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Vol 17, No 2 (2022)
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THEORETICAL BASES OF CHEMICAL TECHNOLOGY 

  • The conditions of fractionation of the origin multicomponent mixture due to the use of sharp distillation, pre-splitting process, and extractive distillation were revealed.
  • New approaches to the synthesis of energy-efficient multicomponent mixtures separation flowsheets were proposed.
  • Technological flowsheets of separation of acetone–chloroform–ethanol (isopropanol)–water, ethanol–cyclohexane–chloroform–water, ethyl acetate–methyl ethyl ketone–cyclohexane–isopropanol, methanol–tert-butanol–methyl-tret-butyl ether–water mixtures were developed, the columns static parameters were determined.
87-106 554
Abstract

Objectives. To improve the process of developing energy-efficient flowsheets for the distillation separation of multicomponent aqueous and organic mixtures based on a comprehensive study of the phase diagram structures, including those in the presence of additional selective substances.

Methods. Thermodynamic-topological analysis of phase diagrams; modeling of phase equilibria in the AspenTech software package using the equations of local compositions: Non-Random Two Liquid and Wilson; computational experiment to determine the column parameters for separation flowsheets of model and real mixtures of various nature.

Results. The fractionation conditions of the origin multicomponent mixture due to the use of sharp distillation, pre-splitting process, extractive distillation with individual and binary separating agents were revealed. The columns operation parameters and the energy consumption of the separation flowsheets ensuring the achievement of the required product quality with minimal energy consumption were determined.

Conclusions. Using the original methods developed by the authors earlier and based on the generalization of the results obtained, new approaches to the synthesis of energy-efficient multicomponent mixtures separation flowsheets were proposed. The provisions that form the methodological basis for the development of flowsheets for the separation of multicomponent mixtures and supplement the standard flowsheet synthesis plan with new procedures were formulated.

CHEMISTRY AND TECHNOLOGY OF MEDICINAL COMPOUNDS AND BIOLOGICALLY ACTIVE SUBSTANCES 

  • The review analyzed macrocyclic bifunctional chelators forming stable in vivo complexes with 68Ga and acyclic chelators.
  • In order to create effective bifunctional chelating agents, it is necessary to take into account such factors as the stability and inertness of the chelator and its complexes under physiological conditions, lipophilicity, complexation kinetics, chelation selectivity, combinatoriality of the basic structure, along with economic aspects, e.g., the availability of raw materials and the complexity of the synthesis scheme.
107-130 590
Abstract

Objectives. The chemistry of 67Ga and 68Ga radionuclides plays a key role in nuclear medicine for applications in radiopharmaceuticals, in particular, in noninvasive in vivo molecular imaging techniques. The use of radiometals for labeling biomolecules typically requires the use of bifunctional chelators, which contain a functional group for covalent bonding with the targeting vector in addition to the polydentate fragment coordinating the metal. The aim of the present review article is to analyze the currently accumulated experimental material on the development and application of bifunctional chelators of gallium cations in medical research, as well as to identify the main requirements for the structure of the chelator and its complexes with 68Ga, which are used to create effective Gabased pharmaceutical preparations.

Results. The review analyzed macrocyclic bifunctional chelators forming stable in vivo complexes with 68Ga and acyclic chelators, whose main advantage is faster complexation kinetics due to the short half-life of 68Ga. The advantages and disadvantages of both types of ligands were evaluated. In addition, a critical analysis of the binding constants and the conditions for the formation of complexes was presented. Examples of the influence of the geometry, lipophilicity, and total charge of the metal complex on the biodistribution of target radiopharmaceuticals were also given.

Conclusions. Despite the progress made in the considered areas of bifunctional chelators, the problem of correlating the chemical structure of a metal-based radiopharmaceutical with its behavior in vivo remains important. Comparative studies of drugs having an identical targeting vector but containing different bifunctional chelating agents could help further elucidate the effectof metal chelate moiety on pharmacokinetics. In order to create effective bifunctional chelating agents, it is necessary to take into account such factors as the stability and inertness of the chelator and its complexes under physiological conditions, lipophilicity, complexation kinetics, chelation selectivity, combinatoriality of the basic structure, along with economic aspects, e.g., the availability of raw materials and the complexity of the synthesis scheme.

  • The extracts of ten plant were characterized by determination of the TFC, TPC, and XO inhibitory activity.
  • Piper betle  had significant XO inhibitory activity.
  • The leaf was the part of the Piper betle L. that showed strong XO inhibitory activity and also antioxidant activity compared with stem, and whole plant extract.
131-139 665
Abstract

Objectives. The study aimed to test the ethanol extracts of ten medicinal plants for xanthine oxidase inhibitory activity.

Methods. The degree of xanthine oxidase inhibitory activity was determined by measuring the absorbance spectrophotometrically at 290 nm, which is associated with uric acid formation. The selected medicinal plants included Piper lolot C.DC. (Piperaceae), Pandanus amaryllifolius R.(Pandanaceae), Brassica juncea L. (Brassicaceae), Piper betle L. (Piperaceae), Perilla frutescens L. (Lamiaceae), Anacardium occidentale L. (Anacardiaceae), Polygonum barbatum L. (Polygonaceae), Artocarpus Altilis P. (Moraceae), Vitex negundo L. (Verbenaceae), Annona squamosal L. (Annonaceae), which were selected based on folk medicine.

