Macroheterocyclic Compounds Research Articles

Bispidine-Based Macrocycles: Achievements and Perspectives

This review presents all currently known macroheterocyclic compounds that include a bispidine (3,7-diazabicyclo[3.3.1]nonane) fragment in their structure. A classification of bispidine-containing macroheterocycles, which is based on the ring size and the nature of bispidinic nitrogen atoms, is suggested. Synthetic approaches to the studied compounds are classified and considered. The features of the crystal structures and solution behavior of bispidine macroheterocycles are analyzed. Prospects for the development of these organic receptors are proposed.

SYNTHESIS, PROPERTIES, AND APPLICATIONS OF SUPRAMOLECULAR LIQUID CRYSTAL MATERIALS AND ACRYLAMIDE PORPHYRIN POLYMERS

A review of the work in the field of design, study of properties, and application of liquid crystal materials and acrylamide porphyrin polymers, performed at the Department of Chemistry and Technology of High-molecular Compounds, in the laboratory of Supramolecular and liquid crystal systems and in the laboratory of Polymer materials of the Research Institute of Macroheterocyclic compounds of the Ivanovo State University of Chemical Technology over the past 10 years, is presented. Synthetic methods were developed, mesogenic compounds and mixed liquid crystal compositions based on classical and supramolecular mesogens doped with additives containing polar, amphiprotic and chiral groups were obtained and studied. The mechanisms of chiral transport in the mesophase were studied. The results on the use of liquid crystals as light and heat stabilizers of polymeric materials are presented. Stationary phases for gas-liquid chromatography based on supramolecular mesogens, macroheterocyclic compounds with high structural selectivity with respect to various isomers were developed. Methods have been developed for the synthesis of water-soluble porphyrin polymers and porphyrin-containing hydrogels based on acrylamide and synthetic porphyrin monomers, realizable both under thermal heating and under microwave radiation. It is shown that a change in the ratio and nature of the components, as well as the polymerization conditions in the synthesis of porphyrin polymers provides targeted control of the properties of the resulting compounds. The molecular-mass and spectral characteristics of the obtained polymers, their surface morphology and sorption properties of porphyrin-containing acrylamide hydrogels are investigated. For citation: Burmistrov V.A., Aleksandriiskii V.V., Novikov I.V., Pechnikova N.L., Shilov I.V., Lyubimtsev A.V., Ageeva T.A., Koifman O.I. Synthesis, properties, and applications of supramolecular liquid crystal materials and acrylamide porphyrin polymers. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 7. P. 31-51. DOI: 10.6060/ivkkt.20236607. 6832j.

ACHIEVEMENTS IN THE FIELD OF CHEMISTRY OF MACROHETEROCYCLIC COMPOUNDS AT THE DEPARTMENT OF TECHNOLOGY OF FINE ORGANIC SYNTHESIS

The material presented in this review is devoted to scientific research carried out at one of the oldest graduating departments of ISUCT - the Department of Fine Organic Synthesis Technology. For citation: Danilova E.A., Galanin N.E., Islyaikin M.K., Maizlish V.E., Berezina G.R., Rumyantseva T.A., Suvorova Yu.V., Znoiko S.A., Kustova T.V. Achievements in the field of chemistry of macroheterocyclic compounds at the department of technology of fine organic synthesis. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 7. P. 111-119. DOI: 10.6060/ivkkt.20236607. 6826j.

CHEMISTRY OF LIQUID SYSTEMS AND FUNCTIONAL MATERIALS BASED ON COORDINATION COMPOUNDS OF LINEAR AND CYCLIC POLYPYRROLES

The review presents a generalization of research on the chemistry of solutions and materials based on linear and cyclic polypyrrole compounds carried out at the Department of Inorganic Chemistry of the Ivanovo State University of Chemistry and Technology. The review focuses on key areas related to synthetic approaches to the preparation of boron complexes with pyrrole derivatives, as well as complexes of a wide range of metals of the periodic system with substituted derivatives of the phthalocyanine ligand. Spectroscopic, luminescent, acid-base properties of synthesized compounds and their practical application in sensor systems are considered separately. In addition, the possibilities of obtaining hybrid and functional materials, including derivatives of borondipyrrins and tetrapyrrole macroheterocyclic compounds, which have increased catalytic and biological activity in liquid-phase processes are shown. For citation: Vashurin A.S., Bobrov A.V., Botnar A.A., Bychkova A.N., Gornukhina O.V., Grechin O.V., Erzunov D.A., Kovanova M.A., Ksenofontova K.V., Kuznetsov V.V., Lefedova O.V., Latypova A.R., Litova N.A., Marfin Yu.S., Pukhovskaya S.G., Tarasyuk I.A., Tikhomirova T.V., Rumyantsev E.V., Usoltsev S.D., Filippov D.V. Chemistry of liquid systems and functional materials based on coordination compounds of linear and cyclic polypyrroles. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 7. P. 76-97. DOI: 10.6060/ivkkt.20236607. 6840j.

