Research activities at the PALS research infrastructure

The Prague Asterix Laser System (PALS) Research Infrastructure (RI) in Prague, one of only four kJ-class laser facilities in EU, has been offering its beam time to European researchers for already 14 years, since 2004 in the framework of the LASERLAB-Europe consortium. Till June 2014, the PALS RI has provided 4313 experimental days for a total of 41 projects with 303 international users from 42 different research institutions. Its principal experimental facility is a terawatt sub-ns iodine laser (1315?nm) with an optional plasma-based zinc XUV laser (21.2?nm), and an auxiliary Ti:Sapphire fs laser (1?J, 70?fs) exploited for femtosecond plasma probing and experiments with synchronised femtosecond and sub-nanosecond laser pulses at mean laser intensities of up to 30?PW/cm². The lasers are equipped with several target facilities and rich sets of instruments for both active and passive plasma diagnostics. The PALS main research areas include development and applications of secondary laser sources of high-energy ions and both coherent and non-coherent high-intensity XUV radiation, laboratory astrophysical and inertial fusion-relevant studies. In this paper, the main results having been achieved at PALS in the framework of LASERLAB-EUROPE international access activities during the last four years are highlighted.     

Anion–π and Cation–π Interactions on the Same Surface

Herein, we address the question whether anion–π and cation–π interactions can take place simultaneously on the same aromatic surface. Covalently positioned carboxylate–guanidinium pairs on the surface of 4‐amino‐1,8‐naphthalimides are used as an example to explore push–pull chromophores as privileged platforms for such “ion pair–π” interactions. In antiparallel orientation with respect to the push–pull dipole, a bathochromic effect is observed. A red shift of 41 nm found in the least polar solvent is in good agreement with the 70 nm expected from theoretical calculations of ground and excited states. Decreasing shifts with solvent polarity, protonation, aggregation, and parallel carboxylate–guanidinium pairs imply that the intramolecular Stark effect from antiparallel ion pair–π interactions exceeds solvatochromic effects by far. Theoretical studies indicate that carboxylate–guanidinium pairs can also interact with the surfaces of π‐acidic naphthalenediimides and π‐basic pyrenes.     

Measurement of lithium diffusion coefficient in thin metallic multilayer by neutron depth profiling

Diffusion of Li ions in thin sandwich films with copper or lead encompassing layers (obtained by ion beam sputtering deposition technique) has been studied. These metals are promising candidates for electrodes in lithium-ion batteries. It is because they exhibit an ability to store and release Li ions during charging and discharging processes. Lithium diffusion was induced in samples by thermal annealing cycles. The lithium depth profile was measured using a nondestructive neutron depth profiling technique after each thermal annealing step. The analysis of experimental data allowed to evaluate the lithium depth profiles and directly calculate the diffusion coefficients.     

Resistivity and Thermal Expansion (4.2–820 K) of Skutterudites after Severe Plastic Deformation via HPT

Thermoelectric materials with a high figure of merit, ZT, are the essential basis to build thermoelectric generators, which can directly convert heat into electricity. Severe plastic deformation (SPD) via high-pressure torsion (HPT) was successfully applied to enhance ZT of ball-milled and hot-pressed skutterudites as well as to produce bulk nanostructured skutterudites directly from powders. SPD introduces many defects into the sample and in parallel the crystallite size is significantly reduced. During measurement-induced heating these defects anneal partially out, and the grains grow. In this work for the first time systematically the changes of the temperature-dependent electrical resistivity and of thermal expansion were compared. It could be shown that for p- and n-type skutterudites, being hot-pressed and HPT-processed as well as directly HPT-processed from compacted powder, these changes occur more or less simultaneously within the same temperature ranges. This evaluation gives a much deeper insight into the thermoelectric behavior of HPT samples under the influence of changing temperature.     

