Effect of chitosan-epoxy ratio in bio-based adhesive on physical and mechanical properties of medium density fiberboards from mixed hardwood fibers.

Chitosan and bio-based epoxy resins have emerged as promising formaldehyde-free replacements for traditional urea-formaldehyde (UF) adhesives in engineered wood products. This study evaluated five chitosan-to-epoxy weight ratios (3:1, 2:1, 1:1, 1:2, 1:3) as adhesives for hot-pressing medium density fiberboards (MDF) using mixed hardwood fibers. Increasing the epoxy ratio reduced viscosity and gel time, facilitating spraying and fast curing. The density of the formulated MDFs increased with higher epoxy ratios, ranging from 679 kg/m3 for the 3:1 ratio to 701 kg/m3 for the 1:3 formulation, meeting the 500-900 kg/m3 density range specified in EN 323. The 1:3 epoxy-rich formulation enhanced modulus of rupture (MOR) to 31 MPa and modulus of elasticity (MOE) to 2392 MPa, exceeding the minimum requirements of 16 MPa and 1500 MPa set out in EN 310 and EN 316, respectively. Dimensional stability peaked at 5% thickness swelling for the 1:3 formulation after 24 h water soaking, fulfilling the < 25% requirement per EN 316. Internal bond strength reached a maximum of 0.98 MPa for the 3:1 chitosan-rich formulation, satisfying the 0.40 MPa minimum per EN 319. One-way ANOVA tests showed the adhesive ratio had a significant effect on mechanical properties and dimensional stability at 95-99% confidence levels. Duncan's multiple range test revealed the 1:3 ratio boards exhibited statistically significant improvements compared to untreated group. Overall, tailoring the ratios achieved well-balanced properties for MOR, MOE, and dimensional stability, demonstrating potential to replace UF resins.

Testing of Polymer Composites for Manufacturing of Sprayer Nozzles.

Wear is the leading cause of nozzle failure. The durability of the nozzle is affected by the material it is made from. Traditional materials are ceramics, stainless steel, brass, and polymers. One of the possible ways to improve the wear resistance of polymer nozzles is through the incorporation of dispersed fillers into them. This paper presents the results of testing polymer composites for their chemical resistance to pesticides, examining the effects of different types and amounts of fillers on the chemical and abrasion resistance. When silicon carbide was used as a filler, the strength increased by 30.2%. The experiments on chemical resistance to pesticides revealed that the nature, shape, and volume content of filler particles do not significantly affect the resistance of the compounds obtained. Tests on hydro-abrasive wear have shown that graphite and silicon carbide are effective fillers capable of reducing wear by up to 7.5 times. Based on previous research, it is recommended to use a composite compound with 15% volume of silicon carbide for nozzle manufacturing.

Case Study of Diesters of o-Phthalic Acid in Surface Waters with Background Levels of Pollution.

Lake Baikal was studied as a model for elucidating the general pattern of o-phthalic acid diester (PAE) distributions in surface waters with background pollution levels. The influence of factors including congeners, concentrations, sampling points, seasons, years, and potential sources was considered and the environmental risk for various hydrobionts was established. Priority PAEs in Baikal waters are represented by dimethyl phthalate (DMP), diethyl phthalates (DEP), di-n-butyl phthalate (DnBP) and di-(2-ethylhexyl)phthalate (DEHP). Statistically valuable average concentrations and ranges for DMP, DEP, DnBP, and DEHP were 0.02 (0.01-0.02), 0.07 (0.06-0.09), 0.55 (0.47-0.66), and 0.30 (0.26-0.34) µg/L, respectively. The main factors determining PAE concentrations were the year and season of sampling, whereas sampling points were not among the factors influencing PAE levels. The distribution of PAEs in the water body was characterized by (i) an even distribution of minor hydrophilic DMP and DEP congeners in the whole water body, (ii) a maximum concentration of hydrophobic DnBP and DEHP congeners in the upper and near-bottom layers of the water column, and (iii) a low concentration of hydrophobic congeners in the near-shore area. The main PAE source was found to be the atmospheric transfer of polluted air masses, while the supply of PAEs from coastal sources to the pelagic zone was low. The contribution of biogenic sources to the background level of PAEs in the surface waters of Lake Baikal was established. The ecological risk of the background concentration level of PAEs for Lake Baikal biota was estimated. It was found that (i) DMP and DEP congeners do not represent a risk, or represent a very low risk, (ii) the concentration levels of dominant DnBP and DEHP congeners represent a low risk for crustaceans and fishes but (iii) a rather high risk for algae at a DEHP concentration of 0.30 µg/L.

Game of Aliphatics: A Density Functional Theory Study of Base-Catalyzed Substrate-Controlled Dimerizations of Aliphatic Alkynones.