Results. The results showed that the Piper betle L. has a strong ability to inhibit xanthine oxidase with an IC50 value of up to 1.18 μg/mL, compared to allopurinol 1.57 μg/mL. Different parts of Piper betle L. were compared and the leaves of Piper betle L. showed the best value for xanthine oxidase inhibitory and antioxidant activity.

Conclusions. Piper betle L. showed the best potential for inhibition of xanthine oxidase among ten medicinal plants. Piper betle L. leaf extract showed strong xanthine oxidase inhibitory and antioxidant activity, compared to the whole plant, and the stem extract, which promises to be applied in the treatment of gout.

BIOCHEMISTRY AND BIOTECHNOLOGY 

  • The low cytotoxicity of siRNA complexes for cells was shown according to the MTT test results when the expression of several genes was simultaneously suppressed.
  • siRNA complexes that simultaneously reduce the activity of two or more of these genes suppress viral reproduction in vitro, assessed using viral titration by the cytopathic effect and real time RT-PCR.
  • Data were obtained on the correlation between a decrease in the expression of several cellular genes simultaneously and a decrease in viral reproduction.
140-151 509
Abstract

Objectives. Evaluation of changes in the viral activity of influenza A/WSN/33 after complex knockdown of combinations of cellular genes FLT4, Nup98 and Nup205 in human lung cell culture A549.

Methods. The work was carried out using the equipment of the Center for Collective Use of the I. Mechnikov Research Institute of Vaccines and Sera, Russia. The authors performed transfection of combinations of small interfering ribonucleic acid (siRNA) complexes that cause simultaneous disruption of the expression of cellular genes FLT4, Nup98, and Nup205. Within three days from the moment of transfection and infection, the supernatant fluid and cell lysate were taken for subsequent viral reproduction intensity determination using the titration method for cytopathic action. The dynamics of changes in the concentration of viral ribonucleic acid (vRNA) was determined by real-time reverse transcription polymerase chain reaction (real-time RT-PCR). The nonparametric Mann–Whitney test was used to calculate statistically significant differences between groups.

Results. Using all of the combinations of siRNA complexes, cell viability did not decrease below the threshold level of 70%. In cells treated with complex FLT4.2 + Nup98.1 + Nup205 at the multiplicity of infection (MOI) equal to 0.1, a significant decrease in viral reproduction by 1.5 lg was noted on the first day in relation to nonspecific and viral controls. The use of siRNA complexes at MOI 0.01 resulted in a more pronounced antiviral effect. The viral titer in cells treated with siRNA complexes FLT4.2 + Nup98.1 and Nup98.1 + Nup205 decreased by 1.5 lg on the first day. In cells treated with complexes FLT4.2 + Nup205 and FLT4.2 + Nup98.1 + Nup205, it decreased by 1.8 and 2.0 lg on the first day and by 1.8 and 2.5 lg on the second day, respectively, in relation to nonspecific and viral controls. When conducting real-time RT-PCR, a significant decrease in the concentration of vRNA was noted. At MOI 0.1, a 295, 55, and 63-fold decrease in the viral load was observed with the use of siRNA complexes FLT4.2 + Nup98.1, Nup98.1 + Nup205, and FLT4.2 + Nup98.1 + Nup205, respectively. On the second day, a decrease in vRNA was also observed in cells treated with complex A. A 415-fold decrease in vRNA on the third day was noted in cells treated with complex FLT4.2 + Nup205. At MOI 0.01, the concentration of vRNA decreased 9.5 times when using complex B relative to nonspecific and viral control.

Conclusions. The study showed a pronounced antiviral effect of siRNA combinations while simultaneously suppressing the activity of cellular genes (FLT4, Nup98, and Nup205), whose expression products are playing important role in the viral reproduction process, and obtained original designs of siRNA complexes. The results obtained are of great importance for the creation of emergence prophylactic and therapeutic drugs, whose action is based on the mechanism of RNA interference.

SYNTHESIS AND PROCESSING OF POLYMERS AND POLYMERIC COMPOSITES 

  • Using the case study of nitrile-butadiene-based rubbers, the effect of surfactants such as rosin and stearic acid, accelerated aging conditions, and methods for extracting rubber from latex on the surface energy of elastomeric materials was studied.
  • It was shown that a change in the physical and mechanical properties of vulcanizates occurred along with a change in the critical surface tension.
152-163 400
Abstract

Objectives. The influence of the technological additive content and accelerated aging conditions on the surface energy and elastic-strength properties of nitrile butadiene rubbers with an average acrylic acid nitrile content and rubbers based on them were studied in the paper.

Methods. The free surface energy of the samples was determined under the standard conditions and in the accelerated aging conditions with the use of the Owens, Wendt, Rabel, and Kaelble method.

