ATP-Triggered Fe(CN)CO Synthon Transfer from the Maturase HypCD to the Active Site of Apo-[NiFe]-Hydrogenase.

[NiFe]-hydrogenases catalyze the reversible activation of H using a unique NiFe(CN)CO metal site, which is assembled by a sophisticated multiprotein machinery. The [4Fe-4S] cluster-containing HypCD complex, which possesses an ATPase activity with a hitherto unknown function, serves as the hub for the assembly of the Fe(CN)CO subfragment. HypCD is also thought to be responsible for the subsequent transfer of the iron fragment to the apo-form of the catalytic hydrogenase subunit, but the underlying mechanism has remained unexplored.

Lattice Dynamics of CuZnSn(S ,Se ) Kesterite Thin-Film Solar Cells Studied by Nuclear Inelastic Scattering.

Phonons play a crucial role in thermalization and non-radiative recombination losses in semiconductors, impacting the power conversion efficiency of solar cells. To shed light on the lattice dynamics in CuZnSn(S ,Se ) (CZTSSe) thin-film solar cells and validate the extensive number of theoretical studies, we determine the Sn-partial phonon density of states (Sn-PDOS) by nuclear inelastic X-ray scattering. CZTSSe-based devices, one with near-stoichiometric and two with off-stoichiometric compositions, are investigated, and the results are correlated with the corresponding power conversion efficiencies (PCEs) of 3.

Vibrations and Phase Stability in Mixed Valence Antimony Oxide.

α-SbO (cervantite) and β-SbO (clinocervantite) are mixed valence compounds with equal proportions of Sb and Sb as represented in the formula SbSbO. Their structure and properties can be difficult to calculate owing to the Sb lone-pair electrons. Here, we present a study of the lattice dynamics and vibrational properties using a combination of inelastic neutron scattering, Mössbauer spectroscopy, nuclear inelastic scattering, and density functional theory (DFT) calculations.

Stepwise assembly of the active site of [NiFe]-hydrogenase.

[NiFe]-hydrogenases are biotechnologically relevant enzymes catalyzing the reversible splitting of H into 2e and 2H under ambient conditions. Catalysis takes place at the heterobimetallic NiFe(CN)(CO) center, whose multistep biosynthesis involves careful handling of two transition metals as well as potentially harmful CO and CN molecules. Here, we investigated the sequential assembly of the [NiFe] cofactor, previously based on primarily indirect evidence, using four different purified maturation intermediates of the catalytic subunit, HoxG, of the O-tolerant membrane-bound hydrogenase from Cupriavidus necator.

Substrate-Gated Transformation of a Pre-Catalyst into an Iron-Hydride Intermediate [(NO)(CO)Fe(μ-H)Fe(CO)(NO)] for Catalytic Dehydrogenation of Dimethylamine Borane.

Continued efforts are made on the development of earth-abundant metal catalysts for dehydrogenation/hydrolysis of amine boranes. In this study, complex [K-18-crown-6-ether][(NO)Fe(μ-Pyr)(μ-CO)Fe(NO)] (, Pyr = 3-methylpyrazolate) was explored as a pre-catalyst for the dehydrogenation of dimethylamine borane (DMAB). Upon evolution of H from DMAB triggered by , parallel conversion of into [(NO)Fe(,'-PyrBHNMe)] () and an iron-hydride intermediate [(NO)(CO)Fe(μ-H)Fe(CO)(NO)] () was evidenced by X-ray diffraction/nuclear magnetic resonance/infrared/nuclear resonance vibrational spectroscopy experiments and supported by density functional theory calculations.

Substituent Effects in Iron Porphyrin Catalysts for the Hydrogen Evolution Reaction.

For a future hydrogen economy, non-precious metal catalysts for the water splitting reactions are needed that can be implemented on a global scale. Metal-nitrogen-carbon (MNC) catalysts with active sites constituting a metal center with fourfold coordination of nitrogen (MN ) show promising performance, but an optimization rooted in structure-property relationships has been hampered by their low structural definition. Porphyrin model complexes are studied to transfer insights from well-defined molecules to MNC systems.

