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result(s) for
"Ionin, A. A."
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Molecular Characteristics and Antioxidant Activity of Spruce (Picea abies) Hemicelluloses Isolated by Catalytic Oxidative Delignification
by
Malyar, Yuriy N.
,
Seliverstova, Anastasia A.
,
Samoylova, Ekaterina D.
in
Acids
,
antioxidant activity
,
Antioxidants - chemistry
2022
Spruce (Piceaabies) wood hemicelluloses have been obtained by the noncatalytic and catalytic oxidative delignification in the acetic acid-water-hydrogen peroxide medium in a processing time of 3–4 h and temperatures of 90–100 °C. In the catalytic process, the H2SO4, MnSO4, TiO2, and (NH4)6Mo7O24 catalysts have been used. A polysaccharide yield of up to 11.7 wt% has been found. The hemicellulose composition and structure have been studied by a complex of physicochemical methods, including gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. The galactose:mannose:glucose:arabinose:xylose monomeric units in a ratio of 5:3:2:1:1 have been identified in the hemicelluloses by gas chromatography. Using gel permeation chromatography, the weight average molar mass Mw of hemicelluloses has been found to attain 47,654 g/mol in noncatalytic delignification and up to 42,793 g/mol in catalytic delignification. Based on the same technique, a method for determining the α and k parameters of the Mark–Kuhn–Houwink equation for hemicelluloses has been developed; it has been established that these parameters change between 0.33–1.01 and 1.57–472.17, respectively, depending on the catalyst concentration and process temperature and time. Moreover, the FTIR spectra of the hemicellulose samples contain all the bands characteristic of heteropolysaccharides, specifically, 1069 cm−1 (C–O–C and C–O–H), 1738 cm−1 (ester C=O), 1375 cm−1 (–C–CH3), 1243 cm−1 (–C–O–), etc. It has been determined by the thermogravimetric analysis that the hemicelluloses isolated from spruce wood are resistant to heating to temperatures of up to ~100 °C and, upon further heating, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses has been examined using the compounds simulating the 2,2-diphenyl-2-picrylhydrazyl free radicals.
Journal Article
Modification of Arabinogalactan Isolated from Larix sibirica Ledeb. into Sulfated Derivatives with the Controlled Molecular Weights
by
Malyar, Yuriy N.
,
Skripnikov, Andrei M.
,
Zimonin, Dmitriy V.
in
Acids
,
Anticoagulants
,
arabinogalactan
2021
The process of sulfation of arabinogalactan—a natural polysaccharide from Larix sibirica Ledeb.—with sulfamic acid in 1,4-dioxane using different activators has been studied for the first time. The dynamics of the molecular weight of sulfated arabinogalactan upon variation in the temperature and time of sulfation of arabinogalactan with sulfamic acid in 1,4-dioxane has been investigated. It has been found that, as the sulfation time increases from 10 to 90 min, the molecular weights of the reaction products grow due to the introduction of sulfate groups without significant destruction of the initial polymer and sulfation products. Sulfation at 95 °C for 20 min yields the products with a higher molecular weight than in the case of sulfation at 85 °C, which is related to an increase in the sulfation rate; however, during the further process occurring under these conditions, sulfation is accompanied by the destruction and the molecular weight of the sulfated polymer decreases. The numerical optimization of arabinogalactan sulfation process has been performed. It has been shown that the optimal parameters for obtaining a product with a high sulfur content are a sulfamic acid amount of 20 mmol per 1 g of arabinogalactan, a process temperature of 85 °C, and a process time of 2.5 h.
Journal Article
Nonlinear Propagation and Filamentation on 100 Meter Air Path of Femtosecond Beam Partitioned by Wire Mesh
by
Couairon, Arnaud
,
Pushkarev, Dmitrii V.
