Ultrafast structural changes direct the first molecular events of vision.

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 intramolecular mechanism by which the photoactivated retinal induces the activation events inside rhodopsin remains experimentally unclear. Here we use ultrafast time-resolved crystallography at room temperature3 to determine how an isomerized twisted all-trans retinal stores the photon energy that is required to initiate the protein conformational changes associated with the formation of the G protein-binding signalling state. The distorted retinal at a 1-ps time delay after photoactivation has pulled away from half of its numerous interactions with its binding pocket, and the excess of the photon energy is released through an anisotropic protein breathing motion in the direction of the extracellular space. Notably, the very early structural motions in the protein side chains of rhodopsin appear in regions that are involved in later stages of the conserved class A GPCR activation mechanism. Our study sheds light on the earliest stages of vision in vertebrates and points to fundamental aspects of the molecular mechanisms of agonist-mediated GPCR activation.

Probing Surface Transformations of Lanthanum Nickelate Electrocatalysts during Oxygen Evolution Reaction.

Monitoring the spontaneous reconstruction of the surface of metal oxides under electrocatalytic reaction conditions is critical to identifying the active sites and establishing structure-activity relationships. Here, we report on a self-terminated surface reconstruction of Ruddlesden-Popper lanthanum nickel oxide (La2NiO4+δ) that occurs spontaneously during reaction with alkaline electrolyte species. Using a combination of high-resolution scanning transmission electron microscopy (HR-STEM), surface-sensitive X-ray photoelectron spectroscopy (XPS), and soft X-ray absorption spectroscopy (sXAS), as well as electrochemical techniques, we identify the structure of the reconstructed surface layer as an amorphous (oxy)hydroxide phase that features abundant under-coordinated nickel sites. No further amorphization of the crystalline oxide lattice (beyond the ∼2 nm thick layer formed) was observed during oxygen evolution reaction (OER) cycling experiments. Notably, the formation of the reconstructed surface layer increases the material's oxygen evolution reaction (OER) activity by a factor of 45 when compared to that of the pristine crystalline surface. In contrast, a related perovskite phase, i.e., LaNiO3, did not show noticeable surface reconstruction, and also no increase in its OER activity was observed. This work provides detailed insight into a surface reconstruction behavior dictated by the crystal structure of the parent oxide and highlights the importance of surface dynamics under reaction conditions.

Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System.

Establishing generic catalyst design principles by identifying structural features of materials that influence their performance will advance the rational engineering of new catalytic materials. In this study, by investigating metal-substituted manganese oxide (spinel) nanoparticles, Mn3 O4 :M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn3 O4 :M for the electrocatalytic oxygen reduction reaction (ORR) on the enthalpy of formation of the binary MO oxide, Δf H°(MO), and the Lewis acidity of the M2+ substituent. Incorporation of elements M with low Δf H°(MO) enhances the oxygen binding strength in Mn3 O4 :M, which affects its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis relying on the rational substitution/doping by redox-inactive elements.

Femtosecond X-ray spectroscopy of haem proteins.

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. We also present a preliminary account of femtosecond X-ray absorption studies on MbNO, pointing to the presence of more than one species formed upon photolysis.

Reduction Mechanisms of Anticancer Osmium(VI) Complexes Revealed by Atomic Telemetry and Theoretical Calculations.

Resonant X-ray emission spectroscopy (RXES) has developed in the past decade as a powerful tool to probe the chemical state of a metal center and in situ study chemical reactions. We have used it to monitor spectral changes associated with the reduction of osmium(VI) nitrido complexes to the osmium(III) ammine state by the biologically relevant reducing agent, glutathione. RXES difference maps are consistent with the proposed DFT mechanism and the formation of two stable osmium(IV) intermediates, thereby supporting the overall pathway for the reduction of these high-valent anticancer metal complexes for which reduction by thiols within cells may be essential to the antiproliferative activity.

Determination of Crystal-Field Splitting Induced by Thermal Oxidation of Titanium.

The electronic structure of transition-metal oxides is a key component responsible for material's optical and chemical properties. Specifically for metal-oxide structures, the crystal-field interaction determines the shape, strength, and occupancy of electronic orbitals. Consequently, the crystal-field splitting and resulting unoccupied state populations can be foreseen as modeling factors of the photochemical activity. Herein, we study the formation of crystal-field effects during thermal oxidation of titanium in an ambient atmosphere and range of temperatures. The X-ray absorption spectroscopy is employed for quantitative analysis of average t2g-eg crystal-field splitting (Δoct) and relative t2g/eg bands occupancy. The obtained result shows that Δoct changes as a function of temperature from 1.97 eV for a passive oxide layer created on a Ti metal surface at room temperature to 2.41 eV at 600 °C when the material changes into the TiO2 rutile phase. On the basis of XAS data analysis, we show that the Δoct values determined from L2 and L3 absorption edges are equal, indicating that the 2p1/2 and 2p3/2 core holes screen the t2g and eg electronic states in a similar manner.

Comparative study of the around-Fermi electronic structure of 5d metals and metal-oxides by means of high-resolution X-ray emission and absorption spectroscopies.

