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In this work, we introduce a simplified approach to efficiently extend the high harmonic generation (HHG) cutoff in gases without the need for laser frequency conversion via parametric processes. Instead, we employ postcompression and red-shifting of a Yb:CaF 2 laser via stimulated Raman scattering (SRS) in a nitrogen-filled stretched hollow core fiber. This driving scheme circumvents the low-efficiency window of parametric amplifiers in the 1100-1300 nm range. We demonstrate this approach being suitable for upscaling the power of a driver with an optimal wavelength for HHG in the highly desirable XUV range between 200 and 300 eV, up to the carbon K-edge. Due to the combination of power scalability of a low quantum defect ytterbium-based laser system with the high conversion efficiency of the SRS technique, we expect a significant increase in the generated photon flux in comparison with established platforms for HHG in the water window. We also compare HHG driven by the SRS scheme with the conventional self-phase modulation (SPM) scheme., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

In concert with carbonyl compounds, Lewis acids have been identified as a versatile class of photocatalysts. Thus far, research has focused on activation of the substrate, either by changing its photophysical properties or by modifying its photochemistry. In this work, we expand the established mode of action by demonstrating that UV photoexcitation of a Lewis acid-base complex can lead to homolytic cleavage of a covalent bond in the Lewis acid. In a study on the complex of benzaldehyde and the Lewis acid BCl 3 , we found evidence for homolytic B-Cl bond cleavage leading to formation of a borylated ketyl radical and a free chlorine atom only hundreds of femtoseconds after excitation. Both time-dependent density functional theory and transient absorption experiments identify a benzaldehyde-BCl 2 cation as the dominant species formed on the nanosecond time scale. The experimentally validated B-Cl bond homolysis was synthetically exploited for a BCl 3 -mediated hydroalkylation reaction of aromatic aldehydes (19 examples, 42-76% yield). It was found that hydrocarbons undergo addition to the C═O double bond via a radical pathway. The photogenerated chlorine radical abstracts a hydrogen atom from the alkane, and the resulting carbon-centered radical either recombines with the borylated ketyl radical or adds to the ground-state aldehyde-BCl 3 complex, releasing a chlorine atom. The existence of a radical chain was corroborated by quantum yield measurements and by theory. The photolytic mechanism described here is based on electron transfer between a bound chlorine and an aromatic π-system on the substrate. Thereby, it avoids the use of redox-active transition metals.

Femtosecond extreme ultraviolet wave packet interferometry (XUV-WPI) was applied to study resonant interatomic Coulombic decay (ICD) in the HeNe dimer. The high demands on phase stability and sensitivity for vibronic XUV-WPI of molecular-beam targets are met using an XUV phase-cycling scheme. The detected quantum interferences exhibit vibronic dephasing and rephasing signatures along with an ultrafast decoherence assigned to the ICD process. A Fourier analysis reveals the molecular absorption spectrum with high resolution. The demonstrated experiment shows a promising route for the real-time analysis of ultrafast ICD processes with both high temporal and high spectral resolution.

Lewis acids have recently been recognized as catalysts enabling enantioselective photochemical transformations. Mechanistic studies on these systems are however rare, either due to their absorption at wavelengths shorter than 260 nm, or due to the limitations of theoretical dynamic studies for larger complexes. In this work, we overcome these challenges and employ sub-30-fs transient absorption in the UV, in combination with a highly accurate theoretical treatment on the XMS-CASPT2 level. We investigate 2-cyclohexenone and its complex to boron trifluoride and analyze the observed dynamics based on trajectory calculations including non-adiabatic coupling and intersystem crossing. This approach explains all ultrafast decay pathways observed in the complex. We show that the Lewis acid remains attached to the substrate in the triplet state, which in turn explains why chiral boron-based Lewis acids induce a high enantioselectivity in photocycloaddition reactions., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We present diffraction-limited photocurrent (PC) microscopy in the visible spectral range based on broadband excitation and an inherently phase-stable common-path interferometer. The excellent path-length stability guarantees high accuracy without the need for active feedback or post-processing of the interferograms. We illustrate the capabilities of the setup by recording PC spectra of a bulk GaAs device and compare the results to optical transmission data.

The recent development of ultrafast extreme ultraviolet (XUV) coherent light sources bears great potential for a better understanding of the structure and dynamics of matter. Promising routes are advanced coherent control and nonlinear spectroscopy schemes in the XUV energy range, yielding unprecedented spatial and temporal resolution. However, their implementation has been hampered by the experimental challenge of generating XUV pulse sequences with precisely controlled timing and phase properties. In particular, direct control and manipulation of the phase of individual pulses within an XUV pulse sequence opens exciting possibilities for coherent control and multidimensional spectroscopy, but has not been accomplished. Here, we overcome these constraints in a highly time-stabilized and phase-modulated XUV-pump, XUV-probe experiment, which directly probes the evolution and dephasing of an inner subshell electronic coherence. This approach, avoiding any XUV optics for direct pulse manipulation, opens up extensive applications of advanced nonlinear optics and spectroscopy at XUV wavelengths.

