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The scope of this paper is to outline the main marks and performances of the MagneDyn beamline, which was designed and built to perform ultrafast magnetodynamic studies in solids. Open to users since 2019, MagneDyn operates with variable circular and linear polarized femtosecond pulses delivered by the externally laser-seeded FERMI free-electron laser (FEL). The very high degree of polarization, the high pulse-to-pulse stability, and the photon energy tunability in the 50-300 eV range allow performing advanced time-resolved magnetic dichroic experiments at the K-edge of light elements, e.g., carbon and at the M- and N-edge of the 3d-transition-metals and rare earth elements, respectively. To this end, two experimental end-stations are available. The first is equipped with an in situ dedicated electromagnet, a cryostat, and an extreme ultraviolet Wollaston-like polarimeter. The second, designed for carry-in user instruments, hosts also a spectrometer for pump-probe resonant x-ray emission and inelastic spectroscopy experiments with a sub-eV energy resolution. A Kirkpatrick-Baez active optics system provides a minimum focus of similar to 20x20 mu m(2) FWHM at the sample. A pump laser setup, synchronized with the FEL-laser seeding system, delivers sub-picosecond pulses with photon energies ranging from the mid-IR to near-UV for optical pump-FEL probe experiments with a minimal pump-probe jitter of few femtoseconds. The overall combination of these features renders MagneDyn a unique state-of-the-art tool for studying ultrafast magnetic and resonant emission phenomena in solids. Published under an exclusive license by AIP Publishing.

The human telomeric G-quadruplex structural motif of DNA has come to be known as a new and stimulating target for anticancer drug discovery. Small molecules that interact with G-quadruplex structures in a selective way have gained impressive interest in recent years as they may serve as potential therapeutic agents. Here, we show how circular dichroism, UV resonance Raman and small angle X-ray scattering spectroscopies can be effectively combined to provide insights into structural and molecular aspects of the interaction between human telomeric quadruplexes and ligands. This study focuses on the ability of berberine and palmatine to bind with human telomeric quadruplexes and provides analysis of the conformational landscape visited by the relevant complexes upon thermal unfolding. With increasing temperature, both free and bound G-quadruplexes undergo melting through a multi-state process, populating different intermediate states. Despite the structural similarity of the two ligands, valuable distinctive features characterising their interaction with the G-quadruplex emerged from our multi-technique approach.

The quality of a sample has always to be considered with respect to its purposes and to the technique used for assessing it. The aim of this work is to point out the most common interfering agents that vibrational spectroscopists may find when analyzing nucleic acids extracted from cellular cultures. Fourier transformed infrared and ultraviolet‐resonant Raman measurements have been carried out on DNA and RNA samples extracted from B16 cell cultures by standard protocols used in molecular biology. The routinely adopted quality control procedure, based on ultraviolet spectrophotometry absorption measurements, could only indicate the absence of protein, phenol, or other contaminants that absorb strongly at or near 280 nm. However, DNA and RNA samples of good quality from a biological perspective clearly showed the presence of chemicals interfering with the vibrational measurements, mainly ethanol and guanidinium salts. Here, we propose fast and inexpensive strategies for tailoring the extraction protocols in light of the requirements of both vibrational spectroscopies that allowed obtaining nucleic acid samples with ethanol concentration below the detection limit of both techniques and with a significantly reduced spectral interference from guanidinium salts.

The advent of extreme ultraviolet (EUV) and soft x-ray free electron lasers (FELs) has enabled nonlinear optical experiments at wavelengths shorter than the visible-UV range. An important class of experiments is those based on the four-wave-mixing (FWM) approach, which are often based on interactions between pulses at different wavelengths. The exploitation of multiple EUV/soft x-ray wavelengths is not straightforward, but it can significantly expand the range of applications. In this manuscript we report on an experimental approach, based on the concomitant use of a non-collinear split-delay-and-recombination unit (“mini-Timer”) and on a two-color seeded FEL emission scheme (“twin-seed mode”). We used a diamond sample for demonstrating the capability of this setup of generating and detecting a FWM signal stimulated by two-color EUV FEL pulses. This approach can be further exploited for developing experimental methods based on non-linear EUV/x-ray optics.

Understanding and controlling the thermal transport at nanoscale is a key ingredient for the development of future nanoelectronical devices. In this study of thin silicon carbide (SiC) membrane we demonstrate the potential of free electron laser extreme ultraviolet (EUV) transient grating (TG) technique as contactless probe for thermoelastic response at length scales of 84 nm, where the Fourier heat diffusion law is no longer valid. The results have revealed that the mechanical behavior of the system can be fully described in the framework of Lamb waves. Moreover, by use of a bidimensional spatial detector to measure the TG signal, a new feature is the observed, time dependence in the emission angle of the transient diffraction, correlated to the transient grating signal intensity.

