VUV to IR Emission Spectroscopy and Interferometry Diagnostics for the European Shock Tube for High-Enthalpy Research.

The European Shock Tube for High-Enthalpy Research is a new state-of-the-art facility, tailored for the reproduction of spacecraft planetary entries in support of future European exploration missions, developed by an international consortium led by Instituto de Plasmas e Fusão Nuclear and funded by the European Space Agency. Deployed state-of-the-art diagnostics include vacuum-ultraviolet to ultraviolet, visible, and mid-infrared optical spectroscopy setups, and a microwave interferometry setup. This work examines the specifications and requirements for high-speed flow measurements, and discusses the design choices for the main diagnostics. The spectroscopy setup covers a spectral window between 120 and 5000 nm, and the microwave interferometer can measure electron densities up to 1.5 × 1020 electrons/m3. The main design drivers and technological choices derived from the requirements are discussed in detail herein.

Capabilities of time-resolved X-ray excited optical luminescence of the Taiwan Photon Source 23A X-ray nanoprobe beamline.

Time-resolved X-ray excited optical luminescence (TR-XEOL) was developed successfully for the 23A X-ray nanoprobe beamline located at the Taiwan Photon Source (TPS). The advantages of the TR-XEOL facility include (i) a nano-focused X-ray beam (<60 nm) with excellent spatial resolution and (ii) a streak camera that can simultaneously record the XEOL spectrum and decay time. Three time spans, including normal (30 ps to 2 ns), hybrid (30 ps to 310 ns) and single (30 ps to 1.72 µs) bunch modes, are available at the TPS, which can fulfil different experimental conditions involving samples with various lifetimes. It is anticipated that TR-XEOL at the TPS X-ray nanoprobe could provide great characterization capabilities for investigating the dynamics of photonic materials.

Red shift in the spectrum of a chlorophyll species is essential for the drought-induced dissipation of excess light energy in a poikilohydric moss, Bryum argenteum.

Some mosses are extremely tolerant of drought stress. Their high drought tolerance relies on their ability to effectively dissipate absorbed light energy to heat under dry conditions. The energy dissipation mechanism in a drought-tolerant moss, Bryum argenteum, has been investigated using low-temperature picosecond time-resolved fluorescence spectroscopy. The results are compared between moss thalli samples harvested in Antarctica and in Japan. Both samples show almost the same quenching properties, suggesting an identical drought tolerance mechanism for the same species with two completely different habitats. A global target analysis was applied to a large set of data on the fluorescence-quenching dynamics for the 430-nm (chlorophyll-a selective) and 460-nm (chlorophyll-b and carotenoid selective) excitations in the temperature region from 5 to 77 K. This analysis strongly suggested that the quencher is formed in the major peripheral antenna of photosystem II, whose emission spectrum is significantly broadened and red-shifted in its quenched form. Two emission components at around 717 and 725 nm were assigned to photosystem I (PS I). The former component at around 717 nm is mildly quenched and probably bound to the PS I core complex, while the latter at around 725 nm is probably bound to the light-harvesting complex. The dehydration treatment caused a blue shift of the PS I emission peak via reduction of the exciton energy flow to the pigment responsible for the 725 nm band.

Comparison of excitation energy transfer in cyanobacterial photosystem I in solution and immobilized on conducting glass.

Excitation energy transfer in monomeric and trimeric forms of photosystem I (PSI) from the cyanobacterium Synechocystis sp. PCC 6803 in solution or immobilized on FTO conducting glass was compared using time-resolved fluorescence. Deposition of PSI on glass preserves bi-exponential excitation decay of ~4-7 and ~21-25 ps lifetimes characteristic of PSI in solution. The faster phase was assigned in part to photochemical quenching (charge separation) of excited bulk chlorophylls and in part to energy transfer from bulk to low-energy (red) chlorophylls. The slower phase was assigned to photochemical quenching of the excitation equilibrated over bulk and red chlorophylls. The main differences between dissolved and immobilized PSI (iPSI) are: (1) the average excitation decay in iPSI is about 11 ps, which is faster by a few ps than for PSI in solution due to significantly faster excitation quenching of bulk chlorophylls by charge separation (~10 ps instead of ~15 ps) accompanied by slightly weaker coupling of bulk and red chlorophylls; (2) the number of red chlorophylls in monomeric PSI increases twice-from 3 in solution to 6 after immobilization-as a result of interaction with neighboring monomers and conducting glass; despite the increased number of red chlorophylls, the excitation decay accelerates in iPSI; (3) the number of red chlorophylls in trimeric PSI is 4 (per monomer) and remains unchanged after immobilization; (4) in all the samples under study, the free energy gap between mean red (emission at ~710 nm) and mean bulk (emission at ~686 nm) emitting states of chlorophylls was estimated at a similar level of 17-27 meV. All these observations indicate that despite slight modifications, dried PSI complexes adsorbed on the FTO surface remain fully functional in terms of excitation energy transfer and primary charge separation that is particularly important in the view of photovoltaic applications of this photosystem.

