Chris Milne

European XFEL

X-ray Free Electron Lasers (XFELs) allow the collection of high-quality serial femtosecond crystallography data. The next generation of megahertz superconducting FELs promises to drastically reduce data collection times, enabling the capture of more structures with higher signal-to-noise ratios and facilitating more complex experiments. Currently,...

A new method for time‐resolved X‐ray absorption near edge structure (XANES) spectroscopy that enables faster data acquisition and requires smaller sample quantities for high‐quality data, thus allowing the analysis of more samples in a shorter time is introduced. The method uses large bandwidth free electron laser pulses to measure laser‐excited XA...

Introduction The diagnostics of the X-ray beam properties has a critical importance at the Euro-pean X-ray Free Electron Laser facility. Besides existing diagnostic components, utilization of a diamond sensor was proposed to achieve radiation-hard, non-invasive beam position and pulse energy measurements for hard X-rays [1]. In particular, at very...

High-intensity femtosecond pulses from an X-ray free-electron laser enable pump–probe experiments for the investigation of electronic and nuclear changes during light-induced reactions. On timescales ranging from femtoseconds to milliseconds and for a variety of biological systems, time-resolved serial femtosecond crystallography (TR-SFX) has provi...

The synthesis and control of properties of p-type ZnO is crucial for a variety of optoelectronic and spintronic applications; however, it remains challenging due to the control of intrinsic midgap (defect) states. In this study, we demonstrate a synthetic route to yield colloidal ZnO quantum dots (QD) via an enhanced sol−gel process that effectivel...

Introduction The diagnostics of the X-ray beam properties has a critical importance at the Euro-pean X-ray Free Electron Laser facility. Besides existing diagnostic components, utilization of a diamond sensor was proposed to achieve radiation-hard, non-invasive beam position and pulse energy measurements for hard X-rays [1]. In particular, at very...

To fully exploit ultra-short X-ray pulse durations routinely available at X-ray free-electron lasers to follow out-of-equilibrium dynamics, inherent arrival time fluctuations of the X-ray pulse with an external perturbing laser pulse need to be measured. In this work, two methods of arrival time measurement were compared to measure the arrival time...

Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C–H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the two-way, metal to ligand (MLCT) and ligand to metal (LMCT), charge-transfer between an incoming alkane C–H group and the transition metal...

Serial crystallography at X-ray free-electron lasers (XFELs) permits the determination of radiation-damage free static as well as time-resolved protein structures at room temperature. Efficient sample delivery is a key factor for such experiments. Here, we describe a multi-reservoir, high viscosity extruder as a step towards automation of sample de...

Photolyases, a ubiquitous class of flavoproteins, use blue light to repair DNA photolesions. In this work, we determined the structural mechanism of the photolyase-catalyzed repair of a cyclobutane pyrimidine dimer (CPD) lesion using time-resolved serial femtosecond crystallography (TR-SFX). We obtained 18 snapshots that show time-dependent changes...

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photolumi-nescence is excited at 4.66 eV, well above the band edge, and shows...

Molecular photoswitches are versatile natural or synthetic molecules that undergo reversible conformational changes in response to light. In chemistry azobenzenes act as ubiquitous synthetic photoswitches ¹ with applications ranging from opto-electronics ² , over molecular machines ³ to photopharmacology ⁴ . Their isomerization mechanism defines th...

The Femtosecond X-ray Experiments (FXE) instrument at the European X-ray Free-Electron Laser (EuXFEL) provides an optimized platform for investigations of ultrafast physical, chemical and biological processes. It operates in the energy range 4.7–20 keV accommodating flexible and versatile environments for a wide range of samples using diverse ultra...

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy and ab-initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows th...

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy and ab-initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows th...

New synthetic hybrid materials and their increasing complexity have placed growing demands on crystal growth for single-crystal X-ray diffraction analysis. Unfortunately, not all chemical systems are conducive to the isolation of single crystals for traditional characterization. Here, small-molecule serial femtosecond crystallography (smSFX) at ato...

Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C-H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the bidirectional charge-transfer between an incoming alkane C-H group and the transition metal is the decisive interaction in the C-H activa...

Transition metal reactivity toward carbon-hydrogen (C-H) bonds hinges on the interplay of electron donation and withdrawal at the metal center. Manipulating this reactivity in a controlled way is difficult because the hypothesized metal-alkane charge-transfer interactions are challenging to access experimentally. Using time-resolved x-ray spectrosc...

Single‐ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and...

We have produced hard x-ray free-electron laser (FEL) pulses, which are chirped both in photon energy and in spatial position. The experiments have been carried out at the hard x-ray beamline Aramis at SwissFEL, located at the Paul Scherrer Institute in Switzerland. The FEL beamline was operated without any external focusing and with a tilted, ener...