The present work focuses on a comprehensive density functional theory (DFT) study of newly discovered base-catalyzed substrate-controlled dimerizations of aliphatic alkynones. In order to understand the origin of selectivity of the cascade assemblies of 6-methylene-5-oxaspiro[2.4]heptanones and 2-alkenylfurans, structural and electronic properties of neutral and deprotonated alkynone molecules, thermodynamic and kinetic characteristics of the deprotonation of alkynones having diverse C-H active substituents at the carbonyl function under the action of a base, and thermodynamic and kinetic characteristics of possible mechanisms of the discussed cascade reactions were theoretically assessed. The obtained computational results have confirmed and clarified an early qualitative assumption on the key role of the nature of the aliphatic substituent. Apart from fully rationalizing the experimental results, the theoretical DFT data give valuable details and data for predicting the outcome of related base-catalyzed reactions between various electrophilic substrates and nucleophilic species formed from C-H active aliphatic alkynones.

Assessment of stable carbon isotope 13С/12С ratio in phthalates from surface waters using HPLC-HRMS-TOF approach.

A method for estimating the ratio of stable carbon isotopes 13С/12С in the composition of phthalates from surface water at a trace concentration level is proposed. It is based on the concentration of hydrophobic components of water using an analytical reversed phase HPLC column followed by their gradient separation and detection of eluted phthalates using a high-resolution time-of-flight mass spectrometer (ESI-HRMS-TOF) in the form of molecular ions. The ratio of stable carbon isotopes 13С/12C in phthalates is calculated as a ratio of integrals under the monoisotopic [M+1+H]+ and [M+H]+ peaks. The Δ13C value is calculated relatively to the 13C/12C ratio in commercial DnBP and DEHP phthalates used as standards. The minimal concentration of DnBP and DEHP in water required for a reliable determination of Δ13C value is estimated by the level of ca. 0.2 µg L-1. The technique has been verified during the monitoring of priority phthalates in the waters of Lake Baikal.

Water Quality, Toxicity and Diversity of Planktonic and Benthic Cyanobacteria in Pristine Ancient Lake Khubsugul (Hövsgöl), Mongolia.

For the first time, microcystin-producing cyanobacteria have been detected in Khubsugul, which is ancient, pristine and one of the world's largest lakes. The microcystin synthetase genes belonged to the genera Nostoc, Microcystis and possibly Snowella spp. No microcystins were found in the water of the lake. Using the HPLC-HRMS/TOF, five microcystin congeners were identified in biofilms from stony substrates sampled in the coastal zone. The concentration of microcystins in biofilms was low: 41.95 µg g-1 d. wt. by ELISA and 55.8 µg g-1 d. wt. using HPLC. The taxonomic composition of planktonic and benthic cyanobacterial communities was determined by means of microscopy and high-throughput sequencing of 16S rDNA amplicons. Nostocales cyanobacteria dominated benthos of Lake Khubsugul and Synechococcales-plankton. The abundance of cyanobacteria was low both in plankton and benthos; there was no mass development of cyanobacteria. Hydrochemical and microbiological analyses showed that the water in the lake was clean; the number of faecal microorganisms was significantly below the acceptable guideline values. Hydrochemical and hydrophysical parameters, and the concentration of chlorophyll a, were low and within the range of values recorded in the 1970s to 1990s, and corresponded to the oligotrophic state of the lake. There were no signs of anthropogenic eutrophication of the lake and no conditions for the cyanobacterial blooms.

Densification and Proton Conductivity of La1-xBaxScO3-δ Electrolyte Membranes.

Bain La1-xBaxScO3-δ impairs sintering and leads to a decrease in its ceramic density. Two approaches have been studied for obtaining dense ceramics: using a high processing temperature and the introduction of a Co3O4 sintering additive. An addition of only 0.5 wt% of Co3O4 sintering additive, despite the positive sintering effect, causes a noticeable violation of stoichiometry, with partial decomposition of the material. This can lead to the formation of cationic vacancies, which form associates with oxygen vacancies and significantly reduce the oxygen ion and proton conductivity of the materials. There is also a partial substitution of Co for Sc in La1-xBaxScO3-δ, which reduces the stability of protons: it reduces the enthalpy of the hydration reaction, but increases the mobility of protons. Thus, the Co3O4 sintering additive causes a complex of negative effects on the conductivity of La1-xBaxScO3-δ materials. Only high-temperature (1800 °C) processing with protection against Ba loss contributes to the production of dense La1-xBaxScO3-δ ceramics. The chemical composition of such ceramics corresponds well to the specified one, which ensures high water uptake and, consequently, high proton conductivity.

By-Products from Food Industry as a Promising Alternative for the Conventional Fillers for Wood-Polymer Composites.