Tetrapyrrole Macroheterocyclic Compounds. Structure–Property Relationships

Tetrapyrrole Macroheterocyclic Compounds. Structure–Property Relationships

Experimental and theoretical insights about the effect of some newly designed azomethine group‐contained macroheterocycles on oxidative stress and DNA repair gene profiles in neuroblastoma cell lines

We report herein the synthesis of new azomethine group containing forty-, sixty-eight- and seventy-two-membered macroheterocyclic compounds and the investigation of their activity against the neuroblastoma cell line. The synthesis of targeted compounds was done by condensation of dialdehydes with polyamines and their structures were investigated by 1H and 13C NMR and MALDI MS methods. Anticancer activity of these newly synthesized molecules was studied in the neuroblastoma (SH-SY5Y) cell line at eight different concentrations (1–100 µg/ml) for 24 h, 48 ​​hrs and 72 h by MTT method. In addition to it, oxidative stress (GPX1, PRDX1, CAT, SOD1, NQO1) and DNA repair (ATR, ERCC1, CDKN1A, PRKDC) gene profiles were also investigated by RT-PCR method. It was found that all synthesized compounds showed the highest activity after 72 h of incubation. PRDX1 gene expression in the case of all investigated compounds was found to be higher than the control group, whereas ABCB1 (MDR) gene expression increased only in the case of molecule 1. Results also demonstrate that the expression levels of GPX and SOD1 genes were high in the case of molecule 2, whereas molecule 1 manifested low expression levels of ERCC1, ATR, CDKN1A, PRKDC, GPX1, ABCB1(MDR), CAT, SOD1 and NQO1 genes. Along with experimental studies, theoretical studies were also carried out. The String v11 program was used to determine the interaction of proteins involved in oxidative stress and DNA repair mechanisms with other proteins. The results of the molecular docking analysis were found to be in good agreement with the experiments.

Investigation of phthalocyanine diamidophosphate-nickel by thermal analysis

The article presents the results of a study of the synthesis of a new type of pigment - nickel phthalocyanine diphosphate (DAPNiPc), which contains macroheterocyclic compounds. The influence of the method of obtaining a pigment in the liquid and solid phases on its physicochemical properties and intensity has been studied. The gross formula of the pigment is given and the areas of its practical application are shown. Thermal analysis on a Setaram LabSys Evo instrument (France) was used to study the thermal stability of a highly intense pigment of the organic nickel phthalocyanine pigment, which was compared with the closest analog, the copper phthalocyanine pigment. Thermal studies of exothermic and endothermic processes were carried out in the temperature range of 100-500 °C. The results of the mass loss of the pigment upon heating are presented. It is shown that, due to the content of phosphorus-containing compounds, the synthesized pigment has high heat resistance and intensity.

Prospects for the use of macrocyclic photosensitizers for inactivation of SARS-CoV-2: selection of compounds leaders based on the molecular docking data

The treatment of coronavirus COVID-19, like other viral diseases, is currently underdeveloped. This fact necessitates the search for new drugs and treatment methods that will effectively disrupt the life cycle of the virus. A big problem in the therapy of viral diseases is the ability of viruses to evade the host's immune response. We suppose that the search for drugs that can change the evasiveness of the virus from the immune response of the host is a very promising strategy, as it can help the body to cope with the infection. Protein SARS-CoV-2 ORF8 is one of the key proteins that can suppress antiviral immunity. This paper considers the available information on the structure and functioning of ORF8, as well as the results of molecular docking of ORF8 to a wide range of tetrapyrrole macroheterocyclic compounds capable of generating reactive oxygen species upon photoirradiation. This principle of photoinactivation of biosubstrates underlies the methods of photodynamic therapy of cancer. Application of photoinactivation of drug-resistant forms of bacteria and some viruses can be useful in the fight against COVID-19 and other viral infections. In this work, the structure of ORF8 complexes with macrocyclic compounds is considered in detail, the dependence of their binding affinity on the nature of macrocycles and the nature of peripheral substituents is analyzed and spectral studies of the binding of ORF8 to chlorin is performed. This paper is a part of a large project to investigate the possibility of using macrocyclic compounds for the treatment of viral diseases. Communicated by Ramaswamy H. Sarma

