Investigation of encapsulated water wire within self-assembled hydrophilic nanochannels, in a modified γ4-amino acid crystals: Tracking thermally induced changes of intermolecular interactions within a crystalline hydrate.

Nanostructures formed by the self-assembly of modified/unmodified amino acids have the potential to be useful in several biological/nonbiological applications. In that regard, the greater conformational space provided by γ-amino acids, owing to their additional backbone torsional degrees of freedom and enhanced proteolytic stability, compared to their α-counterparts, should be explored. Though, modified single amino acid-based nanomaterials such as nanobelts or hydrogels are developed by utilizing the monosubstituted γ-amino acids derived from the backbone homologation of phenylalanine (Phe). Examples of a single γ-amino acid-based porous nanostructure capable of accommodating solvent molecules are not really known. The crystal structures of a modified γ4(R)Phe residue, Boc-γ4(R)Phe-OH, at different temperatures, showed that hydrogen-bonded water molecules are forming a wire inside hydrophilic nanochannels. The dynamics of intermolecular interactions between the water wire and the inner wall of the channel with relation to the temperature change was investigated by analyzing the natural bonding orbital (NBO) calculation results performed with the single crystal structures obtained at different temperature points. The NBO results showed that from 325 K onward, the strength of water-water interactions in the water wire are getting weaker, whereas, for the water-inner wall interactions, it getting stronger, suggesting a favorable change in the orientation of water molecules with temperatures, for the latter.

Crystal structure of 2-methyl-1H-imidazol-3-ium 3,5-di-carb-oxy-benzoate.

The structure of the title salt, C4H7N2 +·C9H5O6 - (1), is reported. The compound is built from a protonated 2-methyl-imidazole and a singly deprotonated trimesic acid. Detailed analysis of bond distances and angles for both ions reveals subtle differences compared with their neutral mol-ecule counterpart. Analysis of the crystal packing in compound 1 reveals the formation of undulating chains by the ions through hydrogen bonding. The chains stack along the b axis through π-π inter-actions and inter-connect with other chains in an out-of-phase arrangement along the ac plane through further hydrogen-bonding inter-actions.

Electron population dynamics in resonant non-linear x-ray absorption in nickel at a free-electron laser.

Free-electron lasers provide bright, ultrashort, and monochromatic x-ray pulses, enabling novel spectroscopic measurements not only with femtosecond temporal resolution: The high fluence of their x-ray pulses can also easily enter the regime of the non-linear x-ray-matter interaction. Entering this regime necessitates a rigorous analysis and reliable prediction of the relevant non-linear processes for future experiment designs. Here, we show non-linear changes in the L3-edge absorption of metallic nickel thin films, measured with fluences up to 60 J/cm2. We present a simple but predictive rate model that quantitatively describes spectral changes based on the evolution of electronic populations within the pulse duration. Despite its simplicity, the model reaches good agreement with experimental results over more than three orders of magnitude in fluence, while providing a straightforward understanding of the interplay of physical processes driving the non-linear changes. Our findings provide important insights for the design and evaluation of future high-fluence free-electron laser experiments and contribute to the understanding of non-linear electron dynamics in x-ray absorption processes in solids at the femtosecond timescale.

Structural dynamics of a thermally silent triiron(II) spin crossover defect grid complex.

The structural evolution of spin crossover (SCO) complexes during their spin transition at equilibrium and out-of-equilibrium conditions needs to be understood to enable their successful utilisation in displays, actuators and memory components. In this study, diffraction techniques were employed to study the structural changes accompanying the temperature increase and the light irradiation of a defect [2 × 2] triiron(II) metallogrid of the form [FeII3LH2(HLH)2](BF4)4·4MeCN (FE3), LH = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole. Although a multi-temperature crystallographic investigation on single crystals evidenced that the compound does not exhibit a thermal spin transition, the structural analysis of the defect grid suggests that the flexibility of the grid, provided by a metal-devoid vertex, leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. Time-resolved photocrystallography results reveal that upon excitation with a ps laser pulse, the defect grid shows the first two steps of the out-of-equilibrium process, namely the photoinduced and elastic steps, occurring at the ps and ns time scales, respectively. Similar to a previously reported [2 × 2] tetrairon(II) metallogrid, FE3 exhibits a local distortion of the entire grid during the photoinduced step and a long-range distortion of the lattice during the elastic step. Although the lifetime of the pure photoinduced high spin (HS) state is longer in the tetranuclear grid than in the defect grid, suggesting that the global nuclearity plays a crucial role for the lifetime of the photoinduced species, the influence of the co-crystalising solvent on the lifetime of the photoinduced HS state remains unknown. This study sheds light on the out-of-equilibrium dynamics of a thermally silent defect triiron SCO metallogrid.