,
Ionin, Andrey A.
in
Atmospheric aerosols
,
beam regularization
,
Experiments
2022
High-intensity (∼1 TW/cm2 and higher) region formed in the propagation of ∼60 GW, 90 fs Ti:Sapphire laser pulse on a ∼100 m path in air spans for several tens of meters and includes a plasma filament and a postfilament light channel. The intensity in this extended region is high enough to generate an infrared supercontinuum wing and to initiate laser-induced discharge in the gap between the electrodes. In the experiment and simulations, we delay the high-intensity region along the propagation direction by inserting metal-wire meshes with square cells at the laser system output. We identify the presence of a high-intensity region from the clean-spatial-mode distributions, appearance of the infrared supercontinuum wing, and occurrence of the laser-induced discharge. In the case of free propagation (without any meshes), the onset of the high-intensity zone is at 40–52 m from the laser system output with ∼30 m extension. Insertion of the mesh with 3 mm cells delays the beginning of the high-intensity region to 49–68 m with the same ∼30 m extension. A decrease in the cell size to 1 mm leads to both delay and shrinking of the high-intensity zone to 71–73 m and 6 m, respectively. Three-dimensional simulations in space confirm the mesh-induced delay of the high-intensity zone as the cell size decreases.
Journal Article
Broadband Sum-Frequency Generation of a CO Laser in Antireflection-Coated and Uncoated ZnGeP2 Crystals
2023
We report an experimental study of broadband sum-frequency generation of a nonselective
Q
-switched CO laser (pulse duration, ~0.3 μs; repetition rate, ~90 Hz) in ZnGeP
2
crystals with and without an antireflective interference coating. The uncoated crystal surface is found to be optically damaged at a laser radiation intensity of 0.033 GW/cm
2
. Under the same conditions, no damage to the antireflection-coated surface of the crystal is observed. The maximum efficiency of broadband sum-frequency generation of the CO laser in the antireflection-coated sample is 4.8% and turns out to be two times higher than in the uncoated sample. The spectral characteristics of the radiation at sum frequencies do not change in using antireflection-coated and uncoated samples.
Journal Article
Comprehensive Study of the Ammonium Sulfamate–Urea Binary System
by
Bousiakou, Leda G.
,
Berezhnaya, Yaroslava D.
,
Al-Dossary, Omar M.
in
Acids
,
ammonium sulfamate
,
binary system
2023
The physicochemical properties of binary systems are of great importance for the application of the latter. We report on the investigation of an ammonium sulfamate–urea binary system with different component ratios using a combination of experimental (FTIR, XRD, TGA/DSC, and melting point) and theoretical (DFT, QTAIM, ELF, RDG, ADMP, etc.) techniques. It is shown that, at a temperature of 100 °C, the system under study remains thermally and chemically stable for up to 30 min. It was established using X-ray diffraction analysis that the heating time barely affects the X-ray characteristics of the system. Data on the aggregate states in specified temperature ranges were obtained with thermal analysis and determination of the melting point. The structures of the ammonium sulfamate–urea system with different component ratios were optimized within the density functional theory. The atom-centered density matrix propagation calculation of the ammonium sulfamate–urea system with different component ratios was performed at temperatures of 100, 300, and 500 K. Regardless of the component ratio, a regular increase in the potential energy variation (curve amplitude) with an increase in temperature from 100 to 500 K was found.
Journal Article
Long-Wave Mid-IR Range Spectrograph Based on a Pyroelectric Linear Array
by
Kozlov, A. Yu
,
Kinyaevskiy, I. O.
,
Sinitsyn, D. V.
in
Aperture
,
Carbon dioxide
,
Electrical Engineering
2024
A compact IR spectrograph based on a line array of pyroelectric sensors and operating in the vicinity of 10-μm-wavelength has been developed. The development was motivated by various tasks requiring prompt measurement of the spectral characteristics of multifrequency radiation in this spectral range. The spectrometer’s performance was tested using a wavelength-tunable CO
2
-laser. With a fixed position of the diffraction grating, the spectrometer covers a wavelength range of approximately 0.6 µm (wavenumber range of approximately 50 cm
–1
) with a spectral resolution of approximately 0.02 µm (which is approximately 0.2 cm
–1
), which allows one to reliably separate two adjacent CO
2
-laser lines.
Journal Article
A Study of Effective Nonlinearity of BaGa2GeS6 Crystal by CO Laser Sum-Frequency Generation with Type-I and Type-II Phase Matching
2024
The sum-frequency generation of broadband CO laser radiation (λ ≈ 5–6 μm) in a new nonlinear BaGa
2
GeS
6
crystal at type I and II phase matching at the variation of polar and azimuth angles of this crystal has been experimentally investigated. A small mismatch (~3°) between the values of measured and calculated phase matching angles was found. Also, based on experimental data and their comparison with calculations, a set of coefficients was determined of the nonlinear susceptibility tensor of BaGa
2
GeS
6
, which best describes the experimental results.
