Quantum chemical modeling of the thermodynamics of the formation of Au(III), Pd(II), and Pt(II) chloride complexes.

Quantitative prediction of physical properties of liquids and equilibrium constants is important for many applications. Computational methods based on either explicit or implicit solvent models can be used to approximate thermodynamics of complexation. A practical method for calculating the stability constant of d chlorocomplexes (PdCl, PtCl, AuCl) in aqueous solution has been developed by using DFT and DLPNO-CCSD with the SMD solvation model and 100 unique explicit water molecules.

Crystal structure of semi-synthetic obelin-v after calcium induced bioluminescence implies coelenteramine as the main reaction product.

Coelenterazine-v (CTZ-v), a synthetic vinylene-bridged π-extended derivative, is able to significantly alter bioluminescence spectra of different CTZ-dependent luciferases and photoproteins by shifting them towards longer wavelengths. However, Ca-regulated photoproteins activated with CTZ-v display very low bioluminescence activities that hampers its usage as a substrate of photoprotein bioluminescence. Here, we report the crystal structure of semi-synthetic Ca-discharged obelin-v bound with the reaction product determined at 2.

Resorbable Nanomatrices from Microbial Polyhydroxyalkanoates: Design Strategy and Characterization.

From a series of biodegradable natural polymers of polyhydroxyalkanoates (PHAs)-poly-3-hydroxybutyrate (P(3HB) and copolymers containing, in addition to 3HB monomers, monomers of 3-hydroxyvalerate (3HV), 3-hydroxyhexanoate (3HHx), and 4-hydroxybutyrate (4HB), with different ratios of monomers poured-solvent casting films and nanomembranes with oriented and non-oriented ultrathin fibers were obtained by electrostatic molding. With the use of SEM, AFM, and measurement of contact angles and energy characteristics, the surface properties and mechanical and biological properties of the polymer products were studied depending on the method of production and the composition of PHAs. It has been shown in cultures of mouse fibroblasts of the NIH 3T3 line and diploid human embryonic cells of the M22 line that elastic films and nanomembranes composed of P(3HB-co-4HB) copolymers have high biocompatibility and provide adhesion, proliferation and preservation of the high physiological activity of cells for up to 7 days.

Biosynthesis and Properties of a P(3HB--3HV--4HV) Produced by B-10646.

Synthesis of P(3HB--3HV--4HV) copolymers by the wild-type strain B-10646 on fructose or sodium butyrate as the main C-substrate with the addition of γ-valerolactone as a precursor of 3HV and 4HV monomers was studied. Bacterial cells were cultivated in the modes that enabled production of a series of copolymers with molar fractions of 3HV (from 7.3 to 23.

Degradable Poly(3-hydroxybutyrate)-The Basis of Slow-Release Fungicide Formulations for Suppressing Potato Pathogens.

Three-component slow-release fungicide formulations with different modes of action of the active ingredients for suppressing potato pathogens were constructed for the first time. The difenoconazole, mefenoxam, prothioconazole, and azoxystrobin fungicides were embedded in the degradable polymer P(3HB)/birch wood flour blend and examined using SEM, IR spectroscopy, X-ray analysis, DTA, and DSC. Results showed that no chemical bonds were established between the components and that they were physical mixtures that had a lower degree of crystallinity compared to the initial P(3HB), which suggested different crystallization kinetics in the mixtures.

Study of the Effect of Modified Aluminum Oxide Nanofibers on the Properties of PLA-Based Films.

To find out whether AlO nanofiller is effective in improving the characteristics of polymer composites, composite polymer films based on biodegradable polylactide and epoxidized aluminum oxide nanofibers were obtained by solution casting. Surface morphology, mechanical and thermal properties of composites were studied by SEM, IR-Fourier spectroscopy, DSC and DMA. It was shown that, below and above the percolation threshold, the properties of the films differ significantly.

Effectiveness of slow-release fungicide formulations for suppressing potato pathogens.

Background: For the first time, the biological activity of slow-release fungicide formulations for suppressing potato pathogens deposited in a degradable poly-3-hydroxybutyrate/sawdust base has been obtained and investigated.

Results: The slow-release fungicide formulations (azoxystrobin, azoxystrobin + mefenoxam, and difenoconazole) were studied in vitro and in vivo in comparison with commercial analogues. In in vitro cultures of phytopathogens, the deposited fungicides showed an inhibitory effect comparable to commercial analogues, limiting the growth of colonies of Phytophthora infestans, Alternaria longipes, Rhizoctonia solani and Fusarium solan (2.