The present paper describes the application of two types of food-industry by-products, brewers' spent grain (BSG), and coffee silverskin (LK) as promising alternatives for the conventional beech wood flour (WF) for wood-polymer composites. The main goal was to investigate the impact of partial and complete WF substitution by BSG and LK on the processing, structure, physicochemical, mechanical, and thermal properties of resulting composites. Such modifications enabled significant enhancement of the melt flowability, which could noticeably increase the processing throughput. Replacement of WF with BSG and LK improved the ductility of composites, which affected their strength however. Such an effect was attributed to the differences in chemical composition of fillers, particularly the presence of proteins and lipids, which acted as plasticizers. Composites containing food-industry by-products were also characterized by the lower thermal stability compared to conventional WF. Nevertheless, the onset of decomposition exceeding 215 °C guarantees a safe processing window for polyethylene-based materials.

Theoretical Density Functional Theory Study of Electrocatalytic Activity of MN4-Doped (M = Cu, Ag, and Zn) Single-Walled Carbon Nanotubes in Oxygen Reduction Reactions.

The mechanism of oxygen reduction reaction (ORR) on transition metal-doped nitrogen codoped single-walled nanotubes, C114H24MN4 (MN4-CNT where M = Zn, Cu, or Ag; N = pyridinic nitrogen), has been studied with the density functional theory method at the ωB97XD/DGDZVP level of theory. The charge density analysis revealed two active sites of the catalyst toward ORR: the MN4 site and the C=C bond of the N-C=C-N metal-chelating fragment (C2 site). The structure of O-containing adsorbates (O2 *, HOO*, O*, HO*, etc.) on the two sites and the corresponding adsorption energies were determined. The analysis of the free energy diagrams allows to conclude that the 4e - mechanism of ORR is thermodynamically preferable for all the studied catalysts. The probability of the 2e - mechanism of ORR with the formation of hydrogen peroxide decreases in the order Cu > Ag > Zn. The most and the least exergonic steps of the conventional 4e - mechanism of ORR on each active site of model catalysts as well as the electrode potentials of deceleration and of maximum catalytic activity in both acidic and alkaline media are determined. The relative catalytic activity toward ORR increases in the order Zn < Ag ≪ Cu and is mainly attributed to the C2 site rather than the MN4 site, while combined catalytic activity of the two sites (AgN4/C2 sites) is predicted for the AgN4-CNT catalyst.

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study.

A theoretical analysis of the reaction of oxidative sulfamidation of several alkenes was performed in order to explain the various experimental observations and different reactivity of triflamide and non-fluorinated sulfonamides. Transformations occurring in the system alkene-sulfonamide in the presence of oxidative system (ButOCl + NaI) were analyzed at the MP2/DGDZVP//B3LYP/DGDZVP level of theory using the IEF-PCM method for taking into account the solvent acetonitrile (MeCN) effect. As the model substrates, styrene, trimethyl(vinyl)silane, dimethyl(divinyl)silane and diphenyl(divinyl)silane were chosen and mesylamide, triflamide, tosylamide and p-nosylamide were taken as the reagents. ButOI generated from ButOCl and NaI reacts with sulfonamides to give N-iodinated sulfonamides RSO2NHI and RSO2NI2 as active intermediates, the iodinating activity of the latter being notably higher. The analysis allowed to answer such challenging questions as different reactivity of nonfluorinated sulfonamides leading to aziridination and of triflamide resulting in the formation the main products of bis-triflamidation, or different regioselectivity of halogenation of styrene and trimethyl(vinyl)silane caused by a linear intermediate iodonium cation in the former case and a cyclic one in the latter.

Single Si-Doped Graphene as a Catalyst in Oxygen Reduction Reactions: An In Silico Study.

Single Si-doped graphene C53H18Si with one carbon atom replaced by a three-coordinate silicon atom is studied by density functional theory (DFT) calculations as a catalyst for the oxygen reduction reactions (ORRs) in both acidic and alkaline media. The active sites for oxygen adsorption were determined from the distribution of the charge density difference analysis. At the equilibrium electrode potential, the most stable intermediate was found to have the structure HO*O*-C53H18Si with both oxygen atoms bound to the support, one of them being incorporated in between Si and C atoms, corresponding to the transfer of one hydrogen atom [H+ + e-]. The 2e ORR mechanism is shown to be very unlikely because the alternative 4e ORR pathway occurring via intermediates with a broken O-O bond is much more exothermic. In addition to the commonly adopted ORR mechanism, new reaction pathways have been discovered and shown to be potentially preferable over the traditional mechanism. The new proposed four-electron ORR route was predicted to proceed spontaneously in acidic media at U < 0.99 V and in alkaline media at U < 0.22.

Water Uptake and Transport Properties of La1-xCaxScO3-α Proton-Conducting Oxides.