Vision is initiated by the rhodopsin family of light-sensitive G protein-coupled receptors (GPCRs)¹. A photon is absorbed by the 11-cis retinal chromophore of rhodopsin, which isomerizes within 200 femtoseconds to the all-trans conformation², thereby initiating the cellular signal transduction processes that ultimately lead to vision. However, the...

We report femtosecond Fe K-edge absorption (XAS) and nonresonant X-ray emission (XES) spectra of ferric cytochrome C (Cyt c) upon excitation of the haem (>300 nm) or mixed excitation of the haem and tryptophan (<300 nm). The XAS and XES transients obtained in both excitation energy ranges show no evidence for electron transfer processes between pho...

Serial crystallography at X-ray free-electron lasers (XFELs) permits the determination of radiation-damage free static as well as time-resolved protein structures at room temperature. Efficient sample delivery is a key factor for such experiments. Here, we describe a multi-reservoir, high viscosity extruder as a step towards automation of sample de...

The binding and release of ligands from their protein targets is central to fundamental biological processes as well as to drug discovery. Photopharmacology introduces chemical triggers that allow the changing of ligand affinities and thus biological activity by light. Insight into the molecular mechanisms of photopharmacology is largely missing be...

Photochemical reactions in solution are governed by a complex interplay between transient intramolecular electronic and nuclear structural changes and accompanying solvent rearrangements. State-of-the-art time-resolved X-ray solution scattering has emerged in the last decade as a powerful technique to observe solute and solvent motions in real time...

The reactivity towards C-H bond activation of alkanes with transition metals is determined by the ability of the metal to donate and withdraw electron density in due proportion. Manipulating this reactivity in a controlled way is difficult, because the hypothesized metal-alkane charge-transfer interactions are challenging to access experimentally....

Photochemical reactions in solution are governed by a complex interplay between transient intramolecular electronic and nuclear structural changes and accompanying solvent rearrangements. State-of-the-art time-resolved X-ray solution scattering has emerged in the last decade as a powerful technique to observe solute and solvent motions in real time...

High-intensity femtosecond pulses from an X-ray free-electron laser enable pump probe experiments for investigating electronic and nuclear changes during light-induced reactions. On time scales ranging from femtoseconds to milliseconds and for a variety of biological systems, time-resolved serial femtosecond crystallography (TR-SFX) has provided de...

https://www.biorxiv.org/content/10.1101/2022.10.14.511948v1

Vision is initiated by the rhodopsin family of light-sensitive G protein-coupled receptors (GPCRs). A photon is absorbed by the 11- cis retinal chromophore of rhodopsin which isomerises within 200 femtoseconds to the all- trans conformation, thereby initiating the cellular signal transduction processes that ultimately lead to vision. However, the i...

The binding and release of ligands from their protein targets is central to fundamental biological processes as well as to drug discovery. Photopharmacology introduces chemical triggers that allow the changing of ligand affinities and thus biological activity by light. Insight into the molecular mechanisms of photopharmacology is largely missing be...

Serial crystallography is a rapidly growing method that can yield structural insights from microcrystals that were previously considered to be too small to be useful in conventional X-ray crystallography. Here, conditions for growing microcrystals of the photosynthetic reaction centre of Blastochloris viridis within a lipidic cubic phase (LCP) crys...

Hematite (α-Fe2O3) is a photoelectrode for the water splitting process because of its relatively narrow bandgap and abundance in the earth's crust. In this study, the photoexcited state of a hematite thin film was investigated with femtosecond oxygen K-edge X-ray absorption spectroscopy (XAS) at the PAL-XFEL in order to follow the dynamics of its p...

We present the development of a gain correction process for the Large Pixel Detector (LPD) developed by the Science and Technology Facilities Council (STFC) for the Femtosecond X-Ray Experiment (FXE) instrument based at the European X-ray Free Electron Laser (EuXFEL). LPD operates at 4.5 MHz as necessitated by EuXFEL's pulse timing structure and ha...

The dynamic interplay between proteins and their ligands is central to molecular biology, pharmacology, and drug development but is difficult to resolve experimentally. Using time-resolved serial crystallography at a synchrotron and X-ray laser, we studied the release of the photochemical affinity switch azo-Combretastatin A4 from the anti-cancer t...

X-ray free electron lasers (XFELs) have provided scientists opportunities to study matter with unprecedented temporal and spatial resolutions. However, access to the attosecond domain (i.e., below 1 femtosecond) remains elusive. Herein, a time-dependent experimental concept is theorized, allowing us to track ultrafast processes in matter with sub-f...

