Initial Reaction Products Research Articles

Exploring Border Conditions for Spontaneous Emergence of Chirality in Allylboration of 1,2,3-Triazolic Aldehydes.

A case of spontaneous chirality generation was observed during a synthetic project studying the allylboration of 1,2,3-triazolic aldehydes. Here, we present computational studies supported by experimental findings targeting the elucidation of border conditions required for the observation of spontaneous chirality generation in the reaction of 1-Ar-1H-1,2,3-triazole-4-carbaldehydes 1a,b with triallylborane. Three possible sources of symmetry breaking were found computationally. Thus, dimerization of the initial reaction products, alcoholates 4a,b, gives dimers 5a,b (homochiral) and 6a,b (heterochiral). The latter were computed to be more stable thermodynamically, which can lead to amplification of the initial stochastic imbalance of the enantiomers of 4a,b via the reservoir mechanism. Furthermore, enantiomeric excess can be increased during the transfer of the second allylic group in the reaction of optically active boronates 4a,b with 1a,b, which was computed to be enantioselective due to the strong activating and stereoregulating properties of the 1,2,3-triazole group. In addition, reactions of borinic esters 8a,b, products of the previous reaction with triallylborane, recovered in each case two molecules of 4a,b of the same handedness, which can lead to additional chirality amplification. Experimentally, reactions of optically active alcohols (+)-R-2a,b with triallylborane provided chiral alcoholates 4a,b, which were reacted with equivalent amounts of corresponding aldehydes 1a,b. Unexpectedly, in two series of 10 experiments each, preferential formation of both enantiomers of the newly formed product was observed: seven times S and three times R in the case of 1a and six times S and four times R in the case of 1b.

Synthesis, characterization, and evaluation of pyrimidinone-linked thiazoles: DFT analysis, molecular docking, corrosion inhibition, and bioactivity studies

The paper describes the construction of a new series of pyrimidinone-linked thiazole derivatives through bromination of the initial Biginelli reaction product followed by the Hantzsch thiazole synthesis route. Various analytical techniques, including FT-IR, 1H NMR, 13C NMR, and LCMS analysis, were employed to confirm the formation of the products. The synthesized compounds were primarily evaluated for their antibacterial activity, with a specific focus on their IC50 values. Compound 4c demonstrated the most potent efficacy, displaying MIC and MBC values that varied from 0.23 to 0.71 mg/mL and 0.46–0.95 mg/mL, respectively. The anti-inflammatory potential was also observed in analogs 4a and 4c with marked activity in the 33.2–82.9 μM concentration range. Moreover, compounds 4a, and 4c demonstrated strong antioxidant effects, as reflected by their excellent IC50 values of 38.6–43.5 μM respectively. DFT investigation showed that B. cereus was more susceptible, and E. coli was more resistant, with chloro-substituted compounds exhibiting potential reactivity. Some molecules with chloro-substituents showed promising results in density functional theory when compared to other substituents. In addition, the molecules underwent a corrosion study and demonstrated a high level of inhibition efficiency (4c) in comparison to other molecules. Further in silico studies of the synthesized thiazoles confirmed the good interactions with the target.

Особенности строительного контроля компонентов и конструкции полимерных зон деформационных швов мостовых сооружений

The article considers the construction control peculiarities of components and design of transition polymer zones of bridge structures expansion joints. The authors have examined the transition zones of expansion joints of in-use bridge structures constructed with polymer concrete. The study revealed the lack of regulatory requirements at the national standardization system documents level. The authors confirmed the possibility of binder composition identification at the organisation of construction control of supplied products in accordance with the requirements of design documentation. The authors also confirmed the possibility of determining the products of chemical reaction during curing of polymer concrete in the transition zone of bridge expansion joints. The authors used a low viscosity liquid epoxy resin based on bisphenol with the inclusion of an amine-type hardener to produce a polymer-concrete mixture. When the components are mixed, a composition is obtained that cures and, when bound to mineral aggregate, provides the product with high strength, water resistance, wear resistance and good adhesion to various substrates. The material obtained for bridge constructions is safe for the environment and does not react with various agents. The method of infrared spectroscopy allows identifying the initial substances and reaction products with the probability of coincidence from 70 to 97%.

