X-ray standing wave characterization of the strong metal-support interaction in Co/TiOx model catalysts.

The strong metal-support interaction (SMSI) is a phenomenon observed in supported metal catalyst systems in which reducible metal oxide supports can form overlayers over the surface of active metal nanoparticles (NPs) under a hydrogen (H2) environment at elevated temperatures. SMSI has been shown to affect catalyst performance in many reactions by changing the type and number of active sites on the catalyst surface. Laboratory methods for the analysis of SMSI at the nanoparticle-ensemble level are lacking and mostly based on indirect evidence, such as gas chemisorption. Here, we demonstrate the possibility to detect and characterize SMSIs in Co/TiOx model catalysts using the laboratory X-ray standing wave (XSW) technique for a large ensemble of NPs at the bulk scale. We designed a thermally stable MoNx/SiNx periodic multilayer to retain XSW generation after reduction with H2 gas at 600°C. The model catalyst system was synthesized here by deposition of a thin TiOx layer on top of the periodic multilayer, followed by Co NP deposition via spare ablation. A partial encapsulation of Co NPs by TiOx was identified by analyzing the change in Ti atomic distribution. This novel methodological approach can be extended to observe surface restructuring of model catalysts in situ at high temperature (up to 1000°C) and pressure (≤3 mbar), and can also be relevant for fundamental studies in the thermal stability of membranes, as well as metallurgy.

Formation of Supplementary Metal-Binding Centers in Proteins under Stress Conditions.

In many proteins, supplementary metal-binding centers appear under stress conditions. They are known as aberrant or atypical sites. Physico-chemical properties of proteins are significantly changed after such metal binding, and very stable protein aggregates are formed, in which metals act as "cross-linking" agents. Supplementary metal-binding centers in proteins often arise as a result of posttranslational modifications caused by reactive oxygen and nitrogen species and reactive carbonyl compounds. New chemical groups formed as a result of these modifications can act as ligands for binding metal ions. Special attention is paid to the role of cysteine SH-groups in the formation of supplementary metal-binding centers, since these groups are the main target for the action of reactive species. Supplementary metal binding centers may also appear due to unmasking of amino acid residues when protein conformation changing. Appearance of such centers is usually considered as a pathological process. Such unilateral approach does not allow to obtain an integral view of the phenomenon, ignoring cases when formation of metal complexes with altered proteins is a way to adjust protein properties, activity, and stability under the changed redox conditions. The role of metals in protein aggregation is being studied actively, since it leads to formation of non-membranous organelles, liquid condensates, and solid conglomerates. Some proteins found in such aggregates are typical for various diseases, such as Alzheimer's and Huntington's diseases, amyotrophic lateral sclerosis, and some types of cancer.

Layer-controlled evolution of electron state in the silicene intercalation compound SrSi2.

Silicene, a Si-based analogue of graphene, holds a high promise for electronics because of its exceptional properties but a high chemical reactivity makes it a very challenging material to work with. The silicene lattice can be stabilized by active metals to form stoichiometric compounds MSi2. Being candidate topological semimetals, these materials provide an opportunity to probe layer dependence of unconventional electronic structures. It is demonstrated here that in the silicene compound SrSi2, the number of monolayers controls the electronic state. A series of films ranging from bulk-like multilayers down to a single monolayer have been synthesized on silicon and characterized with a combination of techniques - from electron and X-ray diffraction to high-resolution electron microscopy. Transport measurements reveal evolution of the chiral anomaly in bulk SrSi2 to weak localization in ultrathin films down to 3 monolayers followed by 3D and 2D strong localization in 2 and 1 monolayers, respectively. The results outline the range of stability of the chiral state, important for practical applications, and shed light on the localization phenomena in the limit of a few monolayers.

XANES Measurements for Studies of Adsorbed Protein Layers at Liquid Interfaces.

X-ray absorption near edge structure (XANES) spectra for protein layers adsorbed at liquid interfaces in a Langmuir trough have been recorded for the first time. We studied the parkin protein (so-called E3 ubiquitin ligase), which plays an important role in pathogenesis of Parkinson disease. Parkin contains eight Zn binding sites, consisting of cysteine and histidine residues in a tetracoordinated geometry. Zn K-edge XANES spectra were collected in the following two series: under mild radiation condition of measurements (short exposition time) and with high X-ray radiation load. XANES fingerprint analysis was applied to obtain information on ligand environments around zinc ions. Two types of zinc coordination geometry were identified depending on X-ray radiation load. We found that, under mild conditions, local zinc environment in our parkin preparations was very similar to that identified in hemoglobin, treated with a solution of ZnCl2 salt. Under high X-ray radiation load, considerable changes in the zinc site structure were observed; local zinc environment appeared to be almost identical to that defined in Zn-containing enzyme alkaline phosphatase. The formation of a similar metal site in unrelated protein molecules, observed in our experiments, highlights the significance of metal binding templates as essential structural modules in protein macromolecules.

