Femtosecond proton transfer in urea solutions probed by X-ray spectroscopy.

Proton transfer is one of the most fundamental events in aqueous-phase chemistry and an emblematic case of coupled ultrafast electronic and structural dynamics1,2. Disentangling electronic and nuclear dynamics on the femtosecond timescales remains a formidable challenge, especially in the liquid phase, the natural environment of biochemical processes. Here we exploit the unique features of table-top water-window X-ray absorption spectroscopy3-6 to reveal femtosecond proton-transfer dynamics in ionized urea dimers in aqueous solution. Harnessing the element specificity and the site selectivity of X-ray absorption spectroscopy with the aid of ab initio quantum-mechanical and molecular-mechanics calculations, we show how, in addition to the proton transfer, the subsequent rearrangement of the urea dimer and the associated change of the electronic structure can be identified with site selectivity. These results establish the considerable potential of flat-jet, table-top X-ray absorption spectroscopy7,8 in elucidating solution-phase ultrafast dynamics in biomolecular systems.

Control of the Two-photon Visual Process in ex vivo Retinas and in Living Mice.

Palcewska et al. first demonstrated near infrared (NIR) visual response in human volunteers upon two-photon absorption (TPA), in a seminal work of 2014, and assessed the process in terms of wavelength- and power-dependence on murine ex-vivo retinas. In the present study, ex-vivo electroretinography (ERG) is further developed to perform a complete characterization of the effect of NIR pulse duration, energy, and focal spot size on the response. The same set of measurements is successively tested on living mice. We discuss how the nonlinear intensity dependence of the photon absorption process is transferred to the amplitude of the visual response acquired by ERG. Finally, we show that the manipulation of the spectral phase of NIR pulses can be translated to predictable change in the two-photon induced response under physiological excitation conditions.

Multiorder Nonlinear Mixing in Metal Oxide Nanoparticles.

Whereas most of the reports on the nonlinear properties of micro- and nanostructures address the generation of distinct signals, such as second or third harmonic, here we demonstrate that the novel generation of dual output lasers recently developed for microscopy can readily increase the accessible parameter space and enable the simultaneous excitation and detection of multiple emission orders such as several harmonics and signals stemming from various sum and difference frequency mixing processes. This rich response, which in our case features 10 distinct emissions and encompasses the whole spectral range from the deep ultraviolet to the short-wave infrared region, is demonstrated using various nonlinear oxide nanomaterials while being characterized and simulated temporally and spectrally. Notably, we show that the response is conserved when the particles are embedded in biological media opening the way to novel biolabeling and phototriggering strategies.

Real-time recording of circadian liver gene expression in freely moving mice reveals the phase-setting behavior of hepatocyte clocks.

The mammalian circadian timing system consists of a master pacemaker in the suprachiasmatic nucleus (SCN) in the hypothalamus, which is thought to set the phase of slave oscillators in virtually all body cells. However, due to the lack of appropriate in vivo recording technologies, it has been difficult to study how the SCN synchronizes oscillators in peripheral tissues. Here we describe the real-time recording of bioluminescence emitted by hepatocytes expressing circadian luciferase reporter genes in freely moving mice. The technology employs a device dubbed RT-Biolumicorder, which consists of a cylindrical cage with reflecting conical walls that channel photons toward a photomultiplier tube. The monitoring of circadian liver gene expression revealed that hepatocyte oscillators of SCN-lesioned mice synchronized more rapidly to feeding cycles than hepatocyte clocks of intact mice. Hence, the SCN uses signaling pathways that counteract those of feeding rhythms when their phase is in conflict with its own phase.

Molecular quantum wakes for clearing fog.

High intensity laser filamentation in air has recently demonstrated that, through plasma generation and its associated shockwave, fog can be cleared around the beam, leaving an optically transparent path to transmit light. However, for practical applications like free-space optical communication (FSO), channels of multi-centimeter diameters over kilometer ranges are required, which is extremely challenging for a plasma based method. Here we report a radically different approach, based on quantum control. We demonstrate that fog clearing can also be achieved by producing molecular quantum wakes in air, and that neither plasma generation nor filamentation are required. The effect is clearly associated with the rephasing time of the rotational wave packet in N2.Pump excitation provided in the form of resonant trains of 8 pulses separated by the revival time are able to transmit optical data through fog with initial extinction as much as -6 dB.