The composition of occupied and unoccupied electronic states in the vicinity of Fermi energies is vital for all materials and relates to their physical, chemical and mechanical properties. This work demonstrates how the combination of resonant and non-resonant X-ray emission spectroscopies supplemented with theoretical modelling allows for quantitative analysis of electronic states in 5d transition metal and metal-oxide materials. Application of X-rays provides element selectivity that, in combination with the penetrating properties of hard X-rays, allows determination of the composition of electronic states under working conditions, i.e. non-vacuum environment. Tungsten metal and tungsten oxide are evaluated to show the capability to simultaneously assess composition of around-band-gap electronic states as well as the character and magnitude of the crystal field splitting.

In situ observation of charge transfer and crystal field formation via high energy resolution X-ray spectroscopy during temperature programmed oxidation.

Herein, it has been demonstrated how resonant X-ray emission spectroscopy can be employed to study the charge transfer dynamics in real-time during the temperature-induced oxidation of metallic tungsten. Application of high energy resolution schemes allowed distinguishing charge transfer to separate orbitals resulting from crystal field splitting. Based on the time-resolved studies, it was possible to determine the corresponding charge transfer rates. From the experimental data, we determined that the electron transfer during the thermal oxidation of the metal dominates in the temperature range of 470-570 °C, reaching a maximum of 0.036 electrons per °C.

The influence of nitrogen doping on the electronic structure of the valence and conduction band in TiO2.

X-ray emission spectroscopy (XES) and X-ray absorption spectroscopy (XAS) provide a unique opportunity to probe both the highest occupied and the lowest unoccupied states in matter with bulk sensitivity. In this work, a combination of valence-to-core XES and pre-edge XAS techniques are used to determine changes induced in the electronic structure of titanium dioxide doped with nitrogen atoms. Based on the experimental data it is shown that N-doping leads to incorporation of the p-states on the occupied electronic site. For the conduction band, a decrease in population of the lowest unoccupied d-localized orbitals with respect to the d-delocalized orbitals is observed. As confirmed by theoretical calculations, the N p-states in TiO2 structure are characterized by higher binding energy than the O p-states which gives a smaller value of the band-gap energy for the doped material.

Hydrogen evolution with hot electrons on a plasmonic-molecular catalyst hybrid system.

Plasmonic systems convert light into electrical charges and heat, mediating catalytic transformations. However, there is ongoing controversy regarding the involvement of hot carriers in the catalytic process. In this study, we demonstrate the direct utilisation of plasmon hot electrons in the hydrogen evolution reaction with visible light. We intentionally assemble a plasmonic nanohybrid system comprising NiO/Au/[Co(1,10-Phenanthrolin-5-amine)2(H2O)2], which is unstable at water thermolysis temperatures. This assembly limits the plasmon thermal contribution while ensuring that hot carriers are the primary contributors to the catalytic process. By combining photoelectrocatalysis with advanced in situ spectroscopies, we can substantiate a reaction mechanism in which plasmon-induced hot electrons play a crucial role. These plasmonic hot electrons are directed into phenanthroline ligands, facilitating the rapid, concerted proton-electron transfer steps essential for hydrogen generation. The catalytic response to light modulation aligns with the distinctive profile of a hot carrier-mediated process, featuring a positive, though non-essential, heat contribution.

Transient X-Ray Absorption Near Edge Structure Spectroscopy Using Broadband Free-Electron Laser Pulses.

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 XANES spectra in transmission mode. A beam-splitting grating configuration allows simultaneous measurements of the spectra of the incoming X-ray Free Electron Laser (XFEL) pulses and transmission XANES, which is crucial for compensating the pulse-dependent intensity and spectrum fluctuations due to the self-amplified spontaneous emission operation. The implementation of this new methodology is applied on a liquid solution of ammonium iron(III) oxalate jet and is compared to previous results, showing great improvements in the speed of acquisition and spectral resolution, and the ability to measure a large 2-D spectral-time map quickly.

Accessing metal-specific orbital interactions in C-H activation with resonant inelastic X-ray scattering.

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 is the decisive interaction in the C-H activation reaction. What is missing, however, are experimental methods to directly probe these interactions in order to reveal what determines reactivity of intermediates and the rate of the reaction. Here, using quantum chemical simulations we predict and propose future time-resolved valence-to-core resonant inelastic X-ray scattering (VtC-RIXS) experiments at the transition metal L-edge as a method to provide a full account of the evolution of metal-alkane interactions during transition-metal mediated C-H activation reactions. For the model system cyclopentadienyl rhodium dicarbonyl (CpRh(CO)2), we demonstrate, by simulating the VtC-RIXS signatures of key intermediates in the C-H activation pathway, how the Rh-centered valence-excited states accessible through VtC-RIXS directly reflect changes in donation and back-donation between the alkane C-H group and the transition metal as the reaction proceeds via those intermediates. We benchmark and validate our quantum chemical simulations against experimental steady-state measurements of CpRh(CO)2 and Rh(acac)(CO)2 (where acac is acetylacetonate). Our study constitutes the first step towards establishing VtC-RIXS as a new experimental observable for probing reactivity of C-H activation reactions. More generally, the study further motivates the use of time-resolved VtC-RIXS to follow the valence electronic structure evolution along photochemical, photoinitiated and photocatalytic reactions with transition metal complexes.