Evolution of the magnetic hyperfine field profiles in an ion-irradiated FeAl film measured by nuclear resonant reflectivity.

Nuclear resonant reflectivity (NRR) from an FeAl film was measured using synchrotron radiation at several grazing angles near the critical angle of total external reflection. Using laterally resolved measurements after irradiation with 20 keV Ne ions of gradually varying fluence of 0-3.0 × 10 ions cm, the progressive creation of the ferromagnetic A2 phase with increasing ion fluence was confirmed.

IRIXS Spectrograph: an ultra high-resolution spectrometer for tender RIXS.

The IRIXS Spectrograph represents a new design of an ultra-high-resolution resonant inelastic X-ray scattering (RIXS) spectrometer that operates at the Ru L-edge (2840 eV). First proposed in the field of hard X-rays by Shvyd'ko [(2015), Phys. Rev.

High-Repetition Rate Optical Pump-Nuclear Resonance Probe Experiments Identify Transient Molecular Vibrations after Photoexcitation of a Spin Crossover Material.

Phonon modes play a vital role in the cooperative phenomenon of light-induced spin transitions in spin crossover (SCO) molecular complexes. Although the cooperative vibrations, which occur over several hundreds of picoseconds to nanoseconds after photoexcitation, are understood to play a crucial role in this phase transition, they have not been precisely identified. Therefore, we have performed a novel optical laser pump-nuclear resonance probe experiment to identify the Fe-projected vibrational density of states (pDOS) during the first few nanoseconds after laser excitation of the mononuclear Fe(II) SCO complex [Fe(PM-BiA)(NCS)].

Towards high-quality nitrogen-doped diamond single crystals for X-ray optics.

In this manuscript, characterization of single-crystalline (111) plates prepared from type-Ib diamonds with a nitrogen content of 100-150 ppm by means of high-resolution rocking-curve imaging (RCI) is reported. Contrary to common opinion regarding the intrinsically poor diffraction quality of type-I diamonds, RCI showed the presence of nearly defect-free areas of several millimetres squared in the central part of the diamond plates. The observed broadening of the rocking curves is a result of the cutting and polishing processes, causing strains around the edges of the plates and rare defects.

Mössbauer, Nuclear Forward Scattering, and Raman Spectroscopic Approaches in the Investigation of Bioinduced Transformations of Mixed-Valence Antimony Oxide.

Mössbauer spectroscopy, nuclear forward scattering, and Raman spectroscopy were applied to study redox transformations of the synthesized mixed-valence (III/V) antimony oxide. The transformations were induced by a culture of a hyperthermophilic archaeon of the genus . The applied methods allowed us to reveal the minor decrease of ca.

Phonon Spectroscopy in Antimony and Tellurium Oxides.

α-SbO (senarmontite), β-SbO (valentinite), and α-TeO (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here, we present a study of the relationship between bonding and lattice dynamics of these compounds.

A portable on-axis laser-heating system for near-90° X-ray spectroscopy: application to ferropericlase and iron silicide.

A portable IR fiber laser-heating system, optimized for X-ray emission spectroscopy (XES) and nuclear inelastic scattering (NIS) spectroscopy with signal collection through the radial opening of diamond anvil cells near 90°with respect to the incident X-ray beam, is presented. The system offers double-sided on-axis heating by a single laser source and zero attenuation of incoming X-rays other than by the high-pressure environment. A description of the system, which has been tested for pressures above 100 GPa and temperatures up to 3000 K, is given.

Hard-X-Ray Spectroscopy with a Spectrographic Approach.

Hard-x-ray spectroscopy relies on a suite of modern techniques for studies of vibrational, electronic, and magnetic excitations in condensed matter. At present, the energy resolution of these techniques can be improved only by decreasing the spectral window of the involved optics-monochromators and analyzers-thereby sacrificing the intensity. Here, we demonstrate hard-x-ray spectroscopy with greatly improved energy resolution without narrowing the spectral window by adapting principles of spectrographic imaging to the hard-x-ray regime.