Axial vs equatorial: Capturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor-bridge-acceptor dyad in nanosecond-time-scale.

Two conformational polymorphs of a donor-bridge-acceptor (D-B-A) dyad, p-(CH3)2N-C6H4-(CH2)2-(1-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH3)2N-C6H4/DMA is connected through a bridging group (B), -CH2-CH2-, to the electron acceptor (A) moiety pyrene. Though molecular dyads like PyCHDMA have the potential to change solar energy into electrical current through the process of photoinduced intramolecular charge transfer (ICT), the major challenge is the real-time investigation of the photoinduced ICT process in crystals, necessary to design solid-state optoelectronic materials. The time-correlated single photon counting (TCSPC) measurements with the single crystals showed that the ICT state lifetime of the thermodynamic form, PyCHDMA1 (pyrene and DMA: axial), is ∼3 ns, whereas, for the kinetic form, PyCHDMA20 (pyrene and DMA: equatorial), it is ∼7 ns, while photoexcited with 375 nm radiation. The polymorphic crystals were photo-excited and subsequently probed with a pink Laue x-ray beam in time-resolved x-ray diffraction (TRXRD) measurements. The TRXRD results suggest that in the ICT state, due to electron transfer from the tertiary N-atom in DMA moiety to the bridging group and pyrene moiety, a decreased repulsion between the lone-pair and the bond-pair at N-atom induces planarity in the C-N-(CH3)2 moiety, in both polymorphs. The Natural Bond Orbital calculations and partial atomic charge analysis by Hirshfeld partitioning also corroborated the same. Although the interfragment charge transfer (IFCT) analysis using the TDDFT results showed that for the charge transfer excitation in both conformers, the electrons were transferred from the DMA moiety to mostly the pyrene moiety, the bridging group has little role to play in that.

Advancements in Liquid Jet Technology and X-ray Spectroscopy for Understanding Energy Conversion Materials during Operation.

ConspectusWater splitting is intensively studied for sustainable and effective energy storage in green/alternative energy harvesting-storage-release cycles. In this work, we present our recent developments for combining liquid jet microtechnology with different types of soft X-ray spectroscopy at high-flux X-ray sources, in particular developed for studying the oxygen evolution reaction (OER). We are particularly interested in the development of in situ photon-in/photon-out techniques, such as in situ resonant inelastic X-ray scattering (RIXS) techniques at high-repetition-frequency X-ray sources, pointing toward operando capabilities. The pilot catalytic systems we use are perovskites having the general structure ABO3 with lanthanides or group II elements at the A sites and transition metals at the B sites. Depending on the chemical substitutions of ABO3, their catalytic activity for OER can be tuned by varying the composition.In this work, we present our in situ RIXS studies of the manganese L-edge of perovskites during OER. We have developed various X-ray spectroscopy approaches like transmission zone plate-, reflection zone plate-, and grating-based emission spectroscopy techniques. Combined with tunable incident X-ray energies, we yield complementary information about changing (inverse) X-ray absorption features of the perovskites, allowing us to deduce element- and oxidation-state-specific chemical monitoring of the catalyst. Adding liquid jet technology, we monitor element- and oxidation-state-specific interactions of the catalyst with water adsorbate during OER. By comparing the different technical spectroscopy approaches combined with high-repetition-frequency experiments at synchrotrons and free-electron lasers, we conclude that the combination of liquid jet with low-resolution zone-plate-based X-ray spectroscopy is sufficient for element- and oxidation-state-specific chemical monitoring during OER and easy to handle.For an in-depth study of OER mechanisms, however, including the characterization of catalyst-water adsorbate in terms of their charge transfer properties and especially valence intermediates formed during OER, high-resolution spectroscopy tools based on a combination of liquid jets with gratings bear bigger potential since they allow resolution of otherwise-overlapping X-ray spectroscopy transitions. Common for all of these experimental approaches is the conclusion that without the versatile developments of liquid jets and liquid beam technologies, elaborate experiments such as high-repetition experiments at high-flux X-ray sources (like synchrotrons or free-electron lasers) would hardly be possible. Such experiments allow sample refreshment for every single X-ray shot for repetition frequencies of up to 5 MHz, so that it is possible (a) to study X-ray-radiation-sensitive samples and also (b) to utilize novel types of flux-hungry X-ray spectroscopy tools like photon-in/photon-out X-ray spectroscopy to study the OER.

