Application of Rock Weathering and Colonization by Biota for the Relative Dating of Moraines from the Arid Part of the Russian Altai Mountains

For the Altai Mountains’ region, especially the arid southeastern part of the Russian Altai, the data on glacier fluctuations in the Pleistocene and Holocene are still inconsistent. The study area was the Kargy River’s valley (2288–2387 m a.s.l.), a location that is not currently affected by glaciation and the glacial history of which is poorly studied. Field observations and geomorphological mapping were used to reveal the configuration of Pleistocene moraines. The relative dating method was applied to define the degree of weathering as an indicator of age. Three moraine groups of different ages (presumably MIS 6, MIS 4, and MIS 2) were identified based on a detailed investigation of their morphological features and the use of relative dating approaches. The latter were primarily based on weathering patterns. Data on the rock mineralogy, porosity, and specificity of biological colonization as an agent of weathering were obtained for the moraine debris. The studied moraines were composed of fine-grained schist, in which the specific surface area and fractality (self-similarity) were more developed in the older moraine. The growth of biota (crustose lichen and micromycetes) colonizing the rock surface led to rock disintegration and the accumulation of autochthonous fragments on the rock surface. Despite the fact that the initial stage(s) of moraine weathering affected by biota was fixed, the correlation trends of biota activity and moraine ages were not determined

Luminescence of Eu 3+ ions in hybrid polymer-inorganic composites based on poly(methyl methacrylate) and zirconia nanoparticles

Spherical nanoparticles of ZrO2 with 2 and 10 mol% EuO1.5 up to 20 nm size were prepared by the method of hydrothermal synthesis for luminescent functionalization of the polymer–inorganic nanocomposites based on poly(methyl methacrylate). Surface modification of oxide nanoparticles was carried out by 3‐(trimethoxysilyl)propyl methacrylate, dimethoxymethylvinyl silane and 2‐hydroxyethyl methacrylate to provide uniform distribution and to prevent agglomeration of nanosized filler in the polymer matrix. Polymer–inorganic composites were synthesized by in situ free radical polymerization in bulk. Structuring of ZrO2‐EuO1.5 nanoparticles in the poly(methyl methacrylate) was studied by very‐small‐angle neutron scattering. According to the results, the dependence of photoluminescent properties of ZrO2‐EuO1.5 nanoparticles on the content of lanthanide, the symmetry of the crystal field, surface treatment and the polymer matrix were established. A correlation was shown between Stark splitting in luminescence spectra of ZrO2‐EuO1.5 nanoparticles and their phase composition. Using MMT‐assay it was shown that composites based on poly(methyl methacrylate) and ZrO2‐EuO1.5 nanoparticles do not have cytotoxic properties, which makes it possible to use them as prosthesis materials with contrasted and luminescent imaging properties

Novel biocompatible Cu2+-containing composite hydrogels based on bacterial cellulose and poly-1-vinyl-1,2,4-triazole

Novel composite hydrogels representing interpenetrating polymeric networks (IPN) have been synthesized and consisted of Gluconacetobacter xylinus cellulose (GxC) and poly-1-vinyl-1,2,4-triazole (PVT) with Cu2⁺. The composite hydrogels’ mesostructure has been studied from 1.6 ​nm to 2.5 ​μm by small-angle and ultra-small-angle neutron scattering methods. It has been found that IPN complexes have three types of inhomogeneities: GxC, PVT, and PVT complex with Cu2⁺. The amount of the absorbed ions can be tuned as confirmed by electron paramagnetic spectroscopy. Besides, three hierarchy levels of GxC remained in the supramolecular structure of composite hydrogels. Reveling structure formation in these composite hydrogels is essential in fabricating hybrid polymeric materials for regenerative medicine, involving antibacterial or antifungal applications

A sol-gel synthesis and gas-sensing properties of finely dispersed ZrTiO4

The transparent titanium-zirconium-containing gel was obtained using heteroligand coordination compounds (namely, alkoxoacetylacetonates) as the precursors. The high-dispersive system “ZrTiO4 – carbon”, formed after drying of such gel and carbonization of the obtained xerogel, was used to study the evolution of microstructure for the product (ZrTiO4) during thermal treatment in air for 1 h in the temperature range from 500 °C to 1000°С. It was stated that the formation of crystalline phase occurred in the narrow range 690-730°С. The thermal treatment at 500 °C and 600°С allowed obtaining micro- and mesoporous X-ray amorphous products of the composition ZrTiO4, with the specific surface area falling in the range 82–150m2/g. At the higher temperatures the single-phase nanocrystalline powder was prepared (the specific surface area amounted to 2.5–15m2/g). Particle coarsening took place more extensively at temperatures ≥700°С was shown. For the ZrTiO4 nanopowder crystallized under the mildest conditions at the temperature of 700 °C, chemoresistive gas-sensitive properties were studied for the first time. The material showed a high reproducible response at 1–20% O2 and 200–10,000 ppm H2 at a relatively low detection operating temperature of 450 °C