High-pressure nuclear inelastic scattering with backscattering monochromatization.

The capability to perform high-pressure low-temperature nuclear inelastic scattering on Te and Sb with a sapphire backscattering monochromator is presented. This technique was applied to measure nuclear inelastic scattering in TeO at pressures up to 10 GPa and temperatures down to 25 K. The evaluated partial Te densities of phonon states were compared with theoretical calculations and with Raman scattering measured under the same conditions.

Nuclear resonant scattering from Ir as a probe of the electronic and magnetic properties of iridates.

The high brilliance of modern synchrotron radiation sources facilitates experiments with high-energy x-rays across a range of disciplines, including the study of the electronic and magnetic correlations using elastic and inelastic scattering techniques. Here we report on Nuclear Resonance Scattering at the 73 keV nuclear level in Ir. The transitions between the hyperfine split levels show an untypically high E2/M1 multi-polarity mixing ratio combined with an increased sensitivity to certain changes in the hyperfine field direction compared to non-mixing transitions.

Angular vibrations of cryogenically cooled double-crystal monochromators.

The effect of angular vibrations of the crystals in cryogenically cooled monochromators on the beam performance has been studied theoretically and experimentally. A simple relation between amplitude of the vibrations and size of the focused beam is developed. It is shown that the double-crystal monochromator vibrations affect not only the image size but also the image position along the optical axis.

Nuclear forward scattering of synchrotron radiation by 99Ru.

We measured nuclear forward scattering spectra utilizing the (99)Ru transition, 89.571(3) keV, with a notably mixed E2/M1 multipolarity. The extension of the standard evaluation routines to include mixed multipolarity allows us to extract electric and magnetic hyperfine interactions from (99)Ru-containing compounds.

Hyperfine splitting and room-temperature ferromagnetism of Ni at multimegabar pressure.

Magnetic and elastic properties of Ni metal have been studied up to 260 GPa by nuclear forward scattering of synchrotron radiation with the 67.4 keV Mössbauer transition of 61Ni. The observed magnetic hyperfine splitting confirms the ferromagnetic state of Ni up to 260 GPa, the highest pressure where magnetism in any material has been observed so far.

Spin reorientation in TlFe1.6Se2 with complete vacancy ordering.

The relationship between vacancy ordering and magnetism in TlFe(1.6)Se(2) has been investigated via single crystal neutron diffraction, nuclear forward scattering, and transmission electron microscopy. The examination of chemically and structurally homogeneous crystals allows the true ground state to be revealed, which is characterized by Fe moments lying in the ab plane below 100 K.

Milli-electronvolt monochromatization of hard X-rays with a sapphire backscattering monochromator.

A sapphire backscattering monochromator with 1.1 (1) meV bandwidth for hard X-rays (20-40 keV) is reported. The optical quality of several sapphire crystals has been studied and the best crystal was chosen to work as the monochromator.

Vibrational properties of nanograins and interfaces in nanocrystalline materials.

The vibrational dynamics of nanocrystalline Fe(90)Zr(7)B(3) was studied at various phases of crystallization. The density of phonon states (DOS) of the nanograins was separated from that of the interfaces for a wide range of grain sizes and interface thicknesses. The DOS of the nanograins does not vary with their size and down to 2 nm grains still closely resembles that of the bulk.

Nuclear forward scattering for high energy mössbauer transitions.

We have studied nuclear forward scattering of synchrotron radiation for the 67.41 keV resonance of 61Ni using a silicon crystal monochromator with low-index reflections and a multielement detector. This approach can be extended to other high-energy Mössbauer transitions and does not pose any restrictions on the sample environment.

Collective nature of the boson peak and universal transboson dynamics of glasses.

Using probe molecules with resonant nuclei and nuclear inelastic scattering, we are able to measure the density of states exclusively for collective motions with a correlation length of more than approximately 20 A. Such spectra exhibit an excess of low-energy modes (boson peak). This peak behaves in the same way as that observed by conventional methods.