Monte Carlo simulations of excitation and electron transfer in grana membranes.

Time-resolved fluorescence measurements on grana membranes with instrumental response function of 3 ps reveal faster excitation dynamics (120 ps) than those reported previously. A possible reason for the faster decay may be a relatively low amount of "extra" LHCII trimers per reaction center of Photosystem II. Monte Carlo modeling of excitation dynamics in C2S2M2 form of PSII-LHCII supercomplexes has been performed using a coarse grained model of this complex, constituting a large majority of proteins in grana membranes. The main factor responsible for the fast fluorescence decay reported in this work was the deep trap constituted by the primary charge separated state in the reaction center (950-1090 cm(-1)). This value is critical for a good fit, whereas typical hopping times between antenna polypeptides (from ~4.5 to ~10.5 ps) and reversible primary charge separation times (from ~4 to ~1.5 ps, respectively) are less critical. Consequently, respective mean migration times of excitation from anywhere in the PSII-LHCII supercomplexes to reaction center range from ~30 to ~80 ps. Thus 1/4-2/3 of the ~120-ps average excitation lifetime is necessary for the diffusion of excitation to reaction center, whereas the remaining time is due to the bottle-neck effect of the trap. Removal of 27% of the Lhcb6 apoprotein pool by mutagenesis of DEG5 gene caused the acceleration of the excitation decay from ~120 to ~100 ps. This effect may be due to the detachment of LHCII-M trimers from PSII-LHCII supercomplexes, accompanied by deepening of the reaction center trap.

Excitation dynamics in Photosystem I from Chlamydomonas reinhardtii. Comparative studies of isolated complexes and whole cells.

Identical time-resolved fluorescence measurements with ~3.5-ps resolution were performed for three types of PSI preparations from the green alga, Chlamydomonas reinhardtii: isolated PSI cores, isolated PSI-LHCI complexes and PSI-LHCI complexes in whole living cells. Fluorescence decay in these types of PSI preparations has been previously investigated but never under the same experimental conditions. As a result we present consistent picture of excitation dynamics in algal PSI. Temporal evolution of fluorescence spectra can be generally described by three decay components with similar lifetimes in all samples (6-8ps, 25-30ps, 166-314ps). In the PSI cores, the fluorescence decay is dominated by the two fastest components (~90%), which can be assigned to excitation energy trapping in the reaction center by reversible primary charge separation. Excitation dynamics in the PSI-LHCI preparations is more complex because of the energy transfer between the LHCI antenna system and the core. The average trapping time of excitations created in the well coupled LHCI antenna system is about 12-15ps longer than excitations formed in the PSI core antenna. Excitation dynamics in PSI-LHCI complexes in whole living cells is very similar to that observed in isolated complexes. Our data support the view that chlorophylls responsible for the long-wavelength emission are located mostly in LHCI. We also compared in detail our results with the literature data obtained for plant PSI.

Picosecond-resolved X-ray absorption spectroscopy at low signal contrast using a hard X-ray streak camera.

A picosecond-resolving hard-X-ray streak camera has been in operation for several years at Sector 7 of the Advanced Photon Source (APS). Several upgrades have been implemented over the past few years to optimize integration into the beamline, reduce the timing jitter, and improve the signal-to-noise ratio. These include the development of X-ray optics for focusing the X-rays into the sample and the entrance slit of the streak camera, and measures to minimize the amount of laser light needed to generate the deflection-voltage ramp. For the latter, the photoconductive switch generating the deflection ramp was replaced with microwave power electronics. With these, the streak camera operates routinely at 88 MHz repetition rate, thus making it compatible with all of the APS fill patterns including use of all the X-rays in the 324-bunch mode. Sample data are shown to demonstrate the performance.