Fluorescence Spectroscopy Shows Porphyrins Produced by Cultured Oral Bacteria Differ Depending on Composition of Growth Media.

Red fluorophores synthesized by oral bacteria are important for fluorescence-based diagnosis and treatment because they are used as markers for bacterially infected tissue, mature plaque, or calculus. A range of porphyrins have been identified as the source of this fluorescence in carious tissue. It is not clear which of these porphyrins are produced by individual oral bacteria or whether this ability depends on other factors. This study examined and compared the fluorescence spectra produced by selected cultured oral bacteria when grown on agars containing different nutrients with spectra for protoporphyrin IX, Zn-protoporphyrin IX, haematoporphyrin, and haematin. Actinomyces israelii (Deutsche Sammlung von Mikroorganismen [DSM], 43320), Actinomyces naeslundii (DSM 43013), Fusobacterium nucleatum (DSM, 20482), Lactobacillus casei (DSM, 20011), Prevotella intermedia (DSM, 20706), Streptococcus mutans (DSM, 20523), Streptococcus oralis (DSM, 20627), Streptococcus salivarius (DSM, 20560) and Streptococcus sobrinus (DSM, 20742) were rehydrated and grown anaerobically on caso, caso blood (containing 5% sheep blood), and caso chlorophyll (containing 5% spinach extract) agar for 3 days at 37°C in the dark. Colonies were harvested, transferred to ethanol, and centrifuged. Fluorescence emission spectra were recorded from the supernatant at 405 nm excitation (Fluorolog 3-22, Jobin Yvon-Spex ISA, Edison, NJ, USA). All Streptococci, L. casei, and F. nucleatum produced red fluorescence when grown on caso and caso chlorophyll agar but not on caso blood agar. A. naeslundii and P. intermedia emitted intense red fluorescence when grown on caso or caso blood agar but not on caso chlorophyll agar. Fluorescence emission spectra of A. naeslundii and P. intermedia grown on caso blood agar correlated exactly with both fluorescence peaks for protoporphyrin-IX at 632 and 701 nm. Most peaks observed could be correlated with at least one of the emission peaks of protoporphyrin IX, Zn-protoporphyrin IX, or haematoporphyrin. Oral bacteria emitted red fluorescence matching known porphyrins, but this depended on nutrients available in the agar.

Short- vs. long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon(II) spin crossover grid complex observed by time-resolved X-Ray crystallography.

Spin crossover complexes (SCO) are among the most studied molecular switches due to their potential use in displays, sensors, actuators and memory components. A prerequisite to using these materials is the understanding of the structural changes following the spin transition at out-of-equilibrium conditions. So far, out-of-equilibrium studies in SCO solids have been focused on mononuclear complexes, though a growing number of oligonuclear SCO complexes showing cooperative effects are being reported. Here, we use time-resolved pink Laue crystallography to study the out-of-equilibrium dynamics of a [2 × 2] tetranuclear metallogrid of the form [FeII4LMe4](BF4)4·2MeCN ([LMe]- = 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazolate). The out-of-equilibrium spin state switching induced by a ps laser pulse demonstrates that the metallogrid exhibits a multi-step response similar to that reported for mononuclear complexes. Contrary to the mononuclear complexes, the metallogrid shows two types of elastic distortions at different time scales. The first is a short-range distortion that propagates over the entire Fe4 grid complex during the ps time scale, and it is caused by the rearrangement of the coordination sphere of the photo-switching ion and the constant feedback between strongly linked metal ions. The second is a long-range distortion caused by the anisotropic expansion of the lattice during the ns time scale, observed in mononuclear materials. The structural analysis demonstrates that the long-range prevails over the short-range distortion, inducing the largest deformation of both the entire grid and the coordination sphere of each metal ion. The present study sheds light on the out-of -equilibrium dynamics of a non-cooperative oligonuclear complex.