Optical-domain Transient Grating (TG) spectroscopy is a versatile background-free four-wave-mixing technique used to probe vibrational, magnetic and electronic degrees of freedom in the time domain. The newly developed coherent X-ray Free Electron Laser sources allow its extension to the X-ray regime. Xrays offer multiple advantages for TG: their large penetration depth allows probing the bulk properties of materials, their element-specificity can address core-excited states, and their short wavelengths create excitation gratings with unprecedented momentum transfer and spatial resolution. We demonstrate for the first time TG excitation in the hard X-ray range at 7.1 keV. In Bismuth Germanate (BGO), the nonresonant TG excitation generates coherent optical phonons detected as a function of time by diffraction of an optical probe pulse. This experiment demonstrates the ability to probe bulk properties of materials and paves the way for ultrafast coherent four-wave-mixing techniques using X-ray probes and involving nanoscale TG spatial periods., Comment: 11 pages, 4 figures

The utility of ionic liquids (ILs) as alternative solvents for stabilizing and preserving the native structure of DNA over the long term may be envisaged for biotechnological and biomedical applications in the near future. The delicate balance between the stabilizing and destabilizing effects of IL-mediated interactions with the structure of DNA is complex and is still not well understood. This work reports a fundamental study dealing with the effect exerted by cations and anions in imidazolium-based ILs on the thermal structural stability of large nucleic acid molecules. Multi-wavelength UV resonance Raman spectroscopy is used for selectively detecting heat-induced structural transitions of DNA localized on specific base tracts. Our study reveals the establishment of preferential interactions between the imidazolium cations of ILs and the guanine bases in the DNA groove that lead to more effective stacking between the guanine bases even at high temperatures. Interestingly, we observe that this trend for ILs sharing the same chloride anion is further enhanced as the alkyl chain on the imidazolium cation gets shorter. The results from the present investigation lead to a more comprehensive view of the IL-mediated interactions with A-T and G-C base pairs during thermal unfolding.

Here, we report on the conceptual design, the hardware realization, and the first experimental results of a novel and compact x-ray polarimeter capable of a single-pulse linear polarization angle detection in the extreme ultraviolet photon energy range. The polarimeter is tested by performing time resolved pump-probe experiments on a Ni80Fe20 Permalloy film at the M-2,M-3 Ni edge at an externally seeded free-electron laser source. Comparison with similar experiments reported in the literature shows the advantages of our approach also in view of future experiments.

The development of ultra-bright extreme ultraviolet (EUV) and X-ray free electron laser (FEL) sources has enabled the extension of wave-mixing approaches into the short wavelength regime. Such a class of experiments relies upon nonlinear interactions among multiple light pulses offering a unique tool for exploring the dynamics of ultrafast processes and correlations between selected excitations at relevant length and time scales adding elemental and site selectivity as well. Besides the availability of a suitable photon source, the implementation of wave mixing methodology requires efforts in developing the instrumental set-up. We have realized at the FERMI FEL two dedicated set-ups to handle multiple FEL beams with preselected parameters in a non-collinear fashion and control their interaction sequence at the target. These unique apparatuses, combined with the exceptional characteristics of the seeded FERMI FEL, have allowed us to make the first steps into this field and further advances are foreseen in the near future.

Amyloids are proteinaceous deposits considered an underlying pathological hallmark of several degenerative diseases. The mechanism of amyloid formation and its inhibition still represent challenging issues, especially when protein structure cannot be investigated by classical biophysical techniques as for the intrinsically disordered proteins (IDPs). In this view, the need to find an alternative way for providing molecular and structural information regarding IDPs prompted us to set a novel, to our knowledge, approach focused on UV Resonance Raman (UVRR) spectroscopy. To test its applicability, we study the fibrillation of hen-egg white lysozyme (HEWL) and insulin as well as their interaction with resveratrol, employing also intrinsic fluorescence spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The increasing of the β-sheet structure content at the end of protein fibrillation probed by FTIR occurs simultaneously with a major solvent exposure of tryptophan (Trp) and tyrosine (Tyr) residues of HEWL and insulin, respectively, as revealed by UVRR and intrinsic fluorescence spectroscopy. However, because the latter technique is successfully used when proteins naturally contain Trp residues, it shows poor performances in the case of insulin, and the information regarding its tertiary structure is exclusively provided by UVRR spectroscopy. The presence of an increased concentration of resveratrol induces mild changes in the secondary structure of both protein fibrils while remodeling HEWL fibril length and promoting the formation of amorphous aggregates in the case of insulin. Although the intrinsic fluorescence spectra of proteins are hidden by resveratrol signal, UVRR Trp and Tyr bands are resonantly enhanced, showing a good sensitivity to the presence of resveratrol and marking a modification in the noncovalent interactions in which they are involved. Our findings demonstrate that UVRR is successfully employed in the study of aggregation-prone proteins and of their interaction with ligands, especially in the case of Trp-lacking proteins.