Calcifying Bacteria Flexibility in Induction of CaCO3 Mineralization

Microbially induced CaCO3 precipitation (MICP) is considered as an alternative green technology for cement self-healing and a basis for the development of new biomaterials. However, some issues about the role of bacteria in the induction of biogenic CaCO3 crystal nucleation, growth and aggregation are still debatable. Our aims were to screen for ureolytic calcifying microorganisms and analyze their MICP abilities during their growth in urea-supplemented and urea-deficient media. Nine candidates showed a high level of urease specific activity, and a sharp increase in the urea-containing medium pH resulted in efficient CaCO3 biomineralization. In the urea-deficient medium, all ureolytic bacteria also induced CaCO3 precipitation although at lower pH values. Five strains (B. licheniformis DSMZ 8782, B. cereus 4b, S. epidermidis 4a, M. luteus BS52, M. luteus 6) were found to completely repair micro-cracks in the cement samples. Detailed studies of the most promising strain B. licheniformis DSMZ 8782 revealed a slower rate of the polymorph transformation in the urea-deficient medium than in urea-containing one. We suppose that a ureolytic microorganism retains its ability to induce CaCO3 biomineralization regardless the origin of carbonate ions in a cell environment by switching between mechanisms of urea-degradation and metabolism of calcium organic salts

Domain Structure, Thermal and Mechanical Properties of Polycaprolactone-Based Multiblock Polyurethane-Ureas under Control of Hard and Soft Segment Lengths

A series of multiblock polyurethane-ureas (PUU) based on polycaprolactone diol (PCL) with a molecular mass of 530 or 2000 g/mol, as well as hard segments of different lengths and structures, were synthesized by the step-growth polymerization method. The chemical structure of the synthesized multiblock copolymers was confirmed by IR- and NMR-spectroscopy. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to determine the relaxation and phase transition temperatures for the entire series of the obtained PUU. The X-ray diffraction (XRD) method made it possible to identify PUU compositions in which the crystallizability of soft segments (SS) is manifested due to their sufficient length for self-organization and structuring. Visualization of the crystal structure and disordering of the stacking of SS with an increase in their molecular mobility during heating are shown using optical microscopy. The change in the size of the hard phase domains and the value of the interdomain distance depending on the PCL molecular mass, as well as the length and structure of the hard block in the synthesized PUU, were analyzed using small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS). The evolution of the domain structure upon passing through the melting and crystallization temperatures of PUU soft blocks was studied using SANS. The studies carried out made it possible to reveal the main correlations between the chemical structure of the synthesized PUU and their supramolecular organization as well as thermal and mechanical properties

Composite Hydrogels Based on Bacterial Cellulose and Poly-1-vinyl-1,2,4-triazole/Phosphoric Acid: Supramolecular Structure as Studied by Small Angle Scattering

New composite hydrogels (CH) based on bacterial cellulose (BC) and poly-1-vinyl-1,2,4-triazole (PVT) doped with orthophosphoric acid (oPA), presenting interpenetrating polymeric networks (IPN), have been synthesized. The mesoscopic study of the supramolecular structure (SMS) of both native cellulose, produced by the strain Komagataeibacter rhaeticus, and the CH based on BC and containing PVT/oPA complex were carried out in a wide range of momentum transfer using ultra- and classical small-angle neutron scattering techniques. The two SMS hierarchical levels were revealed from 1.6 nm to 2.5 μm for the objects under investigation. In addition, it was shown that the native BC had a correlation peak on the small-angle scattering curves at 0.00124 Å−1, with the correlation length ξ being equal to ca. 510 nm. This motive was also retained in the IPN. The data obtained allowed the estimation of the fractal dimensions and ranges of self-similarity and gave new information about the BC mesostructure and its CH. Furthermore, we revealed them to be in coincidence with Brown’s BC model, which was earlier supported by Fink’s results