Spectral and theoretical study of SARS-CoV-2 ORF10 protein interaction with endogenous and exogenous macroheterocyclic compounds

The coronavirus disease 2019 (COVID-19) caused by the SARS-CoV-2 coronavirus has spread rapidly around the world in a matter of weeks. Most of the current recommendations developed for the use of antivirals in COVID-19 were developed during the initial waves of the pandemic, when resources were limited and administrative or pragmatic criteria took precedence. The choice of drugs for the treatment of COVID-19 was carried out from drugs approved for medical use. COVID-19 is a serious public health problem and the search for drugs that can relieve the disease in infected patients at various stages is still necessary. Therefore, the search for effective drugs with inhibitory and/or virucidal activity is a paramount task. Accessory proteins of the virus play a significant role in the pathogenesis of the disease, as they modulate the host's immune response. This paper studied the interaction of one of the SARS-CoV-2 accessory proteins ORF10 with macroheterocyclic compounds – protoporphyrin IX d.m.e., Fe(III)protoporphyrin d.m.e. and 5,10,15,20-tetrakis(3′-pyridyl)chlorin tetraiodide, which are potential inhibitors and virucidal agents. The SARS-CoV-2 ORF10 protein shows the highest affinity for Chlorin, which binds hydrophobically to the alpha structured region of the protein. Protoporphyrin is able to form several complexes with ORF10 close in energy, with alpha- and beta-molecular recognition features, while Fe(III)protoporphyrin forms complexes with the orientation of the porphyrin macrocycle parallel to the ORF10 alpha-helix. Taking into account the nature of the interaction with ORF10, it has been suggested that Chlorin may have virucidal activity upon photoexposure. The SARS-CoV-2 ORF10 protein was expressed in Escherichia coli cells, macroheterocyclic compounds were synthesized, and the structure was confirmed. The interaction between macrocycles with ORF10 was studied by spectral methods. The results of in silico studies were confirmed by experimental data.

Theoretical and experimental study of interaction of macroheterocyclic compounds with ORF3a of SARS-CoV-2

The pandemic infectious disease (Covid-19) caused by the coronavirus (SARS-CoV2) is spreading rapidly around the world. Covid-19 does an irreparable harm to the health and life of people. It also has a negative financial impact on the economies of most countries of the world. In this regard, the issue of creating drugs aimed at combating this disease is especially acute. In this work, molecular docking was used to study the docking of 23 compounds with QRF3a SARS-CoV2. The performed in silico modeling made it possible to identify leading compounds capable of exerting a potential inhibitory and virucidal effect. The leading compounds include chlorin (a drug used in PDT), iron(III)protoporphyrin (endogenous porphyrin), and tetraanthraquinone porphyrazine (an exogenous substance). Having taken into consideration the localization of ligands in the QRF3a SARS-CoV2, we have made an assumption about their influence on the pathogenesis of Covid-19. The interaction of chlorin, iron(III)protoporphyrin and protoporphyrin with the viral protein ORF3a were studied by fluorescence and UV–Vis spectroscopy. The obtained experimental results confirm the data of molecular docking. The results showed that a viral protein binds to endogenous porphyrins and chlorins, moreover, chlorin is a competitive ligand for endogenous porphyrins. Chlorin should be considered as a promising drug for repurposing.

Destruction of Chitosan and Its Complexes with Cobalt(II) and Copper(II) Tetrasulphophthalocyanines.