Oxidation of Phenol and Acetone in a Model Water Flow in Continuous Mode at High Pressure

The oxidation of the “water-phenol-acetone” system, simulating the organic component of the concentrated water runoff from the Bisphenol-A plant of PJSC Kazanorgsintez, was experimentally studied in the temperature range of 523÷873 K, pressure 25 MPa, duration 2÷4 min in continuous mode. Air oxygen taken with excess coefficients equal to 10÷30 was used as an oxidizing agent. The composition of the oxidation reaction product, the indicator of chemical oxygen demand, the pH of the initial sample and reaction products, and the conversion were determined. A decrease in the initial organic compounds in the model runoff has been established.

Kinetics of zinc leaching from intermediate feedstocks

The aim of the work was to study the leaching kinetics of zinc from the compound CaO. ZnO, formed during the sintering of dust from electric arc furnaces with limestone, as well as to identify the mechanisms by means which such chemical interactions occur. The object of the study was the dust sinter of electric arc furnaces with limestone obtained at the Chelyabinsk Zinc Plant. It was found that zinc is contained in sinter in the form of readily soluble CaO. ZnO. The elemental composition of the initial dusts and sinter was determined by the spectral atomic emission method using inductively coupled plasma on a Spectroblue optical emission device and spark spectrometry. The phase composition of the materials was studied on a Bruker D8 Advance X-ray diffractometer. The initial sinter was milled to apowder state having a particle size of ~0.04 mm and with a yield of ~97% of the composition, %: 11.9 Zn; 28.5 Ca; 16.6 Fe; 0.38 Mg; 0.14 Pb; 0.05 Cl. Experiments on the leaching of Zn with NaOH solution were carried out at the following parameters: the initial concentration of zinc in the pulp was 0.202 g-ion/dm3 ; alkali concentration – 5‒9 mol/dm3 NaOH; L:S = 9:1; pulp mixing rate – 10‒20 rad. c-1; temperature – 333‒363 K; duration – 0.5–2.5 hours. It has been shown that zinc from sinter passes into solution as sodium tetrahydroxozincate Na2[Zn(OH)4], while calcium remains in the cake, mainly as insoluble Ca(OH)2, which reacts with carbon dioxide to form insoluble calcium carbonate CaCO3. The process of dissolving zinc from the sinter corresponds to the external diffusion mode of mutual transfer of the initial reagents and reaction products through the surface layer of the liquid at the interface of the “liquid–solid” phases with an activation energy value equal to 12.44 kJ/mol. Thus, with the studied parameters of zinc leaching with NaOH solution, the process proceeds in an external diffusion mode. The results are of interest when identifying conditions corresponding to the intradiffusion and kinetic modes of zinc leaching.

Random processes in modeling durability of building and structure

The problem of buildings and structures durability during their long-term operation in aggressive environments is discussed. It is closely connected with the problem of destruction of composite materials as a random process of birth, development, and death of defects at chemical corrosion. The content of the study is to analyze the influence of non-stationary chemical reactions occurring in real conditions on these processes. The analysis is carried out taking into account the incidental physical phenomena affecting corrosion, the most important of which is the diffusion of initial substances and reaction products occurring under different hydrodynamic conditions, i.e., the nature of fluid motion and its pressure which stimulates corrosion. The synthesis of three processes – chemical kinetics, diffusion, and hydrodynamics – allows us to study one of the possible scenarios of corrosion process development as a Markov process based on the statistical theory of the “weakest” link and the joint distribution of the random material and geometric parameters. Numerical analysis of changes in elastic and electrical properties of composite materials under these conditions allows us to substantiate the technology of non-destructive control of changes in the state of the structure. The research results are based on mathematical and statistical modeling.