Chloride transport by microbial rhodopsins is an essential process for which molecular details—such as the mechanisms that convert light energy to drive ion pumping and ensure the unidirectionality of the transport—have remained elusive. We combined time-resolved serial crystallography with time-resolved spectroscopy and multiscale simulations to e...

Using ultrafast X-ray absorption spectroscopy, we observe how a rhodium carbonyl catalyst is formed on femtosecond timescales and reveal the decisive orbital interactions which facilitate the efficient cleavage of an alkane C-H bond from solution.

Manganese doping of ZnO nanoparticles, by introducing midgap states, is a potential solution to overcome the limitations of rapid recombination of photogenerated carriers. Ultrafast transient anisotropy measurements uncover the trapping dynamics upon Mn doping.

Serial femtosecond crystallography (SFX) at X-ray free-electron lasers (XFELs) enables essentially radiation-damage-free macromolecular structure determination using microcrystals that are too small for synchrotron studies. However, SFX experiments often require large amounts of sample in order to collect highly redundant data where some of the man...

Aqueous iron (III) oxide nanoparticles were irradiated with pure self-amplified spontaneous emission (SASE) X-ray free-electron laser (XFEL) pulses tuned to the energy around the Fe K-edge ionization threshold. For each XFEL shot, the incident X-ray pulse spectrum and Fe Kβ emission spectrum were measured synchronously with dedicated spectrometers...

Ultrafast electron delocalization induced by a femtosecond laser pulse is a well-known process in which electrons are ejected from the ions within the laser pulse duration. However, very little is known about the speed of electron localization out of an electron gas in correlated metals, i.e., the capture of an electron by an ion. Here, we demonstr...

Optical-domain transient grating (TG) spectroscopy is a versatile background-free four-wave-mixing technique that is used to probe vibrational, magnetic and electronic degrees of freedom in the time domain¹. The newly developed coherent X-ray free-electron laser sources allow its extension to the X-ray regime. X-rays offer multiple advantages for T...

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 l...

We present the first lasing results of SwissFEL, a hard X-ray free-electron laser (FEL) that recently came into operation at the Paul Scherrer Institute in Switzerland. SwissFEL is a very stable, compact and cost-effective X-ray FEL facility driven by a low-energy and ultra-low-emittance electron beam travelling through short-period undulators. It...

Long-wavelength pulses from the Swiss X-ray free-electron laser (XFEL) have been used for de novo protein structure determination by native single-wavelength anomalous diffraction (native-SAD) phasing of serial femtosecond crystallography (SFX) data. In this work, sensitive anomalous data-quality indicators and model proteins were used to quantify...

Significance The structure–function relationship in central to biology, while the structural dynamics are driven by electronic changes. Doming of ferrous heme proteins, which is central to the respiratory function of hemoglobin, ensues from populating high-spin states. However, for ferric heme proteins, doming was excluded. Here, we show that high-...

In haemoglobin the change from the low-spin (LS) hexacoordinated haem to the high spin (HS, S = 2) pentacoordinated domed deoxy-myoglobin (deoxyMb) form upon ligand detachment from the haem and the reverse process upon ligand binding are what ultimately drives the respiratory function. Here we probe them in the case of Myoglobin-NO (MbNO) using ele...

Light-driven sodium pumps actively transport small cations across cellular membranes¹. These pumps are used by microorganisms to convert light into membrane potential and have become useful optogenetic tools with applications in neuroscience. Although the resting state structures of the prototypical sodium pump Krokinobacter eikastus rhodopsin 2 (K...

The structure-function relationship is at the heart of biology and major protein deformations are correlated to specific functions. In the case of heme proteins, doming is associated with the respiratory function in hemoglobin and myoglobin, while ruffling has been correlated with electron transfer processes, such as in the case of Cytochrome c (Cy...

In haemoglobin (consisting of four globular myoglobin-like subunits), the change from the low-spin (LS) hexacoordinated haem to the high spin (HS) pentacoordinated domed form upon ligand detachment and the reverse process upon ligand binding, represent the transition states that ultimately drive the respiratory function. Visible-ultraviolet light h...

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu–C and Cu–P bonds represents an underexplored type of luminopho...

Many of the scientific applications for X-ray free-electron lasers seek to exploit the ultrashort pulse durations of intense X-rays to obtain femtosecond time resolution of various processes in a “pump-probe” scheme. One of the limiting factors for such experiments is the timing jitter between the X-rays and ultrashort pulses from more conventional...

Ultrafast electron delocalization induced by a fs laser pulse is a well-known process and is the initial step for important applications such as fragmentation of molecules or laser ablation in solids. It is well understood that an intense fs laser pulse can remove several electrons from an atom within its pulse duration. [1] However, the speed of e...