Synthesis and structure of hexa-aqua-cobalt bis-(2-methyl-1H-imidazol-3-ium) tetra-aqua-bis-(benzene-1,3,5-tri-carboxyl-ato-κO)cobalt.

The title compound, (C4H7N2)2[Co(H2O)6][Co(C9H3O6)2(H2O)4] (1), was synthesized from cobalt(II) chloride, 1,3,5-benzene tri-carb-oxy-lic acid (Hbtc) and 2-methyl-imidazole (H-2mIm) under ambient conditions. The structure of 1 is here reported and compared with the parent complex hexa-aqua-cobalt bis-(1H-imidazol-3-ium) tetra-aqua-bis-(benzene-1,3,5-tri-carboxyl-ato)cobalt (2).

Metal-to-metal communication during the spin state transition of a [2 × 2] Fe(II) metallogrid at equilibrium and out-of-equilibrium conditions.

Spin crossover (SCO) complexes are prototypes of materials with bi- or multi-stability in the solid state. The structural evolution during their spin transition is a key feature to establish the foundations of how to utilize this type of material. So far, ultrafast time-resolved structural investigations of SCO solids have been focused on monometallic complexes, though an increasing number of oligometallic SCO complexes showing cooperativity effects are being reported. Here, we used single crystal X-ray crystallography and time-resolved pink Laue photocrystallography to study the molecular reorganisation during the thermal and photoinduced SCO of a [2 × 2] tetranuclear metallogrid of the form [FeII4LMe4](BF4)4·2MeCN ([LMe]- = 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazolate). A multitemperature crystallographic investigation on single crystals reveals an effective communication between the metal centres during thermal SCO, observed by the simultaneous transformation of the coordination polyhedra of both crystallographic-symmetry independent metal atoms accompanying the SCO in only one of them. Time-resolved photocrystallography results reveal the different molecular responses between mononuclear and oligonuclear complexes, after light irradiation with a picosecond laser pulse. While mononuclear SCO complexes reorganise once during the first nanosecond after excitation, the tetranuclear metallogrid exhibits a multiple structural rearrangement in the same span of time. Such behaviour is attributed to the elastic communication between metal atoms, which allows the propagation of a short-range elastic distortion over the entire Fe4 grid complex. The present study sheds light on the importance of strong elastic coupling of metal atoms during the correlated spin transition of oligometallic complexes.

Ultrafast sorting: Excimeric π-π stacking distinguishes pyrene-N-methylacetamide isomers on the ultrafast time scale.

Pyrene based molecules are inclined to form excimers through self-association upon photoexcitation. In this work, the pyrene core is functionalized with the N-methylacetamide group at the position 1 or 2 to develop pyren-1-methylacetamide (PyMA1) and pyren-2-methylacetamide (PyMA2), respectively. Upon photoexcitation with 345 nm, a portion of molecules in PyMA1 and PyMA2 solutions at ≥1.0 mM have formed static excimers. The steady state spectroscopic measurements suggest that, whether it is the dimerization of molecules in the ground state (GS) or in excimer formation, characteristic signs are more pronounced in PyMA1 than its isomeric counterpart, PyMA2. The shift of the excimer band in their respective emission spectra suggests that the extent of overlap in π-π stacking is greater for PyMA1 than for PyMA2 in the excited state. The optimized geometry of dimers in toluene shows that the overlapping area between the pyrene moieties in π-π stacking between the dimers is greater for PyMA1 than for PyMA2 in GS. The natural bond orbital analysis with the optimized GS geometries shows that the stabilization/interaction energy between the dimers in π-π stacking is higher in PyMA1 compared to PyMA2 in toluene. The transient absorption (TA) measurements in toluene over the fs-ps regime (fs-TA) showed that the formation of static excimers with pre-associated dimers in PyMA1 happens in ∼700 fs whereas the excimers for the pre-associated dimers in PyMA2 have formed in slightly slower time scale (∼1.95 ps). Contrary to what was observed in solution, the extent of overlap in π-π stacking is lower for PyMA1 dimers (∼17%) than for PyMA2 dimers (∼37%) in single crystals.

Ionization and Photofragmentation of Isolated Metalloporphyrin Cations Investigated by VUV Action Spectroscopy*.