Ultrafast time-resolved extreme ultraviolet (EUV) reflectivity measurements of optically pumped amorphous carbon (a-C) have been performed with the FERMI free electron laser (FEL). This work extends the energy range used in previous reflectivity studies and adds polarization dependence. The EUV probe is known to be sensitive to lattice dynamics, since in this range the reflectivity is essentially unaffected by the photo-excited surface plasma. The exploitation of both s- and p-polarized EUV radiation permits variation of the penetration depth of the probe; a significant increase in the characteristic time is observed upon increasing the probing depth (1 vs. 5 ps) due to hydrodynamic expansion and consequent destruction of the excited region, implying that there is only a short window during which the probed region is in the isochoric regime. A weak wavelength dependence of the reflectivity is found, consistent with previous measurements and implying a maximum electronic temperature of 0.8 eV ± 0.4.

G-Quadruplexes (G4s) are noncanonical nucleic acid structures involved in the regulation of several biological processes of many organisms. The rational design of G4-targeting molecules developed as potential anticancer and antiviral therapeutics is a complex problem intrinsically due to the structural polymorphism of these peculiar DNA structures. The aim of the present work is to show how Ultraviolet Resonance Raman (UVRR) spectroscopy can complement other techniques in providing valuable information about ligand/G4 interactions in solution. Here, the binding of BRACO-19 and Pyridostatin - two of the most potent ligands - to selected biologically relevant G4s was investigated by polarized UVRR scattering at 266 nm. The results give new insights into the binding mode of these ligands to G4s having different sequences and topologies by performing an accurate analysis of peaks assigned to specific groups and their changes upon binding. Indeed, the UVRR data not only show that BRACO-19 and Pyridostatin interact with different G4 sites, but also shed light on the ligand and G4 chemical groups really involved in the interaction. In addition, UVRR results complemented by circular dichroism data clearly indicate that the binding mode of a ligand can also depend on the conformation(s) of the target G4. Overall, these findings demonstrate the utility of using UVRR spectroscopy in the investigation of G4s and G4-ligand interactions in solution.

A liquid carbon ($l$-C) sample is generated through constant volume heating exposing an amorphous carbon foil to an intense ultrashort laser pulse. Time-resolved x-ray absorption spectroscopy at the C $K$ edge is used to monitor the dynamics of the melting process revealing a subpicosecond rearrangement of the electronic structure associated with a sudden change of the C bonding hybridization. The obtained $l$-C sample, resulting from a nonthermal melting mechanism, reaches a transient equilibrium condition with a temperature of about 14 200 K and pressure in the order of 0.5 Mbar in about 0.3 ps, prior to hydrodynamic expansion. A detailed analysis of the atomic and electronic structure in solid-density $l$-C based on time-resolved x-ray absorption spectroscopy and theoretical simulations is presented. The method can be fruitfully used for extending the experimental investigation of the C phase diagram in a vast unexplored region covering the ${10}^{3}--{10}^{4}\text{ }\text{ }\mathrm{K}$ temperature range with pressures up to 1 Mbar.

Cytosine plays a preeminent role in DNA methylation, an epigenetic mechanism that regulates gene expression, the misregulation of which can lead to severe diseases. Several methods are nowadays employed for assessing the global DNA methylation levels, but none of them combines simplicity, high sensitivity, and low operating costs to be translated into clinical applications. Ultraviolet (UV) resonant Raman measurements at excitation wavelengths of 272 nm, 260 nm, 250 nm, and 228 nm have been carried out on isolated deoxynucleoside triphosphates (dNTPs), on a dNTP mixture as well as on genomic DNA (gDNA) samples, commercial from salmon sperm and non-commercial from B16 murine melanoma cell line. The 228 nm excitation wavelength was identified as the most suitable energy for enhancing cytosine signals over the other DNA bases. The UV Raman measurements performed at this excitation wavelength on hyper-methylated and hypo-methylated DNA from Jurkat leukemic T-cell line have revealed significant spectral differences with respect to gDNA isolated from salmon sperm and mouse melanoma B16 cells. This demonstrates how the proper choice of the excitation wavelength, combined with optimized extraction protocols, makes UV Raman spectroscopy a suitable technique for highlighting the chemical modifications undergone by cytosine nucleotides in gDNA upon hyper- and hypo-methylation events.