X-rays only when you want them: optimized pump-probe experiments using pseudo-single-bunch operation.

Laser pump-X-ray probe experiments require control over the X-ray pulse pattern and timing. Here, the first use of pseudo-single-bunch mode at the Advanced Light Source in picosecond time-resolved X-ray absorption experiments on solutions and solids is reported. In this mode the X-ray repetition rate is fully adjustable from single shot to 500 kHz, allowing it to be matched to typical laser excitation pulse rates. Suppressing undesired X-ray pulses considerably reduces detector noise and improves signal to noise in time-resolved experiments. In addition, dose-induced sample damage is considerably reduced, easing experimental setup and allowing the investigation of less robust samples. Single-shot X-ray exposures of a streak camera detector using a conventional non-gated charge-coupled device (CCD) camera are also demonstrated.

Monitoring the photochemistry of a formazan over 15 orders of magnitude in time.

2,3,5-triphenyltetrazolium chloride (TTC) may convert into phenyl-benzo[c]tetrazolocinnolium chloride (PTC) and 1,3,5-triphenylformazan (TPF) under irradiation with light. The latter reaction, albeit enzymatically rather than photochemically, is used in so-called TTC assays indicating cellular respiration and cell growth. In this paper, we address the photochemistry of TPF with time-resolved spectroscopy on various time scales. TPF is stabilized by an intramolecular hydrogen bond and switches photochemically via an E-Z isomerization around an N=N double bond into another TPF-stereoisomer, from which further isomerizations around the C=N double bond of the phenylhydrazone group are possible. We investigate the underlying processes by time-resolved spectroscopy in dependence on excitation wavelength and solvent environment, resolving several intermediates over a temporal range spanning 15 orders of magnitude (hundreds of femtoseconds to hundreds of seconds) along the reaction path. In a quantum-chemical analysis, we identify 16 stable ground-state isomers and discuss which ones are identified in the experimental data. We derive a detailed scheme how these species are thermally and photochemically interconnected and conclude that proton transfer processes are involved.

Parallelized shifted-excitation Raman difference spectroscopy for fluorescence rejection in a temporary varying system.

A fluorescence background is one of the common interference factors of the Raman spectroscopic analysis in the biology field. Shifted-excitation Raman difference spectroscopy (SERDS), in which a slow (typically 1 Hz) modulation to excitation wavelength is coupled with a sequential acquisition of alternating shifted-excitation spectra, has been used to separate Raman scattering from excitation-shift insensitive background. This sequential method is susceptible to spectral change and thus is limited only to stable samples. We incorporated a fast laser modulation (200 Hz) and a mechanical streak camera into SERDS to effectively parallelize the SERDS measurement in a single exposure. The developed system expands the scope of SERDS to include temporary varying system. The proof of concept is demonstrated using highly fluorescent samples, including living algae. Quantitative performance in fluorescence rejection and the robustness of the method to the dynamic spectral change during the measurement are manifested.

An electron energy loss spectrometer based streak camera for time resolved TEM measurements.

We propose an experimental setup based on a streak camera approach inside an energy filter to measure time resolved properties of materials in the transmission electron microscope (TEM). In order to put in place the streak camera, a beam sweeper was built inside an energy filter. After exciting the TEM sample, the beam is swept across the CCD camera of the filter. We describe different parts of the setup at the example of a magnetic measurement. This setup is capable to acquire time resolved diffraction patterns, electron energy loss spectra (EELS) and images with total streaking times in the range between 100ns and 10µs.

Characterization of Chromatic Dispersion and Refractive Index of Polymer Optical Fibers.

The chromatic dispersion and the refractive index of poly(methyl methacrylate) polymer optical fibers (POFs) have been characterized in this work by using a tunable femtosecond laser and a Streak Camera. The characterization technique is based on the measurement of the time delays of light pulses propagating along POFs at different wavelengths. Polymer fibers of three different lengths made by two manufacturers have been employed for that purpose, and discrepancies lower than 3% have been obtained in all cases.