We investigated the photoionization and fragmentation of isolated metal protoporphyrin IX cations (MPPIX+ with M=Fe, Co, Zn) by means of vacuum-ultraviolet (VUV) action spectroscopy in the energy range of 8.5-35 eV. Experiments were carried out in the gas phase by interfacing an electrospray ionization tandem mass spectrometer with a synchrotron beamline. The mass spectra and partial ion yields show that photoexcitation of the precursor ions predominantly leads to . CH2 COOH radical side-chain losses of the macrocycle with additional methyl radical (. CH3 ) side-chain losses. Ionization, in contrast, leads to the formation of the intact ionized precursor and various doubly charged fragments which are mostly due to side-chain cleavages. Although statistical fragmentation dominates, we found evidence for non-statistical processes such as new fragments involving for example single and double H2 O losses, indicating that different relaxation mechanisms are at play upon photoionization compared to photoexcitation. The measured ionization energies were 9.6±0.2 eV, 9.4±0.2 eV and 9.6±0.2 eV for FePPIX+ , CoPPIX+ and ZnPPIX+ , respectively.

The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy.

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX+) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant excitations of CoPPIX+ at the cobalt L3-edge lead predominantly to the formation of the intact radical dication and doubly charged fragments through losses of charged and neutral side chains from the macrocycle. The comparison between experiment and theory shows that CoPPIX+ is in a 3A2g triplet ground state and that competing excitations to metal-centred non-bonding and antibonding σ* molecular orbitals lead to distinct deexcitation pathways.

Probing Structural Information of Gas-Phase Peptides by Near-Edge X-ray Absorption Mass Spectrometry.

Near-edge X-ray absorption mass spectrometry (NEXAMS) is an action-spectroscopy technique of growing interest for investigations into the spatial and electronic structure of biomolecules. It has been used successfully to give insights into different aspects of the photodissociation of peptides and to probe the conformation of proteins. It is a current question whether the fragmentation pathways are sensitive toward effects of conformational isomerism, tautomerism, and intramolecular interactions in gas-phase peptides. To address this issue, we studied the cationic fragments of cryogenically cooled gas-phase leucine enkephalin ([LeuEnk+H]+) and methionine enkephalin ([MetEnk+H]+) produced upon soft X-ray photon absorption at the carbon, nitrogen, and oxygen K-edges. The interpretation of the experimental ion yield spectra was supported by density-functional theory and restricted-open-shell configuration interaction with singles (DFT/ROCIS) calculations. The analysis revealed several effects that could not be rationalized based on the peptide's amino acid sequences alone. Clear differences between the partial ion yields measured for both peptides upon C 1s → π*(C═C) excitations in the aromatic amino acid side chains give evidence for a sulfur-aromatic interaction between the methionine and phenylalanine side chain of [MetEnk+H]+. Furthermore, a peak associated with N 1s → π*(C═N) transitions, linked to a tautomeric keto-to-enol conversion of peptide bonds, was only present in the photon energy resolved ion yield spectra of [MetEnk+H]+.

Site-Selective Dissociation upon Sulfur L-Edge X-ray Absorption in a Gas-Phase Protonated Peptide.

Site-selective dissociation induced by core photoexcitation of biomolecules is of key importance for the understanding of radiation damage processes and dynamics and for its promising use as "chemical scissors" in various applications. However, identifying products of site-selective dissociation in large molecules is challenging at the carbon, nitrogen, and oxygen edges because of the high recurrence of these atoms and related chemical groups. In this paper, we present the observation of site-selective dissociation at the sulfur L-edge in the gas-phase peptide methionine enkephalin, which contains only a single sulfur atom. Near-edge X-ray absorption mass spectrometry has revealed that the resonant S 2p → σ*C-S excitation of the sulfur contained in the methionine side chain leads to site-selective dissociation, which is not the case after core ionization above the sulfur L-edge. The prospects of such results for the study of charge dynamics in biomolecular systems are discussed.

A zone-plate-based two-color spectrometer for indirect X-ray absorption spectroscopy.