We will describe a synchrotron-based resonance Raman (RR) instrument working in the ultraviolet (UV) spectral range that exploits the wide and continuously tunable emission of a synchrotron source. This novel spectroscopic facility can address a number of scientific fields ranging from electronic properties of nanostructures and strongly correlated materials to biological macromolecules. Selected case studies will be discussed in order to show the potential of UVRR spectroscopy giving particular emphasis to results obtained on samples of biological interest.

A multi-technique approach, combining circular dichroism spectroscopy, ultraviolet resonance Raman spectroscopy and small angle scattering techniques, has been deployed to elucidate how the structural features of the human telomeric G-quadruplex d[A(GGGTTA)3GGG] (Tel22) change upon thermal unfolding. The system is studied both in the free form and when it is bound to Actinomycin D (ActD), an anticancer ligand with remarkable conformational flexibility. We find that at room temperature binding of Tel22 with ActD involves end-stacking upon the terminal G-tetrad. Structural evidence for drug-driven dimerization of a significant fraction of the G-quadruplexes is provided. When the temperature is raised, both free and bound Tel22 undergo melting through a multi-state process. We show that in the intermediate states of Tel22 the conformational equilibrium is shifted toward the (3+1) hybrid-type, while a parallel structure is promoted in the complex. The unfolded state of the free Tel22 is consistent with a self-avoiding random-coil conformation, whereas the high-temperature state of the complex is observed to assume a quite compact form. Such an unprecedented high-temperature arrangement is caused by the persistent interaction between Tel22 and ActD, which stabilizes compact conformations even in the presence of large thermal structural fluctuations.

Nano-sized TiO2 is widely used as photocatalysts for many applications; however, some aspects in the application in cultural heritage conservation are still unresolved. In particular, in this research, we focused our attention on nanostructured product composed by silica, polydimethylsiloxane (PDMS) and TiO2 nanoparticles. We explored the effect of variable amounts of nanoparticles on the features of coating, since this issue still has some unclear aspects. Several samples of limestone have been treated, and then, analysed. The chromatic variations induced by the treatments have been measured by colorimetric analysis, while the hydrophobic properties of coatings have been evaluated by contact angle measurements and capillary water absorption. The photocatalytic efficiency has been evaluated by methylene blue staining. In addition, two large facilities have been involved in this study, in order to obtain accurate results in a non-invasive way. On one side, middle-UV Raman spectroscopy measurements at IUVS beamline@Elettra (Trieste), by using UV synchrotron radiation (SR) source, revealed successful, with respect to conventional set-up, in order to quantify the amount of the anatase on the surface. On the other side, neutron radiography measurements at RAD Radiography Station@BNC (Budapest) permitted a sensitive monitoring of the water absorption dynamics on untreated and treated samples. (C) 2018 Elsevier Ltd. All rights reserved.

The hydrogen bonding of water and water/salt mixtures around the proline-based tripeptide model glycyl-l-prolyl-glycinamide·HCl (GPG-NH2) is investigated here by multi-wavelength UV resonance Raman spectroscopy (UVRR) to clarify the role of ion–peptide interactions in affecting the conformational stability of this peptide. The unique sensitivity and selectivity of the UVRR technique allow us to efficiently probe the hydrogen bond interaction between water molecules and proline residues in different solvation conditions, along with its influence on trans to cis isomerism in the hydrated tripeptide. The spectroscopic data suggest a relevant role played by the cations in altering the solvation shell at the carbonyl site of proline., while the fluoride and chloride anions were found to promote the establishment of the strongest interactions on the C=O site of proline. This latter effect is reflected in the greater stabilization of the trans conformers of the tripeptide in the presence of these specific ions. The molecular view provided by UVRR experiments was complemented by the results of circular dichroism (CD) measurements that show a strong structural stabilizing effect on the β-turn motif of GPG-NH2 observed in the presence of KF as a co-solute.

UV Resonance Raman (UVRR) scattering offers several advantages with respect to spontaneous Raman one, such as the significant increment of the detection limit and the selectivity needed to incisively monitor specific chromospheres within the sample. Here we present a synchrotron-based Resonance Raman instrument that exploits the wide and continuously tunable UV emission provided by the synchrotron source. As an example, we discuss the solvation dynamics of two model peptides, N-acetyl-leucine-methylamide (NALMA) and N-acetyl-glycine-methylamide (NAGMA), by putting in evidence on the advantages of the use of SR-based UVRR. The experimental results evidence that the fine tuning of the excitation wavelength allows to choose the best working conditions that ensure to reliably detect the spectral changes of the amide signals, as function of concentration and temperature of peptide. The analysis of the spectra provides new insights on the hydrogen-bond interactions at the peptides backbone.