HV discharges triggered by dual- and triple-frequency laser filaments.

We study the use of frequency upconversion schemes of near-IR picosecond laser pulses and compare their ability to guide and trigger electric discharges through filamentation in air. Upconversion, such as Second Harmonic Generation, is favorable for triggering electric discharges for given amount of available laser energy, even taking into account the losses inherent to frequency conversion. We focus on the practical question of optimizing the use of energy from a given available laser system and the potential advantage to use frequency conversion schemes.

High-order harmonic source spanning up to the oxygen K-edge based on filamentation pulse compression.

We present a 0.2 TW sub-two-cycle 1.8 µm carrier-envelope-phase stable source based on two-stage pulse compression by filamentation for driving high-order harmonic generation extending beyond the oxygen K absorption edge. The 1 kHz repetition rate, high temporal resolution enabled by the short 11.8 fs driving pulse duration, and bright high-order harmonics generated in helium make this an attractive source for solid-state and molecular-dynamics studies.

Remote electrical arc suppression by laser filamentation: erratum.

A correction in the transit time of electrons between the filaments and the electrodes leads us to reattribute the remote unloading to ions rather than to electrons. The experimental results reported in [Opt. Express23, 286407 (2015)] about remote electrical unloading and discharge suppression, as well as the analogy with the analogy with a supercorona, remain valid.

Linearity of charge measurement in laser filaments.

We evaluate the linearity of three electric measurement techniques of the initial electron density in laser filaments by comparing their results for a pair of filaments and for the sum of each individual filament. The conductivity measured between two plane electrodes in a longitudinal configuration is linear within 2 % provided the electric field is kept below 100 kV/m. Furthermore, simulations show that the signal behaves like the amount of generated free electrons. The slow ionic current measured with plane electrodes in a parallel configuration is representative of the ionic charge available in the filament, after several µs, when the free electrons have recombined. It is linear within 2 % with the amount of ions and is insensitive to misalignment. Finally, the fast polarization signal in the same configuration deviates from linearity by up to 80 % and can only be considered as a semi-qualitative indication of the presence of charges, e.g., to characterize the filament length.

Sequential Proton Coupled Electron Transfer (PCET): Dynamics Observed over 8 Orders of Magnitude in Time.

Charge transfer mechanisms lay at the heart of chemistry and biochemistry. Proton coupled electron transfers (PCET) are central in biological processes such as photosynthesis and in the respiratory chain, where they mediate long-range charge transfers. These mechanisms are normally difficult to harness experimentally due to the intrinsic complexity of the associated biological systems. Metal-peptide cations experience both electron and proton transfers upon photoexcitation, proving an amenable model system to study PCET. We report on a time-resolved experiment designed to follow this dual charge transfer kinetics in [HG3W+Ag](+) (H = histidine, G = glycine, W = tryptophan) on time scales ranging from femtoseconds to milliseconds. While electron transfer completes in less than 4 ps, it triggers a proton transfer lasting over hundreds of microseconds. Molecular dynamics simulations show that conformational dynamic plays an important role in slowing down this reaction. This combined experimental and computational approach provides a view of PCET as a single phenomenon despite its very wide time-domain span.

Laser-induced plasma cloud interaction and ice multiplication under cirrus cloud conditions.

Potential impacts of lightning-induced plasma on cloud ice formation and precipitation have been a subject of debate for decades. Here, we report on the interaction of laser-generated plasma channels with water and ice clouds observed in a large cloud simulation chamber. Under the conditions of a typical storm cloud, in which ice and supercooled water coexist, no direct influence of the plasma channels on ice formation or precipitation processes could be detected. Under conditions typical for thin cirrus ice clouds, however, the plasma channels induced a surprisingly strong effect of ice multiplication. Within a few minutes, the laser action led to a strong enhancement of the total ice particle number density in the chamber by up to a factor of 100, even though only a 10(-9) fraction of the chamber volume was exposed to the plasma channels. The newly formed ice particles quickly reduced the water vapor pressure to ice saturation, thereby increasing the cloud optical thickness by up to three orders of magnitude. A model relying on the complete vaporization of ice particles in the laser filament and the condensation of the resulting water vapor on plasma ions reproduces our experimental findings. This surprising effect might open new perspectives for remote sensing of water vapor and ice in the upper troposphere.

