O and detect the appearance of laser-generated neutral I atoms by their x-ray near-edge absorption structure (XANES) and by their extended x-ray absorption fine structure (EXAFS). While the S/N ratio critically depends on the photolysis yield, which itself is governed by the optical absorption cross section, the optimum sample concn. varies in a complex fashion as a function of pump laser intensity and optical absorption cross section. However, concns. yielding near total absorption of the pump laser deliver quite optimum S/N ratios. The calcns. presented here provide guidelines for the implementation of time-resolved x-ray absorption expts. in condensed phase chem. systems. [on SciFinder (R)]