The rapid development of extreme ultraviolet (EUV) and x-ray ultrafast coherent light sources such as free electron lasers (FELs) has triggered the extension of wave-mixing techniques to short wavelengths. This class of experiments, based on the interaction of matter with multiple light pulses through the Nth order susceptibility, holds the promise of combining intrinsic ultrafast time resolution and background-free signal detection with nanometer spatial resolution and chemical specificity. A successful approach in this direction has been the combination of the unique characteristics of the seeded FEL FERMI with dedicated four-wave-mixing (FWM) setups, which leads to the demonstration of EUV-based transient grating (TG) spectroscopy. In this perspective paper, we discuss how the TG approach can be extended toward more general FWM spectroscopies by exploring the intrinsic multiparameter nature of nonlinear processes, which derives from the ability of controlling the properties of each field independently.

Although Deoxyribonucleic acid (DNA) is considered substantially stable in aqueous solution, slow hydrolysis can damage its double-helix structure and cause denaturation when it is stored for several months. Therefore, the design of aqueous solvents that are able to stabilize and maintain DNA conformation is a challenging issue. Ionic liquids (ILs) appear as ideal water co-solvents for DNA biotechnology due to their unique properties. We have investigated the thermal stability of DNA in 1-butyl-3-methylimidazolium aqueous solutions by synchrotron-based UV Resonance Raman (UVRR) spectroscopy with the aim to clarify the role played by concentration of IL in stabilizing the DNA natural conformation. The synchrotron-based UV source for UVRR measurements allows us to enhance specific vibrational signals associated to nitrogenous bases of DNA, through an appropriate tuning of the excitation wavelength. Such approach permits to probe the rearrangements in the local environment around specific nucleotides as a function of thermal conditions.

This work shows that bulk ionic liquids (ILs) and their water solution can be conveniently investigated by synchrotron-based UV resonance Raman (UVRR) spectroscopy. The main advantages of this technique for the investigation of the local structure and intermolecular interactions in imidazolium-based ILs are presented and discussed. The unique tunability of synchrotron source allows one to selectively enhance in the Raman spectra the vibrational signals arising from the imidazolium ring. Such signals showed good sensitivity to the modifications induced in the local structure of ILs by i) the change of anion and ii) the progressively longer alkyl chain substitution on the imidazolium ring. Moreover, some UVRR signals are specifically informative on the effect induced by addition of water on the strength of cation-anion H-bonds in IL-water solutions. All of these results corroborate the potentiality of UVRR to retrieve information on the intermolecular interactions in IL-water solutions, besides the counterpart obtained by employing on these systems the spontaneous Raman scattering technique., Comment: 10 pages, 5 figures

Spatially patterned extreme ultraviolet light pulses can be used for probing multiple dynamical processes at the nanoscale., Advances in developing ultrafast coherent sources operating at extreme ultraviolet (EUV) and x-ray wavelengths allow the extension of nonlinear optical techniques to shorter wavelengths. Here, we describe EUV transient grating spectroscopy, in which two crossed femtosecond EUV pulses produce spatially periodic nanoscale excitations in the sample and their dynamics is probed via diffraction of a third time-delayed EUV pulse. The use of radiation with wavelengths down to 13.3 nm allowed us to produce transient gratings with periods as short as 28 nm and observe thermal and coherent phonon dynamics in crystalline silicon and amorphous silicon nitride. This approach allows measurements of thermal transport on the ~10-nm scale, where the two samples show different heat transport regimes, and can be applied to study other phenomena showing nontrivial behaviors at the nanoscale, such as structural relaxations in complex liquids and ultrafast magnetic dynamics.

Hydrated ionic liquids (ILs) have been identified as solvent media able to enhance the structural stability of deoxyribonucleic acid (DNA). In this work, we investigate the molecular interaction between imidazolium-based ILs and DNA during its thermal unfolding pathway, by exploiting synchrotron-based UV Resonance Raman scattering (UVRR) experiments. This technique gives a selective focus on the thermal responses of specific nucleobases in the structure of DNA, providing the experimental sensitivity to both cooperative and local structural changes occurring along the complex unfolding process of DNA. UVRR measurements probe two distinct temperature-dependent phenomena occurring in the DNA double-helix, i.e. a non-cooperative pre-melting mainly involving adenine bases and a cooperative melting transition primarily localized on guanine tracts. The analysis of Raman spectra reveals that both the cation and anion of the ionic liquids strongly interact with the structure of DNA, thus affecting the melting process but not perturbing the pre-melting transition that precedes the complete separation of the strands of DNA. Overall these results suggest that the dominant interaction occurs between the imidazolium cation and the bases of guanine and thymine in the structure of DNA, in agreement with previous results of molecular dynamics simulations.