Plasmonic Tipless Pyramid Arrays for Cell Poration.

Improving the efficiency, cell survival, and throughput of methods to modify and control the genetic expression of cells is of great benefit to biology and medicine. We investigate, both computationally and experimentally, a nanostructured substrate made of tipless pyramids for plasmonic-induced transfection. By optimizing the geometrical parameters for an excitation wavelength of 800 nm, we demonstrate a 100-fold intensity enhancement of the electric near field at the cell-substrate contact area, while the low absorption typical for gold is maintained. We demonstrate that such a substrate can induce transient poration of cells by a purely optically induced process.

Remote electrical arc suppression by laser filamentation.

We investigate the interaction of narrow plasma channels formed in the filamentation of ultrashort laser pulses, with a DC high voltage. The laser filaments prevent electrical arcs by triggering corona that neutralize the high-voltage electrodes. This phenomenon, that relies on the electric field modulation and free electron release around the filament, opens new prospects to lightning and over-voltage mitigation.

Cellular uptake and biocompatibility of bismuth ferrite harmonic advanced nanoparticles.

Bismuth Ferrite (BFO) nanoparticles (BFO-NP) display interesting optical (nonlinear response) and magnetic properties which make them amenable for bio-oriented diagnostic applications as intra- and extra membrane contrast agents. Due to the relatively recent availability of this material in well dispersed nanometric form, its biocompatibility was not known to date. In this study, we present a thorough assessment of the effects of in vitro exposure of human adenocarcinoma (A549), lung squamous carcinoma (NCI-H520), and acute monocytic leukemia (THP-1) cell lines to uncoated and poly(ethylene glycol)-coated BFO-NP in the form of cytotoxicity, haemolytic response and biocompatibility. Our results support the attractiveness of the functional-BFO towards biomedical applications focused on advanced diagnostic imaging. FROM THE CLINICAL EDITOR: Bismuth Ferrite nanoparticles (BFO-NP) have been recently successfully introduced as photodynamic tools and imaging probes. However, how these nanoparticles interact with various cells at the cellular level remains poorly understood. In this study, the authors performed in vitro experiments to assess the effects of uncoated and PEG-coated BFO-NP in the form of cytotoxicity, haemolytic response and biocompatibility.

Organometal halide perovskite solar cell materials rationalized: ultrafast charge generation, high and microsecond-long balanced mobilities, and slow recombination.

Organometal halide perovskite-based solar cells have recently been reported to be highly efficient, giving an overall power conversion efficiency of up to 15%. However, much of the fundamental photophysical properties underlying this performance has remained unknown. Here, we apply photoluminescence, transient absorption, time-resolved terahertz and microwave conductivity measurements to determine the time scales of generation and recombination of charge carriers as well as their transport properties in solution-processed CH3NH3PbI3 perovskite materials. We found that electron-hole pairs are generated almost instantaneously after photoexcitation and dissociate in 2 ps forming highly mobile charges (25 cm(2) V(-1) s(-1)) in the neat perovskite and in perovskite/alumina blends; almost balanced electron and hole mobilities remain very high up to the microsecond time scale. When the perovskite is introduced into a TiO2 mesoporous structure, electron injection from perovskite to the metal oxide is efficient in less than a picosecond, but the lower intrinsic electron mobility of TiO2 leads to unbalanced charge transport. Microwave conductivity measurements showed that the decay of mobile charges is very slow in CH3NH3PbI3, lasting up to tens of microseconds. These results unravel the remarkable intrinsic properties of CH3NH3PbI3 perovskite material if used as light absorber and charge transport layer. Moreover, finding a metal oxide with higher electron mobility may further increase the performance of this class of solar cells.