COMPLEX FORMATION OF GOLD (I) WITH 2-METHYLIMIDAZOLE

The complex formation process of Au (I) with 2-methylimidazole was studied by potentiometric titration. When 2-methylimidazole is added to the [AuCl2]-/Au system, the potential gradually decreases without any jumps. The nonlinearity of the dependence of E on –lg[2MI] indicates the stepwise nature of the complex formation between [AuCl2]- and 2-methylimidazole. The general and thermodynamic stability constants of the complexes were determined in the temperature range of 278-318 K (at T=298 K, lgβ0[AuСl(Н2МИ)]+=13.84±0.03; lgβ10[Au2МИCl]=5.38±0.05; lgβ20[Au(2МИ)2]+=10.60±0.03). The reliability of the determination of the constants is proved by the satisfactory agreement between the experimentally found values of the potentials (Eex.) with theoretical ones (Etheor.). As the temperature increases, the stability of the complexes increases. A change in the ionic strength of the solution has little effect on the stability of the complexes. Comparison of the process of complexation of gold (I) and gold (III) with 2-methylimidazole shows that the stability of the complexes of trivalent gold is superior to similar complexes of gold (I). The thermodynamic functions of the complex formation reaction were calculated by the temperature coefficient method. In this case, the value of ΔrН0 was determined from the tangent of the slope of the direct dependence lgβ0=f(1/T), and the value of ΔrS0 was determined from the segment cut off by this straight line on the y-axis. The change in the isobaric-isothermal potential was calculated by the equation ΔrG0= ΔrН0-TΔrS0. The substitution of chloride ions for a 2MI molecule is accompanied by a positive change in ΔН, which has a negative contribution to the spontaneous course of reactions. For the [AuCl2]- - 2MI system, the number of particles participating in the reaction remains unchanged and the positive change in ΔS is most likely due to the release of water molecules from the hydration shell of the initial substances and reaction products.

Correlating Hydration of Alkali-Activated Slag Modified by Organic Additives to the Evolution of Its Properties

This study investigates the relationships between the hydration kinetics of waterglass-activated slag and the development of its physical-mechanical properties, as well as its color change. To modify the calorimetric response of alkali-activated slag, hexylene glycol was selected from various alcohols for in-depth experiments. In presence of hexylene glycol, the formation of initial reaction products was restricted to the slag surface, which drastically slowed down the further consumption of dissolved species and slag dissolution and consequently delayed the bulk hydration of the waterglass-activated slag by several days. This allowed to show that the corresponding calorimetric peak is directly related to the rapid evolution of the microstructure and physical-mechanical parameters and to the onset of a blue/green color change recorded as a time-lapse video. Workability loss was correlated with the first half of the second calorimetric peak, while the most rapid increase in strengths and autogenous shrinkage was related to the third calorimetric peak. Ultrasonic pulse velocity increased considerably during both the second and third calorimetric peak. Despite the modified morphology of the initial reaction products, the prolonged induction period, and the slightly reduced degree of hydration induced by hexylene glycol, the overall mechanism of alkaline activation remained unchanged in the long-term perspective. It was hypothesized that the main issue of the use of organic admixtures in alkali-activated systems is the destabilizing effect of these admixtures on soluble silicates introduced into the system with an activator.

Improving Fuel Properties and Hydrocarbon Content from Residual Fat Pyrolysis Vapors over Activated Red Mud Pellets in Two-Stage Reactor: Optimization of Reaction Time and Catalyst Content

Catalytic upgrading of vapors from pyrolysis of triglycerides materials is a promising approach to achieve better conversions of hydrocarbons and production of liquid biofuels. Catalytic cracking often shows incomplete conversion due to distillation of initial reaction products and the addition of a second catalytic reactor, whereas pyrolytic vapors are made in contact to a solid catalyst was applied to improve the physical-chemical properties and quality of bio-oil. This work investigated the effect of catalyst content and reaction time by catalytic upgrading from pyrolysis vapors of residual fat at 450 °C and 1.0 atmosphere, on the yields of reaction products, physicochemical properties (density, kinematic viscosity, refractive index, and acid value), and chemical composition of organic liquid products (OLP), over a catalyst fixed bed reactor, in semi pilot scale. Pellets of red mud chemically activated with 1.0 M HCl were used as catalysts. The thermal catalytic cracking of residual fat show OLP yields from 54.4 to 84.88 (wt.%), aqueous phase yields between 2.21 and 2.80 (wt.%), solid phase yields (coke) between 1.30 and 8.60 (wt.%), and gas yields from 11.61 to 34.22 (wt.%). The yields of OLP increases with catalyst content while those of aqueous, gaseous and solid phase decreases. For all experiments, the density, kinematic viscosity, and acid value of OLP decreases with reaction time. The GC-MS of liquid reaction products identified the presence of hydrocarbons and oxygenates. In addition, the hydrocarbon content in OLP increases with reaction time, while those of oxygenates decrease, reaching concentrations of hydrocarbons up to 95.35% (area.). The best results for the physicochemical properties and the maximum hydrocarbon content in OLP were obtained at 450 °C and 1.0 atmosphere, using a catalyst fixed bed reactor, with 5.0% (wt.) red mud pellets activated with 1.0 M HCl as catalyst.