Ethanol is an essential chemical reagent in DNA preparation as its use increases the yield of extraction. All methodologies for DNA isolation involve the use of ethanol in order to prevent DNA dissolution in water and to optimize the binding of DNA to chromatographic membranes. In this note, we show how the presence of ethanol traces in DNA aqueous solution affects ultraviolet Raman spectra, leading to possible misinterpretations. We report a simple method to remove the ethanol Raman features from the spectra, based on heating the DNA sample at 80 ℃, followed by a slow cooling procedure.

The response to pH variation of polymeric cyclodextrin-based hydrogels has been investigated by a multi-technique approach based on UV Raman and Brillouin light scattering (BLS) together with Small Angle Neutron Scattering (SANS). By exploiting the complementary information of these three investigation methods, the structural, viscoelastic and molecular modifications of the polymer brought about by the pH changes have been examined, over a spatial range going from mesoscopic to nanoscopic length-scale. The data provide a picture where an increase of pH promotes the change of the characteristic size of the hydrophilic pores when the cross-linker has the suitable structural and acid-base properties, and leads to the reinforcement of the polymer domains interconnections, providing a stiffer gel network on the length-scale probed by BLS. Raman signals are sensitive both to structural changes of the polymer network and to changes of the intermolecular ordering of water due to solvent-polymer interactions. The destructuring effect on the tetrahedral ice-like configurations of water is especially evident at high pH, and might be ascribed to an increased exposition to the solvent of the ionic portions of the polymer surface.

Experimental approaches based on nonlinear optical processes (wave-mixing) have allowed major breakthroughs in diverse fields of science and technology. Nevertheless, these concepts were restricted to the optical regime due to the lack of coherent photon sources of sufficient peak brightness at sub-optical wavelengths. Nowadays, while the development of free electron lasers (FELs) potentially allows extreme ultraviolet (EUV) and X-ray wave-mixing, their full exploitation still requires efforts in instrumentation developments. The need to control (both in the spatial and temporal coordinates) multiple FEL input pulses, which may have different photon frequencies and polarizations, calls for the developments of instruments with a higher degree of complexity with respect to those typically used at synchrotron and FEL beamlines. Here we report on the progresses in the development of such kind of instrumentation at the FERMI FEL facility. Our FEL-based wave-mixing setups rely upon the transient grating (TG) approach, which represents a relevant benchmark for the development of advanced EUV/soft x-ray four-wave-mixing (FWM) experiments, as for instance coherent Raman scattering and multi-dimensional spectroscopy. © 2018 Elsevier B.V.

© 2018 American Physical Society. Nonlinear optical processes at soft x-ray wavelengths have remained largely unexplored due to the lack of available light sources with the requisite intensity and coherence. Here we report the observation of soft x-ray second harmonic generation near the carbon K edge (∼284 eV) in graphite thin films generated by high intensity, coherent soft x-ray pulses at the FERMI free electron laser. Our experimental results and accompanying first-principles theoretical analysis highlight the effect of resonant enhancement above the carbon K edge and show the technique to be interfacially sensitive in a centrosymmetric sample with second harmonic intensity arising primarily from the first atomic layer at the open surface. This technique and the associated theoretical framework demonstrate the ability to selectively probe interfaces, including those that are buried, with elemental specificity, providing a new tool for a range of scientific problems.

We have examined the transmission of soft X-ray pulses from the FERMI free electron laser through carbon films of varying thickness, quantifying nonlinear effects of pulses above and below the carbon K-edge. At typical of soft X-ray free electron laser intensities, pulses exhibit linear absorption at photon energies above and below the K-edge, ∼308 and ∼260 eV, respectively; whereas two-photon absorption becomes significant slightly below the K-edge, ∼284.2 eV. The measured two-photon absorption cross section at 284.18 eV (∼6 × 10−48 cm4 s) is 7 orders of magnitude above what is expected from a simple theory based on hydrogen-like atoms – a result of resonance effects.

We report on ultraviolet resonance Raman scattering experiments carried out on two model substances: histidine and acetamide using a UV synchrotron radiation source. In the case of aqueous histidine solution each protonated state of histidine tautomers was selectively excited by tuning the incident wavelength and the vibrational state of each protonated state was studied. We also demonstrated that the local pH condition of histidine can be identified directly from the spectra above pH 9. In the case of acetamide, the resonance Raman bands of acetamide with a stronger hydrogen bond at the NH2 site and weaker hydrogen bond at the C=O site were selectively observed. These findings will extend the selectivity and sensitivity of RR spectroscopy that is helpful to understanding protein functionality.

