Vol 61, No 1 (2016)

A solid solution of the GaIn₃Se₆ (2Ga_0.5In_1.5Se₃) composition with a hexagonal lattice (a = 7.051(3) Å, c = 19.148(2) Å, sp. gr. P6₁, z = 6, V = 824.4332(4) ų, ρ = 5.379(2) g/cm³) has been synthesized as a result of alloying Ga, In, and Se elements with a metal ratio of 1: 3. It was established that six out of nine In atoms in the lattice are located in a trigonal bipyramid, while the other three In atoms and three Ga atoms have a tetrahedral coordination.

Single crystals of Cs₄(HSO₄)₃(H₂PO₄) are synthesized and studied for the first time. The new compound is found in the course of studies of the phase diagram of the CsHSO₄–CsH₂PO₄–H₂O triple system. Data on the atomic crystal structure of single-crystalline and powder specimens, as well as on structural phase transitions, are obtained.

The ratio of two forms of tysonite in nominally pure single crystals of RF₃ (R = La–Nd) obtained from melts under identical conditions (the as-grown state) is studied for the first time by X-ray diffraction. Crystals of RF₃ with R = La–Nd belong to the β-LaF₃ structural type (space group $P\overline{3}c1$, Z = 6) and form twins. Samples 0.2–0.4 in diameter contain inclusions of the high-temperature a form (space group P6₃/mmc, Z = 2). It is shown that twinning and dimorphism of the RF₃ crystals (R = La–Nd) have a common structural basis.

The ionic conductivity s of KYF₄ and K₂RF₅ single crystals (R = Gd, Ho, Er) and KNdF₄ and K₂RF₅ ceramic samples (R = Dy, Er) has been studied in the temperature range of 340–500°C. A comparative analysis of the σ values for these objects has been performed. Binary fluorides of potassium and rare earth elements were synthesized by the hydrothermal method (temperature 480°C, pressure 100–150 MPa) in the R₂O₃–KF–H₂O systems. The σ values of tetraf luorides are 3 × 10^–5 S/cm (KYF₄ single crystal) and 3 × 10^–6 S/cm (KNdF₄ ceramics) at 435°C. A K₂ErF₅ single crystal with σ = 1.2 × 10^–4 S/cm at 435°C has the maximum value of ionic conductivity among pentafluorides. The anisotropy of ionic transport was found in K₂HoF₅ single crystals, σ_∥c/σ_⊥c = 2.5, where σ_∥c and σ_⊥c are, respectively, the conductivities along the crystallographic c axis and in the perpendicular direction.

Metallic lithium is used to demonstrate the possibilities of applying non-self-adjoint operators for quantitative description of orbital excitations of electrons in crystals. It is shown that, the nonequilibrium distribution function can be calculated when solving the spectral problem; therefore, the kinetic properties of a material can also be described with the unified band theory.

The molecular state of hen egg white lysozyme in solution has been studied by small-angle X-ray scattering (SAXS) combined with molecular simulation. The addition of a precipitant is shown to change the state of the protein molecules in solution. The SAXS data were processed using the constructed models of different oligomers. Under the crystallization conditions, lysozyme is shown to be present in solution as monomers (96.0%), dimers (1.9%), and octamers (2.1%), whereas tetramers and hexamers are not found. The modeled structure of the octamer is not consistent with the commonly accepted unit cell containing eight lysozyme molecules. Meanwhile, the modeled octamers are well-fitted to the crystal structure and can serve as building blocks in the course of crystal growth.

A new four-core silver complex {Ag₄[NH(CH₂PO₃H)₃]₂(H₂O)₂} · H₂O has been synthesized and investigated. Its crystallographic characteristics are sp. gr. $P\overline{1}$, Z = 1, a = 7.5806(2) Å, b = 8.4946(2) Å, c = 10.1092(3) Å, α = 81.087(2)°, β = 88.356(2)°, γ = 82.132(2)°. The ligand in the form of zwitterion is hexdentate. The complex is chelating; each silver atom closes an eight-membered cycle Ag–O–P–C–N–C–P–O. Simultaneously, two ligand molecules form six bridge bonds with neighboring formula units. Silver atoms form a polycyclic cluster Ag₄O₆, the configuration of which is stabilized by coordination and hydrogen bonds.

Phosphoribosyl pyrophosphate synthetase from Escherichia coli was cloned, purified, and crystallized. Single crystals of the enzyme were grown under microgravity. The X-ray diffraction data set was collected at the Spring-8 synchrotron facility and used to determine the three-dimensional structure of the enzyme by the molecular-replacement method at 2.71 Å resolution. The active and regulatory sites in the molecule of E. coli phosphoribosyl pyrophosphate synthetase were revealed by comparison with the homologous protein from Bacillus subtilis, the structure of which was determined in a complex with functional ligands. The conformations of polypeptide-chain fragments surrounding and composing the active and regulatory sites were shown to be identical in both proteins.