Formation and infrared spectroscopic characterization of carbon suboxide complexes TM-η1 -C3 O2 and the inserted ketenylidene complexes OCTMCCO (TM=Cu, Ag, Au) in solid neon.

The reactions of coinage metal atoms Cu, Ag and Au with carbon suboxide (C3 O2 ) are studied by matrix isolation infrared spectroscopy. The weakly bound complexes TM-η1 -C3 O2 (TM=Cu, Ag, Au), in which the carbon suboxide ligand binds to the metal center in the monohapto fashion are formed as initial reaction products. The complexes subsequently isomerize to the inserted products OCTMCCO upon visible light (λ= 400-500 nm) excitation. The analysis of the electronic structure using modern quantum chemistry methods suggests that the linear OCTMCCO complexes are best described by the bonding interactions between the TM+ cation in the electronic singlet ground state and the [OC…CCO]- ligands in the doublet state forming two TM+ ← ligands σ donation and two TM+ → ligands π backdonation bonding components. In addition, the CuCCO, AgCCO and AuCCO complexes are also formed, which are predicted to be bent.

Изучение кинетических закономерностей и механизма реакции циклоалкилирования фенола с 1-метилциклопентадиеном

The article presents the results of the reaction of phenol with 1-methylcyclopentadiene in the presence of the KU-23 catalyst. Cycloalkylation of phenol have been carried out in a batch laboratory installation. After the reaction, the alkylate is separated from the catalyst and rectified. Firstly, during rectification at atmospheric pressure MCP and phenol that did not enter into the reaction were distilled off (up to 200° C), and then, under vacuum (666.5 Pa) the target reaction product was isolated and its purity and physicochemical parameters were determined. The kinetic regularities of the reaction were studied, and the probable mechanism of its occurrence was established. A kinetic model of the phenol cycloalkylation reaction, consisting of a system of differential equations, that describes the change in the concentration of the initial substances and reaction products over time has been developed. The kinetic constants of differential equations were estimated using a modified random search method with automatic step selection. For this purpose, the developed package of applied programs was used. The orders, activation energies, and rate constants of individual stages are determined. It is shown that the proposed model adequately describes the experimental data.

Changes in harmful Maillard reaction products in low-temperature long-time pasteurization-treated milks reconstituted from whole-milk powders after different storage times

Reconstituted milk treated with low-temperature long-time pasteurization was produced from whole-milk powders stored for 0–18 months. The profiles of initial, intermediate, and advanced stage Maillard reaction products, furosine, furfurals, and advanced glycation end-products in reconstituted milk were investigated. The total lysine content decreased in the reconstituted milk, whereas furosine content increased by 1.8- to 7.4-fold with storage of the corresponding milk powder. 5-(Hydroxymethyl)furfural (HMF) increased by 25–271 % with storage. 2-Furaldehyde (F) and 5-methyl-2-furfural also showed an increasing trend with storage, but 2-furyl methyl ketone (FMC) was detected only in fresh and 4-month-old reconstituted milk powder. The Nε-(carboxymethyl)lysine (CML) content increased by 1.8- to 5.2-fold with storage (from 9.9 ± 1.6 to 28.3 ± 3.3 mg/L). The Nε-(carboxyethyl)lysine content increased by 34–175 %. The increase in the furosine, HMF, F, and CML content in reconstituted milk accelerated between 12 and 18 months of storage. These compounds were more affected by the storage time of the milk powder than other harmful Maillard reaction products.