We report on the quantum storage of a heralded frequency-multiplexed single photon in an integrated laser-written rare-earth doped waveguide. The single photon contains 15 discrete frequency modes separated by 261 MHz and spanning across 4 GHz. It is obtained from a nondegenerate photon pair created via cavity-enhanced spontaneous down-conversion, where the heralding photon is at telecom wavelength and the heralded photon is at 606 nm. The frequency-multimode photon is stored in a praseodymium-doped waveguide using the atomic frequency comb (AFC) scheme, by creating multiple combs within the inhomogeneous broadening of the crystal. Thanks to the intrinsic temporal multimodality of the AFC scheme, each spectral bin includes 9 temporal modes, such that the total number of stored modes is about 130. We demonstrate that the storage preserves the nonclassical properties of the single photon, and its normalized frequency spectrum.

Many intracellular reactions are dependent on the dielectric ("polarity") and viscosity properties of their milieu. Fluorescence imaging offers a convenient strategy to report on such environmental properties. Yet, concomitant and independent monitoring of polarity and viscosity in cells at submicron scale is currently hampered by the lack of fluorescence probes characterized by unmixed responses to both parameters. Here, the peculiar photophysics of a green fluorescent protein chromophore analog is exploited for quantifying and imaging polarity and viscosity independently in living cells. We show that the polarity and viscosity profile around a novel hybrid drug-delivery peptide changes dramatically upon cell internalization via endosomes, shedding light on the spatiotemporal features of the release mechanism. Accordingly, our fluorescent probe opens the way to monitor the environmental effects on several processes relevant to cell biochemistry and nanomedicine., (Copyright © 2018. Published by Elsevier Inc.)

Three-dimensional (3D) particle focusing in microfluidics is a fundamental capability with a wide range of applications, such as on-chip flow cytometry, where high-throughput analysis at the single-cell level is performed. Currently, 3D focusing is achieved mainly in devices with complex layouts, additional sheath fluids, and complex pumping systems. In this work, we present a compact microfluidic device capable of 3D particle focusing at high flow rates and with a small footprint, without the requirement of external fields or lateral sheath flows, but using only a single-inlet, single-outlet microfluidic sequence of straight channels and tightly curving vertical loops. This device exploits inertial fluidic effects that occur in a laminar regime at sufficiently high flow rates, manipulating the particle positions by the combination of inertial lift forces and Dean drag forces. The device is fabricated by femtosecond laser irradiation followed by chemical etching, which is a simple two-step process enabling the creation of 3D microfluidic networks in fused silica glass substrates. The use of tightly curving three-dimensional microfluidic loops produces strong Dean drag forces along the whole loop but also induces an asymmetric Dean flow decay in the subsequent straight channel, thus producing rapid cross-sectional mixing flows that assist with 3D particle focusing. The use of out-of-plane loops favors a compact parallelization of multiple focusing channels, allowing one to process large amounts of samples. In addition, the low fluidic resistance of the channel network is compatible with vacuum driven flows. The resulting device is quite interesting for high-throughput on-chip flow cytometry., Competing Interests: The authors declare no conflict of interest.

We introduce a novel in-situ strong field ionization tomography approach for characterizing the spatial density distribution of gas jets. We show that for typical intensities in high harmonic generation experiments, the strong field ionization mechanism used in our approach provides an improvement in the resolution close to factor of 2 (resolving about 8 times smaller voxel volume), when compared to linear/single-photon imaging modalities. We find, that while the depth of scan in linear tomography is limited by resolution loss due to the divergence of the driving laser beam, in the proposed approach the depth of focus is localized due to the inherent physical nature of strong-field interaction and discuss implications of these findings. We explore key aspects of the proposed method and compare it with commonly used single- and multi-photon imaging mechanisms. The proposed method will be particularly useful for strong field and attosecond science experiments.

This paper provides an overview of femtosecond laser microfabrication in polymeric materials, with emphasis on lab-on-chip applications. Due to the nonlinear interaction of femtosecond laser pulses with polymers, laser-induced modifications are localized to the focal volume, enabling high resolution patterning in 3D. Femtosecond laser microfabrication offers unmatched versatility in fabricating surface microchannels and diffractive optics by means of laser ablation, buried optical waveguides and micro-optics through refractive index modification and complex 3D microstructures in photoresists by two-photon polymerization. Femtosecond laser microfabrication technology opens the door to fabricating integrated lab-on-chip devices with a single tool., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Equilibrium fluctuations of thermodynamic variables, such as density or concentration, are known to be small and typically occur at a molecular length scale. In contrast, theory predicts that non-equilibrium fluctuations grow very large both in amplitude and spatial size. On earth, the presence of gravity and buoyancy forces severely limits the development of the fluctuations. We will present the results of a 14-year long international collaboration on an experiment on non-equilibrium fluctuations in a single liquid and in a polymer solution under microgravity conditions. Non-equilibrium conditions are generated by applying a temperature gradient across millimetre-size liquid slabs. Phase modulations introduced by fluctuations are measured using a quantitative shadowgraph method, with the optical axis parallel to the temperature gradient. Thousands of images are analysed and their two-dimensional power spectra yield the fluctuation structure function S(q), once data are reduced accounting for the instrumental transfer function T(q). The mean-squared amplitude of the fluctuations exhibits an impressive power-law dependence at larger q and a crossover at low q showing that the fluctuation size is limited by the sample thickness. The shape of the structure function, its increase due to removing gravity, and its dependence on applied gradient are in reasonable agreement with available theoretical predictions.

We introduce a novel configuration for broadband, time-resolved CARS spectroscopy/microscopy in which pump, Stokes and probe pulses are all derived from a single femtosecond Yb:KYW laser. The 1-MHz repetition rate of the system allows very intense CARS signals to be obtained over short acquisition times, while a delayed probe pulse ensures an efficient non-resonant background suppression.