Four-wave mixing processes are achieved at suboptical wavelengths by using a free-electron laser as a source to generate extreme ultraviolet pulses that produce transient gratings. The phenomenon of four-wave mixing (FWM) occurs when two wavelengths of light interact to produce two extra wavelengths in the signal. It has been exploited in many optics technologies, from optical fibre communication to spectroscopy. Until now FWM has been limited to optical wavelengths. Here Filippo Bencivenga et al. show how to stimulate four-wave mixing processes at suboptical wavelengths using the FERMI free-electron laser as a source to generate extreme ultraviolet pulses that produce transient gratings. The extension of FWM to shorter wavelengths — combined with new developments in free-electron lasers — promises higher resolution for many techniques and the possibility of probe excitations to higher energies. Four-wave mixing (FWM) processes, based on third-order nonlinear light–matter interactions, can combine ultrafast time resolution with energy and wavevector selectivity, and enable the exploration of dynamics inaccessible by linear methods1,2,3,4,5,6,7. The coherent and multi-wave nature of the FWM approach has been crucial in the development of advanced technologies, such as silicon photonics8, subwavelength imaging9 and quantum communications10. All these technologies operate at optical wavelengths, which limits the spatial resolution and does not allow the probing of excitations with energy in the electronvolt range. Extension to shorter wavelengths—that is, the extreme ultraviolet and soft-X-ray ranges—would allow the spatial resolution to be improved and the excitation energy range to be expanded, as well as enabling elemental selectivity to be achieved by exploiting core resonances5,6,7,11,12,13,14. So far, FWM applications at such wavelengths have been prevented by the absence of coherent sources of sufficient brightness and of suitable experimental set-ups. Here we show how transient gratings, generated by the interference of coherent extreme-ultraviolet pulses delivered by the FERMI free-electron laser15, can be used to stimulate FWM processes at suboptical wavelengths. Furthermore, we have demonstrated the possibility of observing the time evolution of the FWM signal, which shows the dynamics of coherent excitations as molecular vibrations. This result opens the way to FWM with nanometre spatial resolution and elemental selectivity, which, for example, would enable the investigation of charge-transfer dynamics5,6,7. The theoretical possibility of realizing these applications has already stimulated ongoing developments of free-electron lasers16,17,18,19,20: our results show that FWM at suboptical wavelengths is feasible, and we hope that they will enable advances in present and future photon sources.

The molecular mechanism responsible for the thermosensitive behaviour exhibited by pH-responsive cyclodextrin-based hydrogels is explored here with the twofold aim of clarifying some basic aspects of H-bond interactions in hydrogel phases and contributing to a future engineering of cyclodextrin hydrogels for targeted delivery and release of bioactive agents. The degree of H-bond association of water molecules entrapped in the gel network and the extent of intermolecular interactions involving the hydrophobic/hydrophilic moieties of the polymer matrix are probed by UV Raman and IR experiments, in order to address the question of how these different and complementary aspects combine to determine the pH-dependent thermal activation exhibited by these hydrogels. Complementary vibrational spectroscopies are conveniently employed in this study with the aim of safely disentangling the spectral response arising from the two main components of the hydrogel systems, i.e. the polymer matrix and water solvent. The experimental evidence suggests that the dominant effects in the mechanism of solvation of cyclodextrin-based hydrogels are due to the changes occurring, upon increasing of temperature, in the hydrophobicity character of specific chemical moieties of the polymer, as triggered by pH variations. The achievements of this work corroborate the potentiality of the UV Raman scattering technique, in combination with more conventional IR experiments, to provide a "molecular view" of complex macroscopic phenomena exhibited in hydrogel phases.

Time-resolved investigations have begun a new era of chemistry and physics, enabling the monitoring in real time of the dynamics of chemical reactions and matter. Induced transient optical absorption is a basic ultrafast electronic effect, originated by a partial depletion of the valence band, that can be triggered by exposing insulators and semiconductors to sub-picosecond extreme-ultraviolet pulses. Besides its scientific and fundamental implications, this process is very important as it is routinely applied in free-electron laser (FEL) facilities to achieve the temporal superposition between FEL and optical laser pulses with tens of femtoseconds accuracy. Here, a set of methodologies developed at the FERMI facility based on ultrafast effects in condensed materials and employed to effectively determine the FEL/laser cross correlation are presented.A description of the novel timing methodologies developed at the FERMI FEL facility is given.

