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 methods. The coherent and multi-wave nature of the FWM approach has been crucial in the development of advanced technologies, such as silicon photonics, subwavelength imaging and quantum communications. 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 resonances. 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 laser, 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 dynamics. The theoretical possibility of realizing these applications has already stimulated ongoing developments of free-electron lasers: our results show that FWM at suboptical wavelengths is feasible, and we hope that they will enable advances in present and future photon sources.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, SBMB, SIK, UILJ, UKNU, UL, UM, UPUK
Ultrafast optical-domain spectroscopies allow to monitor in real time the motion of nuclei in molecules. Achieving element-selectivity had to await the advent of time resolved X-ray spectroscopy, ...which is now commonly carried at X-ray free electron lasers. However, detecting light element that are commonly encountered in organic molecules, remained elusive due to the need to work under vacuum. Here, we present an impulsive stimulated Raman scattering (ISRS) pump/carbon K-edge absorption probe investigation, which allowed observation of the low-frequency vibrational modes involving specific selected carbon atoms in the Ibuprofen RS dimer. Remarkably, by controlling the probe light polarization we can preferentially access the enantiomer of the dimer to which the carbon atoms belong.
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.
A multi-technique biophysical method is used to study the ligand binding to G-quadruplex DNA.
FERMI@Elettra is a free electron-laser (FEL)-based user facility that, after two years of commissioning, started preliminary users' dedicated runs in 2011. At variance with other FEL user facilities, ...FERMI@Elettra has been designed to deliver improved spectral stability and longitudinal coherence. The adopted scheme, which uses an external laser to initiate the FEL process, has been demonstrated to be capable of generating FEL pulses close to the Fourier transform limit. We report on the first instance of FEL wavelength tuning, both in a narrow and in a large spectral range (fine- and coarse-tuning). We also report on two different experiments that have been performed exploiting such FEL tuning. We used fine-tuning to scan across the 1s-4p resonance in He atoms, at 23.74 eV (52.2 nm), detecting both UV-visible fluorescence (4p-2s, 400 nm) and EUV fluorescence (4p-1s, 52.2 nm). We used coarse-tuning to scan the M4,5 absorption edge of Ge (∼29.5 eV) in the wavelength region 30-60 nm, measured in transmission geometry with a thermopile positioned on the rear side of a Ge thin foil.
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.
Exploring the dynamics of matter driven to extreme non-equilibrium states by an intense ultrashort X-ray pulse is becoming reality, thanks to the advent of free-electron laser technology that allows ...development of different schemes for probing the response at variable time delay with a second pulse. Here we report the generation of two-colour extreme ultraviolet pulses of controlled wavelengths, intensity and timing by seeding of high-gain harmonic generation free-electron laser with multiple independent laser pulses. The potential of this new scheme is demonstrated by the time evolution of a titanium-grating diffraction pattern, tuning the two coherent pulses to the titanium M-resonance and varying their intensities. This reveals that an intense pulse induces abrupt pattern changes on a time scale shorter than hydrodynamic expansion and ablation. This result exemplifies the essential capabilities of the jitter-free multiple-colour free-electron laser pulse sequences to study evolving states of matter with element sensitivity.
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 103–104 K temperature range with pressures up to 1 Mbar.
We have studied aqueous solutions of native and chemically modified cyclodextrins (CDs) by means of UV Raman and Brillouin scattering. Analysis of the spectral profile of the OH‐stretching Raman ...signal, which is sensitive to the intermolecular organization of water, reveals a remarkable reduction of the population of ordered tetrahedral water structures inside the hydration shell of substituted CDs. As a remarkable result, this destructuring effect seems to be mainly related to the number of substituted hydroxyl groups in the CD ring rather than to the chemical nature of the substituent group. UV Brillouin scattering experiments confirm the structural picture emerging from the UV Raman study, also providing an estimate of the activation energy associated to the collective H‐bond restructuring mechanism in CD solutions. Overall, the results provide a coherent description of the water–solute interactions in aqueous solutions of CDs.
The intermolecular organization of water around native and chemically modified cyclodextrins have been studied by UV Raman and Brillouin experiments. The progressive disruption of the tetrahedral order of water, found for the substituted forms of cyclodextrins, seems to be mainly related to the average number of substituted OH groups rather than to the chemical nature of the substituent.
We report measurements of the sound attenuation coefficient in vitreous silica, for sound waves of wavelength between 50 and 80 nm, performed with the new inelastic UV light scattering technique. ...These data indicate that in silica glass a crossover between a temperature-dependent (at low frequency) and a temperature-independent (at high frequency) acoustic attenuation mechanism occurs at Q approximately equal to 0.15 nm(-1). The absence of any signature in the static structure factor at this Q value suggests that the observed crossover should be associated with local elastic constant fluctuations.
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 aim of this study is to point out the most common interfering agents that vibrational spectroscopists may find when analyzing extracted nucleic acids. Fourier transform infrared and ultraviolet‐resonant Raman measurements have been carried out on DNA and RNA samples of B16 cells, extracted by tailoring standard protocols used in molecular biology to vibrational spectroscopy. By adopting simple, rapid, and inexpensive precautions, we could obtain reliable and informative vibrational spectra also for noncommercial nucleic acids.
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