Types and Micromorphology of Authigenic Carbonates in the Kolyma Yedoma Ice Complex, Northeast Siberia

The study focuses on authigenic carbonates that are widespread in different deposition environments and are a component part of the terrestrial biogeochemical cycle of carbon. Samples from the Kolyma Yedoma Ice Complex that formed during the Sartan Cryochrone (MIS 2), the coldest period of the Late Pleistocene, in the northeastern Siberian lowlands, have been studied utilizing scanning electron microscopy and energy-dispersive spectroscopy with replica technique. The samples bear signatures of irreversible multistage cryogenic changes in structure and composition, with the formation of authigenic minerals. Authigenic carbonates as secondary phases in the Ice Complex deposits are remarkable by local changes in chemical, physical, and other properties, which induce gradual changes in the lattice and conversion of one mineral species to another. As a result, the sediments may contain stable and metastable minerals. Crystalline species like calcite or aragonite precipitate from aqueous solutions and their presence are restricted to free pore space in segregation ice. Metastable phases may be produced as an initial reaction product between the CO2 and the aqueous phase, while mineral surfaces and small pores act as possible nucleation sites. Organic matter is also an important agent in the cryometamorphism of sediments, including precipitation of authigenic phases due to the freezing of colloids and high-molecular compounds.

ПОЛУЧЕНИЕ СУЛЬФИРОВАННОГО ПРОИЗВОДНОГО ЖИРНЫХ КИСЛОТ МАСЛА СПИРУЛИНЫ

A new sulfonated derivative of Spirulina oil fatty acids was obtained in the work.This derivative is obtained from dry biomass of microalgae in several stages: extraction of lipids from dry biomass, lipid methylation, amination of the formed methyl esters of Spirulina fatty acids, modification of amide with maleic anhydrideand subsequent reaction of the synthesized monoester with sodium bisulfate. The conditions for all stages of the synthesis of the sulfonated derivative were optimized.The initial compounds and reaction products were identified by IR spectroscopy.

Kinetic Features of the Hydrogen Sulfide Sorption on the Ferro-Manganese Material

The kinetics of hydrogen sulfide sorption by the surface of a ferromanganese material containing in its composition a mixture of iron (II) and (III) oxides FeO × Fe2O3, takanelite (Mn, Ca) Mn4O9 × 3H2O and quartz SiO2, and which is samples of unrefined ferromanganese ore, was studied in this work. Sorption rate constant and activation energy constant values were calculated. The catalytic effect of iron (III) oxide was established, the presence of which in natural material contributes to a decrease in the H2S sorption activation energy. Based on the results of X-ray phase and chromatographic analysis methods, a chemical (redox) reaction of the conversion of hydrogen sulfide into elemental sulfur and H2O was revealed. The overall process rate is expressed in terms of the physical sorption stage and chemical transformation of the components; the influence of the rate of the third stage—reaction products desorption—on the overall rate of the process is taken into account. The limiting stage of the process is determined—a chemical reaction. The relation between the heat and the activation energy of the chemical transformation is used according to the Bronsted—Polanyi rule for catalytic processes. It was found that with an increase in the chemisorption heat, the activation energy of the chemisorption stage decreases and, as a consequence, its rate increases. The sorption process parameters were calculated—the Fe2O3 coverage degree with the initial substances and reaction products providing the maximum sorption rate, which can be a criterion for evaluating the catalytically active sites of the catalyst surface for carrying out catalytic reactions.

Quantitation of furosine, furfurals, and advanced glycation end products in milk treated with pasteurization and sterilization methods applicable in China

Pasteurization and sterilization, normally carried out in milk, can induce the Maillard reaction, which can produce substances that are harmful to health. Quantitation of initial, intermediate, and advanced Maillard reaction products in milk was conducted for pasteurization (low-temperature long-time [LTLT], high-temperature short-time [HTST]) and sterilization (ultra-high temperature [UHT], in-bottle sterilization [BS]) methods. Total lysine and lactose decreased by 32.8% and 6.7% in BS milk, respectively. The generation of furosine in sterilized milk and pasteurized milk ranged from 2.5- to 5.0-fold and 1.4- to 2.8-fold higher, respectively, than those in raw milk. 5-(Hydroxymethyl)furfural increased by 4.7- and 8.4-fold in UHT and BS milk, and 2-furaldehyde (F) was not quantified in raw and LTLT milk. The concentrations of Nε-(carboxymethyl)lysine (CML) was nearly 4.4- to 6.7-fold higher than that of Nε-(carboxyethyl)lysine in the heated milk samples. CML in UHT and BS milk were around 1.4–fold and 1.6-fold higher than that in raw milk, respectively. The concentration of these Maillard reaction products in sterilized milk was significantly higher than those in raw, LTLT, and HTST milk. The results of this study could improve safety control in the dairy industry with respect to pasteurization and sterilization procedures.