X-ray absorption spectroscopy (XAS) is a powerful element-specific technique that allows the study of structural and chemical properties of matter. Often an indirect method is used to access the X-ray absorption (XA). This work demonstrates a new XAS implementation that is based on off-axis transmission Fresnel zone plates to obtain the XA spectrum of La0.6Sr0.4MnO3 by analysis of three emission lines simultaneously at the detector, namely the O 2p-1s, Mn 3s-2p and Mn 3d-2p transitions. This scheme allows the simultaneous measurement of an integrated total fluorescence yield and the partial fluorescence yields (PFY) of the Mn 3s-2p and Mn 3d-2p transitions when scanning the Mn L-edge. In addition to this, the reduction in O fluorescence provides another measure for absorption often referred to as the inverse partial fluorescence yield (IPFY). Among these different methods to measure XA, the Mn 3s PFY and IPFY deviate the least from the true XA spectra due to the negligible influence of selection rules on the decay channel. Other advantages of this new scheme are the potential to strongly increase the efficiency and throughput compared with similar measurements using conventional gratings and to increase the signal-to-noise of the XA spectra as compared with a photodiode. The ability to record undistorted bulk XA spectra at high flux is crucial for future in situ spectroscopy experiments on complex materials.

Coulomb explosion imaging of CH3I and CH2ClI photodissociation dynamics.

The photodissociation dynamics of CH3I and CH2ClI at 272 nm were investigated by time-resolved Coulomb explosion imaging, with an intense non-resonant 815 nm probe pulse. Fragment ion momenta over a wide m/z range were recorded simultaneously by coupling a velocity map imaging spectrometer with a pixel imaging mass spectrometry camera. For both molecules, delay-dependent pump-probe features were assigned to ultraviolet-induced carbon-iodine bond cleavage followed by Coulomb explosion. Multi-mass imaging also allowed the sequential cleavage of both carbon-halogen bonds in CH2ClI to be investigated. Furthermore, delay-dependent relative fragment momenta of a pair of ions were directly determined using recoil-frame covariance analysis. These results are complementary to conventional velocity map imaging experiments and demonstrate the application of time-resolved Coulomb explosion imaging to photoinduced real-time molecular motion.

X-ray spectroscopy with variable line spacing based on reflection zone plate optics.

X-ray spectroscopy is a method, ideally suited for investigating the electronic structure of matter, which has been enabled by the rapid developments in light sources and instruments. The x-ray fluorescence lines of life-relevant elements such as carbon, nitrogen, and oxygen are located in the soft x-ray regime and call for suitable spectrometer devices. In this Letter, we present a high-resolution spectrum of liquid water, recorded with a soft x-ray spectrometer based on a reflection zone plate (RZP) design. The RZP-based spectrometer with meridional variation of line space density from 2953 to 3757 l/mm offers extremely high detection efficiency and, at the same time, medium energy resolution. We can reproduce the well-known splitting of liquid water in the lone pair regime with 10 s acquisition time.

CAMP@FLASH: an end-station for imaging, electron- and ion-spectroscopy, and pump-probe experiments at the FLASH free-electron laser.

The non-monochromatic beamline BL1 at the FLASH free-electron laser facility at DESY was upgraded with new transport and focusing optics, and a new permanent end-station, CAMP, was installed. This multi-purpose instrument is optimized for electron- and ion-spectroscopy, imaging and pump-probe experiments at free-electron lasers. It can be equipped with various electron- and ion-spectrometers, along with large-area single-photon-counting pnCCD X-ray detectors, thus enabling a wide range of experiments from atomic, molecular, and cluster physics to material and energy science, chemistry and biology. Here, an overview of the layout, the beam transport and focusing capabilities, and the experimental possibilities of this new end-station are presented, as well as results from its commissioning.

Near-Edge Soft X-ray Absorption Mass Spectrometry of Protonated Melittin.

We have investigated the photoionization and photofragmentation yields of gas-phase multiply protonated melittin cations for photon energies at the K-shell absorption edges of carbon, nitrogen, and oxygen. Two similar experimental approaches were employed. In both experiments, mass selected [melittin+qH]q+ (q=2-4) ions were accumulated in radiofrequency ion traps. The trap content was exposed to intense beams of monochromatic soft X-ray photons from synchrotron beamlines and photoproducts were analyzed by means of time-of-flight mass spectrometry. Mass spectra were recorded for fixed photon energies, and partial ion yield spectra were recorded as a function of photon energy. The combination of mass spectrometry and soft X-ray spectroscopy allows for a direct correlation of protein electronic structure with various photoionization channels. Non-dissociative single and double ionization are used as a reference. The contribution of both channels to various backbone scission channels is quantified and related to activation energies and protonation sites. Soft X-ray absorption mass spectrometry combines fast energy deposition with single and double ionization and could complement established activation techniques. Graphical Abstract ᅟ.