Chitosan is a naturally occurring polysaccharide derived from chitin with a wide range of uses. Phthalocyanines are macroheterocyclic compounds that have a number of useful properties such as coloring and catalytic and antioxidant activity. Phthalocyanines are able to immobilize on chitosan, forming complexes with new useful properties. In this work, we evaluated the ability of phthalocyanines to increase the thermal stability of chitosan. Chitosan (CS) forms complexes with copper(II)-(CuPc) and cobalt(II)-(CoPc) tetrasulphophthalocyanines. The processes of destruction of chitosan (CS) and its complexes with sulphophthalocyanines CuPc and CoPc in oxidizing and inert atmospheres have been studied. It was established that, regardless of the atmosphere composition, the first chemical reactions taking place in the studied systems are elimination reactions. The latter ones in the case of chitosan and complex CS-CuPc lead to the formation of spatially crosslinked polymer structures, and it causes the release of CuPc from the polymer complex. It was found that in the case of CS-CoPc elimination reactions did not lead to the formation of crosslinked polymer structures but caused the destruction of the pyranose rings with a partial release of CoPc. Metallophthalocyanines showed antioxidant properties in the composition of complexes with chitosan, increasing the temperature of the beginning of glycosidic bond cleavage reaction by 30–35 °C in comparison with the similar characteristics for chitosan.

Synthesis of Hetaryl-Substituted Asymmetric Porphyrins and Their Affinity to SARS-CoV-2 Helicase.

Novel porphyrin compounds containing benzothiazole, benzoxazole, and benzimidazole moieties have been prepared and their structures have been confirmed. Molecular docking of non-symmetric hetaryl-substituted porphyrins and chlorin e6 with SARS-CoV-2 helicase has been carried out. The affinity of hetaryl-substituted porphyrins to this protein has been found significantly higher than that of the drugs approved by the FDA and chlorin e6. The structure of the complexes of SARS-CoV-2 helicase with the considered macroheterocyclic compounds has been analyzed. Possible ways to inhibit and photoinactivate SARS-CoV helicase have been suggested basing on the localization of porphyrins and chlorin e6 in the helicase domains.

Thermodynamics of the Dissolution of Asymmetric Macroheterocyclic Compounds with Thiadiazol Fragments in Polar Solvents

Thermodynamics of the Dissolution of Asymmetric Macroheterocyclic Compounds with Thiadiazol Fragments in Polar Solvents

Spectral Characterization of Macro-Heterocyclic Compound RhTMPyP / ZnTSPc

Macro-heterocyclic compounds, such as porphyrins and phthalocyanines, are being studied extensively for their important physical and chemical properties. Their ability to absorb light throughout the spectrum and self-organization being adequate for the realization of several applications. Investigations of the spectral properties of the supramolecular assembly RhTMPyP/ ZnTSPc- 5,10,15,20 rhodium tetramethyl-pyridyl porphyrin / 2,9,16,23 zinc tetrasulfonated-phthalocyanine are registered by UV-Vis, FT-IR and Raman spectroscopic techniques.

Sorption of meso-Phenylporphyrin Iodide on Polystyrene–Bentonite Film Composites

Modification of polystyrene (PS) with bentonite was carried out, and film materials with improved sorption properties toward macroheterocyclic compounds were obtained. It has been shown that the efficiency of adsorption of meso-phenylporphyrin iodide on the PS–bentonite composite is increased threefold compared to unmodified polymer. The kinetics of porphyrin adsorption was described by the reaction equations of the pseudo-first and pseudo-second order. It was revealed by IR spectroscopy that the adsorption of meso-phenylporphyrin iodide on the PS–bentonite composite occurs as a result of the donor–acceptor interaction of the porphyrin reaction centers with the oxygen-containing groups of the composite.

Precursors for the Synthesis of Macroheterocyclic Compounds. Modeling of the Mechanism for Formation of 2-Amino-5-methyl-1,3,4-thiadiazole by Quantum Chemistry Methods

Precursors for the Synthesis of Macroheterocyclic Compounds. Modeling of the Mechanism for Formation of 2-Amino-5-methyl-1,3,4-thiadiazole by Quantum Chemistry Methods

Synthesis and Properties of Bisthiadiazoles with Ethyl and Butyl Spacers

This article is devoted to a selection of the most effective preparative method for the synthesis of bis(5-amino-1,3,4-thiadiazole-2-yl)alkanes. These compounds are binuclear diamines consisting of symmetrical 1,3,4-thiadiazole fragments connected by alkyl spacers of various lengths. The structures of the obtained compounds were determined by IR spectroscopy, mass-spectrometry and elemental analysis. The possibility of using these molecules as precursors for the synthesis of macroheterocyclic compounds with expended coordination cavity consisting of six small cycles was demonstrated. Optimal synthesis conditions of bis(5-amino-1,3,4-thiadiazole-2-yl)ethane and bis(5-amino-1,3,4-thiadiazole-2-yl)butane were found by variation of reaction time and temperature. Virtual screening of the obtained compounds was carried out in order to predict antibacterial and biological activities as well as toxic properties of the targeted products. On the basis of the known literature data on polynuclear diamines, the exhibition of the liquid crystal properties of the synthesized molecules is supposed.