Taste improvement of Maillard reaction intermediates derived from enzymatic hydrolysates of pea protein

Maillard reaction intermediates (MRIs) derived from enzymatic hydrolysates of pea protein, mainly initial Maillard reaction products, were prepared at a low temperature (80 °C) and the reaction time was determined by variable-temperature Maillard reaction. Electronic tongue and sensory evaluation were used to analyze the taste qualities of pea protein hydrolysates and their MRIs. Both evaluations showed that bitterness of enzymatic hydrolysates of pea protein reduced but umami taste increased through Maillard reaction. The intensities of umami and saltiness were positively correlated with the concentration of MRIs. Even when the dosage of MRIs was 0.1% (w/w), MRIs could achieve a 20% reduction in NaCl content without decreasing saltiness, which could be great potential substitutes for salt reduction. On the other hand, the increased MRIs promoted aldosterone secretion in saliva, which might enhance human perception of saltiness.

Effect of particle size on the thermal decomposition of nano ε-CL-20 by ReaxFF-lg molecular dynamics simulations

The thermal decomposition processes of the CL-20 nanoparticles with different diameters were simulated at different temperatures by reactive molecular dynamics. We analyzed the effects of the particle size on the thermal decompositions of the nano-CL-20 through the time evolution of potential energy, initial reaction, intermediates, and final products. The thermal decomposition does not originate from the surface but from the interior of the nanoparticles. Then, the effects of the particle size on the kinetic parameters of the decomposition reactions were studied. Finally, the effects of the particle size on the number and formation rate of primary products were determined.

In situ reactions during direct laser deposition of Ti-B4C composites

Direct laser deposition of a mixture of titanium (Ti) and boron-carbide (B4C), using the laser engineered net shaping process, results in a complex multi-phase Ti matrix composite due to the incipient interfacial reactions between liquid titanium and solid/partially melted B4C. Detailed microstructural characterization, at multiple length scales, reveals that titanium boride (TiB) precipitates are the initial reaction product which act as heterogeneous nucleation sites for TiC precipitates. Both the TiB and TiC precipitates in turn act as heterogeneous nucleation sites for fine β-Ti grains, within the retained liquid titanium, which eventually transform into fine equiaxed α-Ti grains comprising the matrix.

Detecting the Quantity of Acrylamide in Potato Chips Utilizing CdTe Surface Functionalized Quantum Dots with Fluorescence Spectroscopy

According to the classification of the International Agency for Research on Cancer (IARC), acrylamide is a compound in “probably carcinogenic for humans” class (Group 2A). Acrylamide is produced through the reactions induced by heating food within the amino group asparagine and the carbonyl group decreasing sugars along side the thermal treatment of initial Maillard reaction products. The purpose of this work is to present and enhance an innovative technique for acrylamide determination in potato chips through CdTe surface-functionalized quantum dots as a reagent for the determination of acrylamide by fluorescence spectroscopy. For this purpose, fluorescence emission spectroscopy was used instead of conventional HPLC/GC methods and data of merit of the suggested technique were assessed. The acrylamide quantity in 4 potato chips specimens, prepared from a local market in Tehran, was determined through utilizing the suggested process. Effective parameters in the process were optimized using the one-factor-at-a-time (OFAT) technique. The optimal quantities of effective parameters such as pH absorption, temperature, and emission wavelength were determined. Comparison between two methods, namely HPLC and fluorescence spectroscopy, was also described. The merit figures for the suggested approach were within the idyllic range. The developed methods showed a high correlation coefficient (0.991), high sensitivity, and repeatability. Results of the fluorescence emission spectroscopy and its comparison with Mass/HPLC revealed the high reliability and performance of the recommended method as an efficient, simple, and quick procedure with reduced cost and time in the determination of acrylamide in potato chip specimens.