Tailoring single-cycle electromagnetic pulses in the 2-9 THz frequency range using DAST/SiO2 multilayer structures pumped at Ti:sapphire wavelength.

We present a numerical parametric study of single-cycle electromagnetic pulse generation in a DAST/SiO2multilayer structure via collinear optical rectification of 800 nm femtosecond laser pulses. It is shown that modifications of the thicknesses of the DAST and SiO2layers allow tuning of the average frequency of the generated THz pulses in the frequency range from 3 to 6 THz. The laser-to-THz energy conversion efficiency in the proposed structures is compared with that in a bulk DAST crystal and a quasi-phase-matching periodically poled DAST crystal and shows significant enhancement.

Characterization of the nonlinear optical properties of nanocrystals by Hyper Rayleigh Scattering.

BACKGROUND: Harmonic Nanoparticles are a new family of exogenous markers for multiphoton imaging exerting optical contrast by second harmonic (SH) generation. In this tutorial, we present the application of Hyper-Rayleigh Scattering (HRS) for a quantitative assessment of the nonlinear optical properties of these particles and discuss the underlying theory and some crucial experimental aspects. METHODS: The second harmonic properties of BaTiO3, KNbO3, KiTiOPO4 (KTP), LiNbO3 and ZnO nanocrystals (NCs) are investigated by HRS measurements after careful preparation and characterization of colloidal suspensions. RESULTS: A detailed analysis of the experimental results is presented with emphasis on the theoretical background and on the influence of some experimental parameters including the accurate determination of the nanocrystal size and concentration. The SH generation efficiency and averaged nonlinear optical coefficients are then derived and compared for six different types of NCs. CONCLUSIONS: After preparation of colloidal NC suspensions and careful examination of their size, concentration and possible aggregation state, HRS appears as a valuable tool to quantitatively assess the SH efficiency of noncentrosymmetric NCs. All the investigated nanomaterials show high SH conversion efficiencies, demonstrating a good potential for bio-labelling applications.

Nonlinear correlation spectroscopy (NLCS).

We present a novel concept for optical spectroscopy called nonlinear correlation spectroscopy (NLCS). NLCS analyses coherent field fluctuations of the second and third harmonic light generated by diffusing nanoparticles. Particles based on noncentrosymmetric nonlinear materials such as KNbO(3) show a strong second as well as third harmonic response. The method and the theory are introduced and experimental NLCS results in fetal calf serum are presented showing the promising selectivity of this technique for measurement in complex biological environments.

Long distance laser filamentation using Yb:YAG kHz laser.

In the framework of the Laser Lightning Rod project, whose aim is to show that laser-induced filaments can guide lightning discharges over considerable distances, we study over a distance of 140 m the filaments created by a laser system with J-range pulses of 1 ps duration at 1 kHz repetition rate. We investigate the spatial evolution of the multiple filamentation regime using the fundamental beam at 1030 nm or using combination with the second and third harmonics. The measurements were made using both a collimated beam and a loosely focused beam.

Laser-guided lightning.

Lightning discharges between charged clouds and the Earth's surface are responsible for considerable damages and casualties. It is therefore important to develop better protection methods in addition to the traditional Franklin rod. Here we present the first demonstration that laser-induced filaments-formed in the sky by short and intense laser pulses-can guide lightning discharges over considerable distances. We believe that this experimental breakthrough will lead to progress in lightning protection and lightning physics. An experimental campaign was conducted on the Säntis mountain in north-eastern Switzerland during the summer of 2021 with a high-repetition-rate terawatt laser. The guiding of an upward negative lightning leader over a distance of 50 m was recorded by two separate high-speed cameras. The guiding of negative lightning leaders by laser filaments was corroborated in three other instances by very-high-frequency interferometric measurements, and the number of X-ray bursts detected during guided lightning events greatly increased. Although this research field has been very active for more than 20 years, this is the first field-result that experimentally demonstrates lightning guided by lasers. This work paves the way for new atmospheric applications of ultrashort lasers and represents an important step forward in the development of a laser based lightning protection for airports, launchpads or large infrastructures.