Journal Article
Food Xanthan Polysaccharide Sulfation Process with Sulfamic Acid
by
Malyar, Yuriy N.
,
Karacharov, Anton A.
,
Fetisova, Olga Yu
in
absorption
,
Absorption spectra
,
Acids
2021
Xanthan is an important polysaccharide with many beneficial properties. Sulfated xanthan derivatives have anticoagulant and antithrombotic activity. This work proposes a new method for the synthesis of xanthan sulfates using sulfamic acid. Various N-substituted ureas have been investigated as process activators. It was found that urea has the greatest activating ability. BBD of xanthan sulfation process with sulfamic acid in 1,4-dioxane has been carried out. It was shown that the optimal conditions for the sulfation of xanthan (13.1 wt% sulfur content) are: the amount of sulfating complex per 1 g of xanthan is 3.5 mmol, temperature 90 °C, duration 2.3 h. Sulfated xanthan with the maximum sulfur content was analyzed by physicochemical methods. Thus, in the FTIR spectrum of xanthan sulfate, in comparison with the initial xanthanum, absorption bands appear at 1247 cm−1, which corresponds to the vibrations of the sulfate group. It was shown by GPC chromatography that the starting xanthan gum has a bimodal molecular weight distribution of particles, including a high molecular weight fraction with Mw > 1000 kDa and an LMW fraction with Mw < 600 kDa. It was found that the Mw of sulfated xanthan gum has a lower value (~612 kDa) in comparison with the original xanthan gum, and a narrower molecular weight distribution and is characterized by lower PD values. It was shown by thermal analysis that the main decomposition of xanthan sulfate, in contrast to the initial xanthan, occurs in two stages. The DTG curve has two pronounced peaks, with maxima at 226 and 286 °C.
Journal Article
TEMPO-Oxidized Spruce Galactoglucomannan–Biopolymer with Enhanced Antioxidant Activity and Selective Heavy-Metal Sorption
by
Malyar, Yuriy N.
,
Ionin, Vladislav A.
,
Zimonin, Dmitriy V.
in
1,1-diphenyl-2-picrylhydrazyl
,
2,2,6,6-tetramethylpiperidin-1-oxyl
,
Adsorption
2025
This study examines galactoglucomannan, a well-studied biopolymer isolated from Siberian spruce (Picea obovata Ledeb). Due to its structure, abundant with hydroxyl groups, galactoglucomannan’s properties, such as heavy-metal ion affinity, are considered to be mediocre. Nevertheless, there are various ways to enhance its functionality via oxidative TEMPO/NaBr/NaOCl processing. This work is concerned with the determination of the oxidation effect on the structure and performance properties, such as thermal decomposition behavior, antioxidant activity, and selective heavy-metal sorption. In the results, TEMPO-oxidized galactoglucomannan yields vary in the range of 78.3 ± 6.4 wt.%. The carboxylate group in the oxidized derivative represents up to 0.084 g/1 g of the sample. According to antioxidant activity tests, the oxidized galactoglucomannan exceeds the initial sample in terms of hydroxyl radical scavenging ability. The spectral characteristics of the initial and oxidized galactoglucomannan samples reveal the differences in absorption units (1725, 1610, and 1371 cm−1). The preservation of the polymeric structure was confirmed by the gel permeation chromatography analysis results. The heavy-metal ion capacity of galactoglucomannan is higher for the oxidized derivative, which demonstrated Cd2+, Fe2+, Cu2+, and Pb2+ adsorption values of 166.8 mg/g, 142.8 mg/g, 150.0 mg/g, and 199.2 mg/g, accordingly. The obtained result of the competitive heavy-metal ion adsorption of oxidized galactoglucomannan also exceeds its initial form, as characterized by its summary 143.1 mg/g capacity.
Journal Article
Tracing Air-Breakdown Plasma Characteristics from Single-Color Filament Terahertz Spectra
2020
In this paper, we measure broadband terahertz spectra from a single 744-nm filament produced in tight, medium, and loose geometrical focusing conditions. Terahertz spectra are measured using interferometer coupled to a helium-cooled bolometer avoiding any cutoff frequencies. Based on THz spectrum maximum position and spectral width, we estimate electron-heavy particle (neutrals and ions) collision rate. Numerical simulations are performed using the state-of-the-art model of unidirectional femtosecond pulse propagation and convergence/divergence of optical radiation at large angles.
Journal Article