Recombinant light-sensitive photoprotein berovin from ctenophore Beroe abyssicola: Bioluminescence and absorbance characteristics.

The bright bioluminescence of ctenophores inhabiting the oceans worldwide is caused by light-sensitive Ca-regulated photoproteins. By now, the cDNAs encoding photoproteins from the four different ctenophore species have been cloned and the recombinant proteins have been characterized to some extent. In this work, we report on the specific activity and the quantum yield of bioluminescence reaction as well as the absorbance characteristics of high-purity recombinant berovin.

Nucleic Acid Aptamers Increase the Anticancer Efficiency and Reduce the Toxicity of Cisplatin-Arabinogalactan Conjugates .

Cisplatin is an effective drug for treating various cancer types. However, it is highly toxic for both healthy and tumor cells. Therefore, there is a need to reduce its therapeutic dose and increase targeted bioavailability.

Evaluation of the effect of background electrolyte composition and independence of parameters in determining binding constants of betulin derivatives to β- and dimethyl-β-cyclodextrins by affinity capillary electrophoresis.

The values of the apparent binding constants for β-cyclodextrin complexes of betulin derivatives determined by mobility shift affinity capillary electrophoresis were found to be independent of the composition of the two background electrolytes used (tetraborate buffer, pH 9.18, and phosphate buffer, pH 8.00, both of them with 20 mM ionic strength).

Droplet Microfluidic Device for Chemoenzymatic Sensing.

The rapid detection of pollutants in water can be performed with enzymatic probes, the catalytic light-emitting activity of which decreases in the presence of many types of pollutants. Herein, we present a microfluidic system for continuous chemoenzymatic biosensing that generates emulsion droplets containing two enzymes of the bacterial bioluminescent system (luciferase and NAD(P)H:FMN-oxidoreductase) with substrates required for the reaction. The developed chip generates "water-in-oil" emulsion droplets with a volume of 0.

Production of Copepod Luciferases via Baculovirus Expression System.

Secreted copepod luciferases (CopLucs) represent highly homologous enzymes which catalyze the oxidation of a low molecular weight substrate, coelenterazine, with the emission of blue light (λ = 485-488 nm), that is called bioluminescence (BL). The well-studied Gaussia (GLuc) and Metridia (MLuc) luciferases originally cloned from the marine copepods Gaussia princeps and Metridia longa belong to the group of the smallest natural luciferases. Their minimal molecular weight, high luminescent activity, cofactor-independent BL, and the ability to be secreted due to the own signal peptide open up the horizons for genetic engineering of CopLuc-based sensitive biosensors for in vivo imaging and in vitro analytical applications.

Production of Metridia Luciferase in Native Form by Oxidative Refolding from E. coli Inclusion Bodies.

The small coelenterazine-dependent luciferase from Metridia longa (MLuc), in view of its high activity, simplicity of bioluminescent (BL) reaction, and stability, has found successful analytical applications as a genetically encoded reporter for in vivo assessment of cellular processes. However, the study on the biochemical and BL properties and the development of in vitro analytical applications of MLuc are hampered by the difficulties of obtaining a sufficient amount of the highly active recombinant protein due to the presence of multiple (up to five) disulfide bonds per molecule. Here, we present a protocol to obtain the recombinant disulfide-rich MLuc using a cheap and simple Escherichia coli expression system without any affinity tags in its native form by refolding from inclusion bodies.

Cytogenotoxic activity of herbicidal and fungicidal pesticides on Triticum aestivum root meristem.

Phytotoxicity, cytotoxicity and genotoxicity of pesticides with various mechanisms of targeted activity were studied in a hydroponic culture of 2-day-old seedlings of Triticum aestivum. All studied pesticides (with the exception of metribuzin) exhibited dose-dependent phytotoxicity (inhibited the growth of the main root and reduced the yield of root biomass). All studied pesticides did not affect mitotic index in the root apex meristem but did affect the duration of some phases of mitosis.

Starch-Coated Magnetic Iron Oxide Nanoparticles for Affinity Purification of Recombinant Proteins.

Starch-coated magnetic iron oxide nanoparticles have been synthesized by a simple, fast, and cost-effective co-precipitation method with cornstarch as a stabilizing agent. The structural and magnetic characteristics of the synthesized material have been studied by transmission electron microscopy, Mössbauer spectroscopy, and vibrating sample magnetometry. The nature of bonds between ferrihydrite nanoparticles and a starch shell has been examined by Fourier transform infrared spectroscopy.

Endohedral Gd-Containing Fullerenol: Toxicity, Antioxidant Activity, and Regulation of Reactive Oxygen Species in Cellular and Enzymatic Systems.