Light-Activated Carbon Monoxide Prodrugs Based on Bipyridyl Dicarbonyl Ruthenium(II) Complexes

Two photoactivatable dicarbonyl ruthenium(II) complexes based on an amide-functionalised bipyridine scaffold (4-position) equipped with an alkyne functionality or a green-fluorescent BODIPY (boron-dipyrromethene) dye have been prepared and used to investigate their light-induced decarbonylation. UV/Vis, FTIR and ¹³C NMR spectroscopies as well as gas chromatography and multivariate curve resolution alternating least-squares analysis (MCR-ALS) were used to elucidate the mechanism of the decarbonylation process. Release of the first CO molecule occurs very quickly, while release of the second CO molecule proceeds more slowly. In vitro studies using two cell lines A431 (human squamous carcinoma) and HEK293 (human embryonic kidney cells) have been carried out in order to characterise the anti-proliferative and anti-apoptotic activities. The BODIPY-labelled compound allows for monitoring the cellular uptake, showing fast internalisation kinetics and accumulation at the endoplasmic reticulum and mitochondria.     

Nutritional Analysis of Red-Purple and White-Fleshed Pitaya (Hylocereus) Species

Pitaya is one of the most preferred and produced tropical fruit species recently introduced to the Mediterrranean region in Turkey. Due to its nutritional fruits with high economic value, the popularity of pitaya increases steadily in Turkey as an alternative crop. No detailed nutritional analysis has been undertaken in Turkey so far on fruits of the pitaya species. In this study, we determined and compared some nutritional parameters in fruit flesh of two pitaya (dragon fruit) species (Hylocereus polyrhizus: Siyam and Hylocereus undatus: Vietnam Jaina) grown in the Adana province located in the eastern Mediterranean region in Turkey. The individual sugars, antioxidant activity, total phenolic content, phenolic compounds and volatiles were determined for the first time in Turkey on two pitaya species. The results showed that total phenol content and antioxidant capacity are notably higher in red-fleshed fruits than white-fleshed ones and the predominant phenolic compound in fruits of both species was quercetin. The total sugar content and most of the phenolic compounds in fruits of two pitaya species were similar. A total of 51 volatile compounds were detected by using two Solid Phase Micro Extraction (SPME) fibers, coupled with Gas Chromatography Mass Spectrometry (GC-MS) techniques, and more volatile compounds were presented in the white-fleshed species. Total phenolic content (TPC) of the red-fleshed and white-fleshed pitaya species were 16.66 and 17.11 mg GAE/100 g FW (fresh weight). This study provides a first look at the biochemical comparison of red-fleshed and white-fleshed pitaya species introduced and cultivated in Turkey. The results also showed, for the first time, the biochemical content and the potential health benefit of Hylocereus grown in different agroecological conditions, providing important information for pitaya researchers and application perspective.     

Luminescence Properties of New Fused Benzothiophene Derivatives and Their Conductive Oligomers Structural and Solvent Effects

The structural and solvent effects on the electronic absorption and fluorescence spectra, and fluorescence quantum yields, of four new fused benzothiophene derivatives, including benzothieno[3,2b]-thiophene (BTT), benzothieno[3,2-b]benzothiophene (BTBT), 6-methoxy[1]benzothieno[3,2b]-thiophene (MeOBTT), and benzothieno[3,2-b]indole (BTI) were investigated at 295 K. The luminescence properties of the corresponding conductive oligomers, poly(BTT) and poly (MeOBTT), electrosynthesized in acetonitrile, were also studied. Satisfactory McRae, Suppan, and Kawski-Chamma-Viallet solvatochromic correlations were established for the four monomers in most solvents. A weak negative solvatochromic behavior was found for these compounds, indicating that their dipole moments are slightly lower in the excited singlet state than in the ground state. Kamlet-Abboud-Taft multiparametric correlations were also obtained for absorption and fluorescence wave numbers and quantum yields, demonstrating the existence of specific solute-solvent interactions. In the case of the oligomers, important red-shifts of the fluorescence emission maxima ( 90–110 nm) relative to the corresponding monomers were observed, which shows the extent of conjugated segments in the oligomer chains.     

The Pontryagin -form

The unit -planes on which the first Pontryagin form of the Grassmann manifolds achieves its maximum are determined. This is a shorter and unified proof of results first obtained in 1995 by H. Gluck et al. and in 1998 by W. Gu.