Conference on X-Ray Lasers and Coherent X-ray Sources - Development and Applications, Prague, CZECH REPUBLIC, APR 24-26, 2017; International audience; Stimulated emission is a fundamental process in nature that deserves to be investigated and understood in the EUV and X-ray regimes. Today this is definitely possible through high energy density FEL beams. In this context, we show evidence for soft x-ray stimulated emission from a MgO solid target pumped by extreme ultraviolet FEL pulses formed in the regime of travelling-wave amplified spontaneous emission in backward geometry. Our results combine two effects separately reported in previous works: emission in a privileged direction and existence of a material-dependent threshold, for the stimulated emission. We have developed a theoretical framework, based on coupled rate and transport equations taking into account the solid density plasma state of the target. Our model, accounts for both observed mechanisms that are the privileged direction for the stimulated emission of the Mg L-2,L-3 characteristic emission and the pumping threshold.

UV Raman and Brillouin light scattering (BLS) experiments have been used in this study to explore the complex phase change behavior occurring in pH-responsive polysaccharide hydrogels as a function of temperature. Due to the different physical quantities measured by the two techniques, the joint analysis of Raman and BLS spectra has provided an unprecedented large-scale characterization of the molecular rearrangements and of the different kinds of hydrophilic and hydrophobic interactions that cooperate to determine the phase transformation observed in these hydrogels during the heating of the gel. As the main result, the analysis of the Raman and BLS spectra showed the existence of a correlation between the local (molecular) and collective properties of the gels during the phase transformation undergone by the system, which is markedly triggered by pH. The joint set of experimental results suggests a model according to which the mechanism of pH dependence in the hydrogels under investigation is dominated by the interactions involving the hydrophobic parts of the polymer skeleton, whereas the solvation process observed under heating of the gels is driven by the progressive distancing of the polymer domains among them, as monitored by the Brillouin sound velocity.

The collective dynamics of concentrated aqueous solutions of the three well-known homologous disaccharides, namely, maltose, sucrose and trehalose, have been studied in an unexplored frequency region by Brillouin ultraviolet light scattering, as a function of temperature and concentration. In trehalose solutions, for water concentrations close to the sugar hydration number, the structural relaxation time above the freezing point of water proves to be 10 % smaller than in maltose/sucrose solutions, presaging a different reorganisation of the sugar matrix. This effect could help in reducing both desiccation stresses and ice formation in anhydrobiotic organisms. The relevance of this behaviour in bioprotection is briefly discussed.

We present a newly developed resonant Raman scattering instrument working in the UV spectral range. This set-up, which exploits the UV synchrotron radiation source available at Elettra (Trieste, Italy), results in an innovative spectroscopic facility to be used for addressing a large array of open problems, ranging from the electronic properties of nanostructures and strongly correlated materials to biochemistry. © 2012 Elsevier B.V.

Free-electron lasers (FELs) currently represent a step forward on time-resolved investigations on any phase of matter through pump-probe methods involving FELs and laser beams. That class of experiments requires an accurate spatial and temporal superposition of pump and probe beams on the sample, which at present is still a critical procedure. More efficient approaches are demanded to quickly achieve the superposition and synchronization of the beams. Here, we present what we believe is a novel technique based on an integrated device allowing the simultaneous characterization and the fast spatial and temporal overlapping of the beams, reducing the alignment procedure from hours to minutes. (C) 2016 Optical Society of America

The development of free electron laser (FEL) sources has provided an unprecedented bridge between the scientific communities working with ultrafast lasers and extreme ultraviolet (XUV) and X-ray radiation. Indeed, in recent years an increasing number of FEL-based applications have exploited methods and concepts typical of advanced optical approaches. In this context, we recently used a seeded FEL to demonstrate a four-wave-mixing (FWM) process stimulated by coherent XUV radiation, namely the XUV transient grating (X-TG). We hereby report on X-TG measurements carried out on a sample of silicon nitride (Si3N4). The recorded data bears evidence for two distinct signal decay mechanisms: one occurring on a sub-ps timescale and one following slower dynamics extending throughout and beyond the probed timescale range (100 ps). The latter is compatible with a slower relaxation (time decay > ns), that may be interpreted as the signature of thermal diffusion modes. From the peak intensity of the X-TG signal we could estimate a value of the effective third-order susceptibility which is substantially larger than that found in SiO2, so far the only sample with available X-TG data. Furthermore, the intensity of the time-coincidence peak shows a linear dependence on the intensity of the three input beams, indicating that the measurements were performed in the weak field regime. However, the timescale of the ultrafast relaxation exhibits a dependence on the intensity of the XUV radiation. We interpreted the observed behaviour as the generation of a population grating of free-electrons and holes that, on the sub-ps timescale, relaxes to generate lattice excitations. The background free detection inherent to the X-TG approach allowed the determination of FEL-induced electron dynamics with a sensitivity largely exceeding that of transient reflectivity and transmissivity measurements, usually employed for this purpose. This journal is © The Royal Society of Chemistry.