The Gd-containing metallofullerene derivatives are perspective magnetic resonance imaging contrast agents. We studied the bioeffects of a water-soluble fullerene derivative, gadolinium-endohedral fullerenol, with 40−42 oxygen groups (Gd@Fln). Bioluminescent cellular and enzymatic assays were applied to monitor toxicity and antioxidant activity of Gd@Fln in model solutions; bioluminescence was applied as a signaling physiological parameter.

Modern aridity in the Altai-Sayan mountain range derived from multiple millennial proxies.

Temperature and precipitation changes are crucial for larch trees growing at high-elevation sites covered by permafrost in the Altai-Sayan mountain range (ASMR). To contextualize the amplitude of recent climate fluctuations, we have to look into the past by analyzing millennial paleoclimatic archives recording both temperature and precipitation. We developed annually resolved 1500-year tree-ring cellulose chronologies (δC, δO), and used these new records to reconstruct the variability in local summer precipitation and air temperature.

Effect of Gamma Radiation on Cytogenetic and Growth Endpoints of Allium cepa Seedlings in Long-Term Experiments.

The effect of γ-radiation on the growth and cytogenetic endpoints of Allium cepa L. seedlings in a long period after irradiation in absorbed doses from 1.0 to 10.

Possible risks for the functioning of cyclic processes in the experimental model of a closed ecosystem.

The purpose of the present study is to consider a number of possible risks that may emerge when processed human wastes are involved into mass exchange processes as fertilizers for plants cultivated in the experimental model of the closed ecosystem (CEEM). The problems relating to the disruption of cycling processes in closed ecosystems can be tentatively divided into two groups: the problems that can be rather easily overcome and the chronic problems. Addition of plant inedible biomass to the soil-like substrate (SLS) can result in a decrease in plant productivity because of allelopathic interactions and enhanced growth of microorganisms.

Sugar Beet Molasses as a Potential C-Substrate for PHA Production by .

To increase the availability and expand the raw material base, the production of polyhydroxyalkanoates (PHA) by the wild strain B-10646 on hydrolysates of sugar beet molasses was studied. The hydrolysis of molasses was carried out using -fructofuranosidase, which provides a high conversion of sucrose (88.9%) to hexoses.

Tracing the invasion of a leaf-mining moth in the Palearctic through DNA barcoding of historical herbaria.

The lime leaf-miner, Phyllonorycter issikii is an invasive micromoth with an unusually higher number of haplotypes in the invaded area (Europe, Western Siberia) compared to its putative native region (East Asia). The origin of the genetic diversity in the neocolonized region remains unclear. We surveyed over 15 thousand herbarium specimens of lime trees (Tilia spp.

Worldwide diversity of endophytic fungi and insects associated with dormant tree twigs.

International trade in plants and climate change are two of the main factors causing damaging tree pests (i.e. fungi and insects) to spread into new areas.

Adaptation of a Bacterial Bioluminescent Assay to Monitor Bioeffects of Gold Nanoparticles.

Our current study aimed to adapt a bioluminescent bacteria-based bioassay to monitor the bioeffects of gold nanoparticles (AuNPs). Luminous marine bacteria and AuNPs modified with polyvinylpyrrolidone were employed; low-concentration (≤10 g/L) bioeffects of AuNPs were studied. Bioluminescence intensity was used as an indicator of physiological activity in bacteria.

Size and structure effects on platinum nanocatalysts: theoretical insights from methanol dehydrogenation.

Methanol dehydrogenation on Pt nanoparticles was studied as a model reaction with the focus on size and structure effects employing the density functional theory approach. The effect of cluster morphology is manifested by the higher adsorption energy of COH intermediates on vertexes and edges of model nanoparticles compared to closely packed terraces. Moreover, due to the size effect, the adsorption sites of Pt nanoparticles (1.

N-extended photoprotein obelin to competitively detect small protein tumor markers.

Two variants of Ca-regulated photoprotein obelin, extended from the N-terminus with small tumor markers - melanoma inhibitory activity protein (MIA) and survivin, one of the protein inhibitors of apoptosis, were designed, obtained and studied. Both domains in the obtained hybrid proteins exhibit the properties of the initial molecules: the main features of Ca-triggered bioluminescence are close to those of obelin, and the tumor markers' domains are recognized and bound by the corresponding antibodies. The obtained hybrids compete with the corresponding tumor markers for binding with antibodies, immobilized on the surface and their use has been shown to be promising as bioluminescent labels in a one-stage solid-phase competitive immunoassay.