Results. It was shown that the elastomeric materials surface energy is influenced by surfactants such as rosin and stearic acid, which are typical ingredients of rubber compounds. It was also found that the thermal aging effect on the physical and mechanical properties of rubbers based on nitrile butadiene rubbers depends on the method of rubber isolation from latex and on the nature of the surfactant components in the samples.

Conclusions. The analysis of the results obtained shows that the change in the vulcanizates physical and mechanical properties, depending on the technological additive content and the temperature effect, occurs along with a change in the critical surface tension.

  • Chemical recycling of polyethylene terephthalate (PET) under the action of oligoesters (less than 15 mol %) with hydroxyl end groups allowed obtaining modified high molecular weight copolyesters.
  • The recycling process was based on the simultaneous glycolysis and interchain exchange reactions.
  • The introduction of phthalate units into PET effectively reduced the glass transition temperature, the copolymer temperature and fusion heat, and also increased its crystallization half-time.
164-171 586
Abstract

Objects. Due to the polymer waste accumulation, the search for new directions for their utilization is urgent. Chemical recycling methods are of considerable interest, which allow one to obtain the original monomers or change the compositions of the copolymers. From the point of view of building a circular economy, a promising material is polyethylene terephthalate (PET), on the basis of which amorphous copolyesters can be obtained. The study aimed to analyze the simultaneous glycolysis and interchain exchange reactions of PET in the presence of the oligoethylene phthalate modifier with hydroxyl end groups and the study of isothermal crystallization of poly(ethylene phthalate-co-terephthalates) with different phthalate contents obtained in this way.

Methods. Oligoethylene phthalate is synthesized by polycondensation. Poly(ethylene phthalateco-terephthalates) were obtained by the interaction of post-consumer PET with oligoethylene phthalate. The composition of the oligomer and copolymers was confirmed using Fourier-transform infrared spectroscopy, thermal characteristics and crystallization half-times were determined by differential scanning calorimetry.

Results. In this work, the use of the post-consumer PET chemical recycling process, aimed at obtaining copolyesters under the influence of small modifier amounts was proposed. The process consisted in carrying out the combined interchain exchange and degradation with a complex oligoester different from PET. Poly(ethylene phthalate-co-terephthalate) copolymers were obtained via reaction of post-consumer poly(ethylene terephthalate) flakes and synthesized oligoethylene phthalate resin in the melt phase in the absence of catalyst. The effect of phthalate concentration in polymer on the isothermal crystallization of phthalate substituted poly(ethylene terephthalate) was estimated.

Conclusions. The hypothesis about the possibility of using an oligoester modifier to obtain the PET-based copolymer at the high rate and without reducing the molecular weight to values characteristic of a monomer or oligomer has been confirmed. The process can be used to obtain random copolyesters based on post-consumer PET. The phthalate unit concentration increase is followed by decrease in the glass transition temperature, temperature and heat of fusion, and increase in crystallization half-times. Phthalate has a better ability to retard PET crystallization than 2-methyl-1,3-propanediol or furandicarboxylic acid, but is inferior to some of the other modifiers known.

CHEMISTRY AND TECHNOLOGY OF INORGANIC MATERIALS 

  • Compounds [Sm(BU)4]I3BU·2H2O and [Sm(BU)4][I5][I]2 complement the row of isostructural lanthanide (La–Gd) complexes with biuret.
  • Complex cations [Ln(BU)4]3+ in iodides and polyiodides differ significantly.
  • Polyiodides, in contrast to iodides, do not contain outer-sphere water and biuret molecules.
  • The presence of infinite linear chains of iodine atoms in polyiodides allows expecting the presence of anisotropic electrical conductivity along this direction.
172-181 409
Abstract

Objectives. Currently, several hundred polyiodide compounds have been synthesized and structurally characterized, but so far, no formation patterns for certain polyiodide ions have been revealed. The purpose of this work is to continue the search for formation regularities of polyiodides, including polyiodides of lanthanide complexes.

Methods. Iodide and polyiodide of samarium complexes with biuret (BU), [Sm(BU)4]I3·BU·2H2O and [Sm(BU)4][I5][I]2, were first synthesized and characterized by X-ray diffraction analysis and infrared spectroscopy, respectively.

Results. The obtained compounds complement the row of isostructural lanthanide (La–Gd) complexes. Structures of corresponding iodides and polyiodides were compared in detail. Both types of the compounds contain complex cations of the same composition; however, their structures differ significantly. The central atom coordination polyhedron can be described as a distorted square antiprism and a distorted dodecahedron, respectively. Even greater differences are observed in the outer sphere of complex compounds. The iodide compound crystals contain uncoordinated iodide ions, a biuret molecule and two water molecules. In the polyiodide compound, cations together with isolated I ions form a three-dimensional framework with the channels, in which linear I5 ions are united in infinite linear chains by weak interactions.

Conclusions. The replacement of an iodide ion with a polyiodide ion in complex compounds of lanthanides with BU leads to changes in both the inner sphere and the outer sphere of the cation complex, including the supramolecular level. The presence of iodine atom infinite linear chains in polyiodides allows expecting the presence of anisotropic electrical conductivity along this direction.



ISSN 2410-6593 (Print)
ISSN 2686-7575 (Online)