In this study, oxide materials La1-xCaxScO3-α (x = 0.03, 0.05 and 0.10) were synthesized by the citric-nitrate combustion method. Single-phase solid solutions were obtained in the case of calcium content x = 0.03 and 0.05, whereas a calcium-enriched impurity phase was found at x = 0.10. Water uptake and release were studied by means of thermogravimetric analysis, thermodesorption spectroscopy and dilatometry. It was shown that lower calcium content in the main phase leads to a decrease in the water uptake. Conductivity was measured by four-probe direct current (DC) and two-probe ascension current (AC) methods at different temperatures, pO2 and pH2O. The effects of phase composition, microstructure and defect structure on electrical conductivity, as well as correlation between conductivity and water uptake experiments, were discussed. The contribution of ionic conductivity of La1-xCaxScO3-α rises with decreasing temperature and increasing humidity. The domination of proton conductivity at temperatures below 500 °C under oxidizing and reducing atmospheres is exhibited. Water uptake and release as well as transport properties of La1-xCaxScO3-α are compared with the properties of similar proton electrolytes, La1-xSrxScO3-α, and the possible reasons for their differences were discussed.

Extensive Contamination of Water with Saxitoxin Near the Dam of the Irkutsk Hydropower Station Reservoir (East Siberia, Russia).

An area of discolored water 50 m wide and 30 m long was found in September 2017 close to the dam of the Irkutsk hydroelectric power station. Water from this spot was sampled for investigation in the present study. Microscopic analysis revealed that the suspended matter in the sample was composed of clumps of filaments, vegetative cells, akinetes and heterocysts that formed short filaments and solitary cells. This matter was found to consist of partially degraded cells of the cyanobacterium Dolichospermum lemmermannii. Nucleotide sequencing of DNA isolated from the biomass revealed the presence of the sxtA gene which is involved in the synthesis of saxitoxin. Water from the polluted area contained 600 ± 100 µg L-1 saxitoxin as measured by HPLC-MS with pre-column modification of the toxin with 2,4-dinitrophenylhydrazine. Immunoassay analysis (ELISA) showed a concentration of saxitoxins in the water of 2900 ± 900 µg L-1. Hydrochemical and microbiological analyses suggested the contaminated area appeared as a result of a D. lemmermannii bloom, followed by its decay and release of saxitoxin and nutrients. The present paper describes the results of a case study. Better understanding of the phenomenon will depend on the possibility to perform implementation of a large-scale monitoring program.

Cyanobacteria Nostoc Punctiforme from Abyssal Benthos of Lake Baikal: Unique Ecology and Metabolic Potential.

A strain of Nostoc punctiforme was isolated from the bottom sediments of the oil seep at Gorevoy Utes (Central Baikal) at a depth of 890 m. The Baikal strain is highly similar (98-99%) to the N. punctiforme CCAP 1453/9 strain and the typical N. punctiforme PCC 73103 strain isolated from soil ecotopes. Based on the analysis of functional genes and mass spectrometry data, we determined that the strain can produce bioactive peptides and polyketides, but does not produce known cyanobacterial toxins, saxitoxin or its analogs, or microcystins. The peptides aeruginosinamide, aeruginosin 606, aeruginosin 98-A, kasumigamide C, and microginin 91-D were recorded in the metabolic profile of the strain. The major ion found in the MALDI mass spectrum is most likely to be an ion of a polyketide substance with unknown function.

Ionofore antibiotic polynactin produced by Streptomyces sp. 156A isolated from Lake Baikal.

The potential antibacterial activity of secondary metabolites produced by Streptomyces sp. 156A isolated from Lake Baikal was investigated. The selective liquid-liquid extraction method was applied to obtain a mixture of nactins (polynactin) produced by the strain. The polynactin consisted of nonactin (3%), monactin (18%), dinactin (36%), trinactin (31%) and tetranactin (12%). The compounds were identified by MS/MS, 1H and 13C NMR methods. The loss of neutral 184 and 198 Da fragments from a sodiated molecular ion, [M + Na]+, of nactins was observed in the MS/MS spectrum. The polynactin was shown to possess the antibiotic activity against Gram-positive strains including opportunistic strains and strains isolated from various ecosystems of Lake Baikal.

First detection of benthic cyanobacteria in Lake Baikal producing paralytic shellfish toxins.

Cyanobacteria were screened from the surface of diseased sponges, stone and bedrock in Lake Baikal for the presence of saxitoxin using enzyme-linked immunosorbent assay. In sequel, eight paralytic shellfish toxin (PST) variants were identified using a MALDI mass spectrometry. Microscopic examination found that Tolypothrix distorta dominated in the biofouling samples. PCR and sequencing detected sxtA gene involved in saxitoxin biosynthesis, thereby providing evidence of the PST producing potential of Baikal cyanobacterial communities inhabiting different substrates.