Investigation on the low-temperature transformations of poly(furfuryl alcohol) deposited on MCM-41.

MCM-41-type mesoporous silica was used as a support for poly(furfuryl alcohol) deposition. This material was produced by precipitation-polycondensation of furfuryl alcohol (FA) in aqueous slurry of the SiO2 support followed by controlled partial carbonization. By tuning the FA/MCM-41 mass ratio in the reaction mixture, various amounts of polymer particles were introduced on the inner and outer surface of the MCM support. The thermal decomposition of the PFA/MCM-41 composites was studied by thermogravimetry (TG) and spectroscopic techniques (DRIFT, XPS), whereas the evolution of textural parameters with increasing polymer content was investigated using low-temperature adsorption of nitrogen. The mechanism of thermal transformations of PFA deposited on the MCM-41 surface was discussed in detail. It was found that heating at a temperature of about 523 K resulted in opening of the furan rings and the formation of γ-diketone moieties, which were found to be the highest effective surface species for the adsorption of polar volatile organic compounds. A further increase in calcination temperature caused a drop in the amounts of surface carbonyls and the appearance of condensed aromatic domains.

OSDA-Free Seeded Cu-Containing ZSM-5 Applied for NH3-SCR-DeNOx.

A series of ZSM-5 zeolite materials were synthesized from organic structure-directing agent (OSDA)-free seeded systems, including nanosized silicalite-1 (12 wt % water suspension or in powder form) or nanosized ZSM-5 (powder form of ZSM-5 prepared at 100 or 170 °C). The physicochemical characterization revealed aggregated species in the samples based on silicalite-1. Contrarily, the catalysts based on ZSM-5 seeds revealed isolated copper species, and thus, higher NO conversion during the selective catalytic reduction of NOx with NH3 (NH3-SCR-DeNOx) was observed. Furthermore, a comparison of the Cu-containing ZSM-5 catalysts, conventionally prepared in the presence of OSDAs and prepared with an environmentally more benign approach (without OSDAs), revealed their comparable activity in NH3-SCR-DeNOx.

From crystal phase mixture to pure metal-organic frameworks - Tuning pore and structure properties.

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal-organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m2/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.

Tracking C-H activation with orbital resolution.

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 spectroscopy, we track the charge-transfer interactions during C-H activation of octane by a cyclopentadienyl rhodium carbonyl complex. Changes in oxidation state as well as valence-orbital energies and character emerge in the data on a femtosecond to nanosecond timescale. The x-ray spectroscopic signatures reflect how alkane-to-metal donation determines metal-alkane complex stability and how metal-to-alkane back-donation facilitates C-H bond cleavage by oxidative addition. The ability to dissect charge-transfer interactions on an orbital level provides opportunities for manipulating C-H reactivity at transition metals.

Hallucinogen-Like Action of the Novel Designer Drug 25I-NBOMe and Its Effect on Cortical Neurotransmitters in Rats.

NBOMes are N-benzylmethoxy derivatives of the 2C family hallucinogens. 4-Iodo-2,5-dimethoxy-N-(2-methoxybenzyl)phenethylamine (25I-NBOMe) is one of the commonly used illicit drugs. It exhibits high binding affinity for 5-HT2A/C and 5-HT1A serotonin receptors. Activation of 5-HT2A receptor induces head-twitch response (HTR) in rodents, a behavioral marker of hallucinogen effect in humans. There is not much data on neurochemical properties of NBOMes. Therefore, we aimed to investigate the effect of 25I-NBOMe on extracellular level of dopamine (DA), serotonin (5-HT), and glutamate (GLU) in the rat frontal cortex, tissue contents of monoamines, and hallucinogenic activity in rats. The extracellular levels of DA, 5-HT, and GLU were studied using microdialysis in freely moving animals. The tissue contents of DA, 5-HT and their metabolites 3,4-dihydroxyphenylacetic acid (DOPAC), homovanillic acid (HVA), and 5-hydroxyindoleacetic acid (5-HIAA) were determined in the rat frontal cortex. We also tested a drug-elicited HTR. 25I-NBOMe at doses 1, 3, and 10 mg/kg (sc) increased extracellular DA, 5-HT, and GLU levels, enhanced tissue content of 5-HT and 5-HIAA, but did not affect tissue level of DA and its metabolites. The compound exhibited an inverted U-shaped dose-response curve with respect to the effect on extracellular DA and 5-HT levels, but a U-shaped dose-response curve was observed for its effect on GLU release and HTR. The data from our study suggest that hallucinogenic activity of 25I-NBOMe seems to be related with the increase in extracellular GLU level-mediated via cortical 5-HT2A receptors. The influence of 25I-NBOMe on 5-HT2C and 5-HT1A receptors may modulate its effect on neurotransmitters and HTR.