Kiyotaka Asakura, Kelly J. Gaffney, Christopher Milne, and Makina Yabashi introduce the PCCP themed issue on X-ray free-electron lasers (XFELs).

We discuss our recently reported femtosecond (fs) X-ray emission spectroscopy results on the ligand dissociation and recombination in Nitrosylmyoglobin (MbNO) in the context of previous studies on ferrous haem proteins....

The photoinduced dynamics of ferric Cytochrome c was investigated by ultrafast non-resonant X-ray emission (XES) and X-Ray Absorption (XAS) spectroscopies, and a cascade through high spin states accompanied by heme doming are observed for the first time.

Transient IR and X-Ray spectroscopies were used to investigate excited state delocalization of a mixed valence Ru based donor-bridge-acceptor complex on a femtosecond timescale revealing the role of the electron density on the Ru-CN-Ru fragment.

Stochastic processes are highly relevant in research fields as different as neuroscience, economy, ecology, chemistry, and fundamental physics. However, due to their intrinsic unpredictability, stochastic mechanisms are very challenging for any kind of investigations and practical applications. Here we report the deliberate use of stochastic X-ray...

A von Hamos geometry based wavelength dispersive spectrometer combined with an in situ reactor cell has been developed to measure non-resonant sulfur Kα emission for the in situ speciation of low concentrations of sulfur. The spectrometer operates at 15 cm focusing radius, is equipped with a curved Si(111) crystal and a position sensitive detector,...

Disentangling the strong interplay between electronic and nuclear degrees of freedom is essential to achieve a full understanding of excited state processes during ultrafast nonadiabatic chemical reactions. However, the complexity of multi-dimensional potential energy surfaces means that this remains challenging. The energy flow during vibrational...

For incident x-ray energies below the core level ionization threshold, one-photon absorption (OPA) leads to off-resonant x-ray excitations that are mediated by a virtual intermediate electronic state. In the linear regime of x-ray interaction, this intermediate state may decay radiatively and the maximum energy of the emitted photon is given by the...

Time-resolved transient grating (TG) spectroscopy facilitates detailed studies of electron dynamics and transport phenomena by means of a periodic excitation of matter with coherent ultrashort light pulses. Several current and next generation free-electron laser (FEL) facilities provide fully coherent pulses with few femtosecond pulse durations and...

The list of authors in the paper by Juranić et al. (2018) [ J. Synchrotron Rad.25 , 1238–1248] is corrected.

"Probe-before-destroy" methodology permitted diffraction and imaging measurements of intact specimens using ultrabright but highly destructive X-ray free-electron laser (XFEL) pulses. The methodology takes advantage of XFEL pulses ultrashort duration to outrun the destructive nature of the X-rays. Atomic movement, generally on the order of >50 fs,...

The evolution of bismuth crystal structure upon excitation of its A1g phonon has been intensely studied with short pulse optical lasers. Here we present the first-time observation of a hard x-ray induced ultrafast phase transition in a bismuth single crystal at high intensities (~1014 W/cm2). The lattice evolution was followed using a recently demo...

The extension of transient grating spectroscopy to the x-ray regime will create numerous opportunities, ranging from the study of thermal transport in the ballistic regime to charge, spin, and energy transfer processes with atomic spatial and femtosecond temporal resolution. Studies involving complicated split-and-delay lines have not yet been succ...

The development of X-ray free-electron lasers (XFELs) has opened the possibility to investigate the ultrafast dynamics of biomacromolecules using X-ray diffraction. Whereas an increasing number of structures solved by means of serial femtosecond crystallography at XFELs is available, the effect of radiation damage on protein crystals during ultrafa...

The evolution of the bismuth crystal structure upon excitation of its A$_{1g}$ phonon has been intensely studied with short pulse optical lasers. Here we present the first-time observation of a hard x-ray induced ultrafast phase transition in a bismuth single crystal, at high intensities (~$10^{14}$ W/cm$^2$). The lattice evolution was followed usi...

The SwissFEL Aramis beamline, covering the photon energies between 1.77 keV and 12.7 keV, features a suite of online photon diagnostics tools to help both users and FEL operators in analysing data and optimizing experimental and beamline performance. Scientists will be able to obtain information about the flux, spectrum, position, pulse length, and...

Look fast Organisms from bacteria to humans sense and react to light. Proteins that contain the light-sensitive molecule retinal couple absorption of light to conformational changes that produce a signal or move ions across a membrane. Nogly et al. used an x-ray laser to probe the earliest structural changes to the retinal chromophore within microc...

Nanostructures of transition metal oxides, such as zinc oxide, have attracted considerable interest for solar-energy conversion and photocatalysis. Both applications are sensitive to the transport and trapping of photoexcited charge carriers. The probing of electron trapping has recently become possible using time-resolved element-sensitive methods...