The evolution of a terrace-step nanostructure (TSN) on the sapphire (0001) surface misoriented by an angle of 0.1° with respect to the ($10\overline{1}0$) plane was observed by atomic force microscopy (AFM) at temperatures from 1273 to 1673 K. It was established that, with an increase in the annealing temperature to 1373 K, the step height attains 0.44 nm at a distance of 220 nm between steps; i.e., heating by 100 K doubles these parameters. In this case, the relief periodicity is retained. Rapid cooling of the substrate to 973 K leads to partial freezing of the surface structure, which makes it possible to observe the transition from one TSN to another. It was established that two steps coalescence upon annealing to 1373 K toward the ($10\overline{1}0$) plane, which has the lowest rigidity and, consequently, the lowest atomic density. The coalescence of two steps at a specified temperature is completed at a sufficiently large distance between the steps, at which their interaction energy is negligible. Upon further annealing of the samples above 1373 K, the steps overgrow to 1 nm; however, their periodicity is broken in this case.

The nanoporosity and structure of natural carbons has been investigated on the example of Karelian carbon-rich shungites by comparing the data of small-angle synchrotron radiation scattering and highresolution microscopy. The analysis of small-angle scattering data is based on the model of scattering spheres with lognormal size distribution. It is found that the structure of samples from the Maksovo and Zazhogino deposits subjected to high temperatures in the geological medium and (also to a lesser extent) a sample from the Shunga deposit can be described as an aggregation of polydisperse scattering spheres with lognormal size distribution; the characteristic scatterer size is determined for them. A comparison with microscopy data shows that these scatterers are mainly associated with pores, and the character of their size distribution is similar to that previously established for nanoglobules in schungites.

We discuss properties of the interaction of slow neutrons with nano-dispersed media and their application for neutron reflectors. In order to increase the accuracy of model simulation of the interaction of neutrons with nanopowders, we perform precise quantum mechanical calculation of potential scattering of neutrons on single nanoparticles using the method of phase functions. We compare results of precise calculations with those performed within first Born approximation for nanodiamonds with the radius of 2–5 nm and for neutron energies 3 × 10^-7–10^-3 eV. Born approximation overestimates the probability of scattering to large angles, while the accuracy of evaluation of integral characteristics (cross sections, albedo) is acceptable. Using Monte-Carlo method, we calculate albedo of neutrons from different layers of piled up diamond nanopowder.

Transmission electron microscopy (TEM) and small-angle neutron scattering (SANS) studies showed that model peptides QNALVCGLRQ (G33) and QNALVCGLRG (G31) corresponding to region 551–560 of the GP protein of the Sudan Ebola virus are prone to oligomerization in solution. Both peptides can form amyloid-like fibrills. The G33 peptide forms fibrils within one day of incubation, whereas the fibrillogenesis of the G31 peptide is observed only after incubation for several months. The possible role of the observed processes in the pathogenesis and the possibility of applying a combination of the TEM and SANS techniques to search for new compounds that are able to influence the protein oligomerization are discussed.

Neutron detectors based on scintillation screens ZnS(Ag)/LiF and solid-state photomultipliers have been developed. Lightguides are used to collect light. The application of a coincidence scheme provides a low dark count and a neutron detection efficiency as high as 70%. A scheme of x-y neutron detector based on wavelength shifting fibers is also proposed. Tests of the proposed versions of detectors in a neutron beam have shown their efficiency.

Neutron scattering patterns have been recorded for a bulk Zn_0.9V_0.1Se cubic crystal at room temperature; they are indicative of macroscopic deformation in the material and its significant inhomogeneity. Specific features of the previously found state, preceding the fcc ↔ hcp structural transformation of the sphalerite lattice upon strong destabilization induced by vanadium ions in the doped ZnSe matrix, are discussed taking into account the data obtained.

The micellization in mixed aqueous systems based on a nonionic surfactant, heptaethylene glycol monotetradecyl ether (C₁₄E₇), and an anionic surfactant, cesium dodecyl sulfate, has been investigated by small-angle neutron scattering. Preliminary data on the behavior of the C₁₄E₇ aqueous solutions (with three concentrations, 0.17, 0.5, and 1%) mixed with a small amount of anionic surfactant, cesium dodecyl sulfate, are reported.

Currently, the best accuracy of neutron lifetime measurements has been attained in the experiment with a gravitational trap for ultracold neutrons (UCNs), performed at the Petersburg Nuclear Physics Institute (PNPI); the measured lifetime was 878.5 ± 0.8 s. A new setup with a big gravitational trap has been designed to continue the methods and approaches used in the previous experiment. It is planned to reduce the measurement error to 0.2 s, i.e., improve the existing accuracy by a factor of 4. The spectrometer was designed at PNPI and installed on the PF2/MAM beam at the Institute Laue–Langevin. Test experiments have been performed.

Glucoamylase from fungus Aspergillus awamori is glycoside hydrolase that catalyzes the hydrolysis of α-1,4- and α-1,6-glucosidic bonds in glucose polymers and oligomers. This glycoprotein consists of a catalytic domain and a starch-binding domain connected by an O-glycosylated polypeptide chain. The conformation of the linker, the relative arrangement of the domains, and the structure of the full-length enzyme are unknown. The structure of the recombinant glucoamylase GA1 was studied by molecular modelling and small-angle neutron scattering (SANS) methods. The experimental SANS data provide evidence that glucoamylase exists as a monomer in solution and contains a glycoside component, which makes a substantial contribution to the scattering. The model of full-length glucoamylase, which was calculated without taking into account the effect of glycosylation, is consistent with the experimental data and has a radius of gyration of 33.4 ± 0.6 Å.