Supramolecular control of the structure and receptor properties of an amphiphilic hemicyanine chromoionophore monolayer at the air/water interface.

Designing sensors for toxic compounds such as mercury salts in aqueous solutions still remains one of the most pressing tasks of modern chemical research, since many existing systems do not show enough sensitivity and/or response. In this regard, the opportunities offered by supramolecular approaches can be used to improve both these characteristics by creating a new self-organized smart system. Herein, we show that barium cations, that according to the data of X-ray standing waves do not bind directly to the ionophore molecules in the monolayers at the air/water interface, could be used to efficiently preorganize such molecules to achieve supramolecular architecture. We demonstrate that such preorganization ensures both low analyte detection threshold and high fluorescent response. We reveal the interrelation of the monolayer structure and receptor characteristics of a sensory system and show that such cation-induced preorganization in Langmuir monolayers of a hemicyanine dithia-aza-crown-substituted chromoionophore inhibits the formation of non-fluorescent aggregates with low receptor function, and allows the quantitative detection of mercury cations using a ratiometric fluorometric approach.

Planar and 3D fibrous polyaniline-based materials for memristive elements.

The memristive elements constructed using polymers - polyaniline (PANI) and polyethyleneoxide (PEO) - could be assembled on planar thin films or on 3D fibrous materials. Planar conductive PANI-based materials were made using the Langmuir-Schaefer (LS) method, and the 3D materials - using the electrospinning method which is a scalable technique. We have analyzed the influence of PANI molar mass, natures of solvent and subphase on the crystalline structure, thickness and conductivity of planar LS films, and the influence of PANI molar mass and the PANI-PEO ratio on the morphological and structural characteristics of 3D fibrous materials.

Structural coupling across the direct EuO/Si interface.

The ferromagnetic semiconductor EuO is believed to be an effective spin injector when directly integrated with silicon (Si). Injection through spin-selective ohmic contact requires superb structural quality of the interface EuO/Si. A recent breakthrough in manufacturing free-of-buffer-layer EuO/Si junctions calls for structural studies of the interface between the semiconductors. The synthesis of EuO employs an advanced protection of the Si substrate surface and a two-step growth protocol. It prevents unwanted chemical reactions at the interface. Ex situ high-resolution x-ray diffraction (XRD) and reflectivity (XRR) accompanied by in situ reflection high-energy electron diffraction reveal direct coupling at the interface. A combined analysis of XRD and XRR data provides a common structural model. The structural quality of the EuO/Si spin contact far exceeds that of previous reports and thus makes a step forward to the ultimate goals of spintronics.

Short period La/B and LaN/B multilayer mirrors for ~6.8 nm wavelength.

In the first part of this article we experimentally show that contrast between the very thin layers of La and B enables close to theoretical reflectance. The reflectivity at 6.8 nm wavelength was measured from La/B multilayer mirrors with period thicknesses ranging from 3.5 to 7.2 nm at the appropriate angle for constructive interference. The difference between the measured reflectance and the reflectance calculated for a perfect multilayer structure decreases with increasing multilayer period. The reflectance of the multilayer with the largest period approaches the theoretical value, showing that the optical contrast between the very thin layers of these structures allows to experimentally access close to theoretical reflectance. In the second part of the article we discuss the structure of La/B and LaN/B multilayers. This set of multilayers is probed by hard X-rays (λ = 0.154 nm) and EUV radiation (λ = 6.8 nm). The structure is reconstructed based on a simultaneous fit of the grazing incidence hard X-ray reflectivity and the EUV reflectivity curves. The reflectivity analysis of the La/B and LaN/B multilayer mirrors shows that the lower reflectance of La/B mirrors compared to LaN/B mirrors can be explained by the presence of 5% of La atoms in the B layer and 63% of B in La layer. After multi-parametrical optimization of the LaN/B system, including the nitridation of La, the highest near normal incidence reflectivity of 57.3% at 6.6 nm wavelength has been measured from a multilayer mirror, containing 175 bi-layers. This is the highest value reported so far.