SYNTHESIS AND INVESTIGATION OF COPOLYMERS OF GLYCIDYLMETHACRYLATE AND COPPER COMPLEX METHYL PHEOPHORBIDE “A” IN SOLUTION

The actual direction in the field of creating new functional materials is a complex study of the influence of tetrapyrrole macroheterocyclic compounds on the processes of radical (co)polymerization with widely used monomers, as well as the development of a general approach to the synthesis and study of the properties of such polymer materials. Promising macroheterocyclic compounds are chlorophyll derivatives of various structures. For this purpose, by the method of solution radical copolymerization in toluene and tetrahydrofuran the copolymers of glycidylmethacrylate and copper complex of methylpheophorbide “a” of various compositions were obtained. Identification of the obtained copolymers and investigation of their structure and properties were performed using data from IR, NMR spectroscopy of compounds, elemental and chemical analysis methods. The synthesized copolymers are characterized by molecular-weight characteristics which were determined by gel-permeation chromatography. It was found that the introduction of a copper complex of methylpheophorbide “a” into the copolymer leads to a decrease in the copolymerization rate, the values of the molecular masses of copolymers and an increase in their polydispersity. The effect of solvents on the time of the copolymerization process and the molecular weight characteristics of copolymers is shown. The composition of the obtained copolymers was determined spectrophotometrically by the optical density of their solutions at the maximum of the first absorption band of the copper complex of methylfeoforbide “a”. Comparison of the intensity of bands in the IR spectra of copolymers of different compositions showed that the content of methylpheophorbid links in the polymer chain increases with the increase in the content of porphyrin in the polymerized mixture. The study of the influence of the nature of the solvent and its structural features on chemical reactions involving porphyrin derivatives allowed us to establish that from a thermodynamic point of view, the best solvent for porphyrinpolymers is toluene.

BGR MACROHETEROCYCLIC COMPOUNDS OF ASYMMETRIC STRUCTURE WITH THIADIAZOL FRAGMENTS. SYNTHESIS AND PROPERTIES

This communication is a continuation of the systematic research of the authors in the field of synthesis and study of the properties of macroheterocyclic compounds. The great potential for structural modification allows us to synthesize macroheterocyclic compounds that differ in composition and the nature of the heteroatoms that make up them and make this class of compounds promising from the point of view of the design for the preparation of substances with valuable practical properties. The interaction of N,N/-bis-(1-imino-2-phenyl-1H-indene-3-iliden)-1,4-phenylenediamine with 2,5-dimiano-1,3,4-thiadiazole and 3,5-diamino-1,2,4-thiadiazole the macroheterocyclic compounds of asymmetric structure were synthesized in the molar ratio of the initial substances. Macroheterocycles are powdered substances with different shades of red color, having melting and crystallization temperatures (investigated in the argon current), soluble in chloroform, DMF, acetone, ethanol. Purification was carried out by column chromatography on aluminum oxide of II degree of activity on Brockman (eluent acetone - chloroform, 1:9 by volume). Identification of synthesis products was performed by thin-layer chromatography on Silufol UV-254 plates (eluent – acetone - chloroform, 1:1 by volume). The obtained compounds were characterized by infrared and electron spectroscopy. The electronic absorption spectra were measured on a Hitachi U-2010 instrument in quartz cuvettes at 20 °C. IR spectra were obtained on the Avatar 360 FT-IR ESP device in KVG. Elemental analysis data were obtained using the CHNS-O Analyzer FlashEA of 1112 Series. A bathochromic shift of the absorption bands was noted when the compound with 1,3,4-thiadiazole was closed in a cycle. The spectral characteristics indicate that the molecules of the synthesized compounds do not have a flat structure and the absorption is due to individual fragments that are part of the molecules of the synthesized structures.

Macroheterocyclic Compounds - a Key Building Block in New Functional Materials and Molecular Devices

Macroheterocyclic Compounds - a Key Building Block in New Functional Materials and Molecular Devices