Maxim V. Bermeshev

Institute of Petrochemical Synthesis · Laboratory of organosilicon and carbocyclic compounds

A series of side-chain liquid crystalline polymers P4VP(CN-DBE) x , where x is the molar ratio of cyanostilbene (CN-DBE) to poly(4-vinylpyridine) (P4VP) repeating unit, were synthesized based on the intermolecular hydrogen bonding between P4VP and CN-DBE. Their luminescent property, liquid crystalline structure and photo-thermo-electric property we...

A novel polyurethane polymer containing perylene diimide (PDI) unit and aniline segment, denoted as PU‐PDI, was designed and synthesized. Their tensile property and photophysical characteristic were investigated using various experimental and theoretical techniques. It is found that the elongation of PU‐PDIs can reach more than 1000%, indicating go...

Dicyclopropanated 5-vinyl-2-norbornene (dcpVNB) is a strained polycyclic hydrocarbon compound with a high energy content, which makes it promising for the development of propellant components based on it. In this work, the genotoxic properties of dcpVNB were studied using whole-cell lux-biosensors based on Escherichia coli and Bacillus subtilis. It...

Optically active polymers are of great interest as materials for dense enantioselective membranes, as well as chiral stationary phases for gas and liquid chromatography. Combining the versatility of norbornene chemistry and the advantages of chiral natural terpenes in one molecule will open up a facile route toward the synthesis of diverse opticall...

Addition polymerization of cycloalkenes (cyclopentene, cyclopentadiene, cyclooctene, cyclooctadiene) in the presence of a new type of catalytic systems—Pd(0) complexes activated with arendiazonium salts—was studied. It was shown that cyclopentene, cyclooctene, and cyclooctadiene are not active in polymerization with these catalytic systems, while c...

In this work, we have proposed a new strategy of the synthesis of norbornene-type monomers with Si–O–C structural motifs via a straightforward and selective dehydrogenative addition reaction between 5-norbornene-2-methanol and trialkylsilanes. As a result, a set of monomers with various trilalkylsiloxy groups (alkyl – CH3, C2H5, and n-C3H7) was syn...

Polymers from norbornenes are of interest for applications in opto- and microelectronic (low dielectric materials, photoresists, OLEDs). Norbornenes with ester motifs are among the most readily available norbornene derivatives. However, little is known about dielectric properties and the gas-transport of polynorbornenes from such monomers. Herein,...

Two types of poly(5-phenyl-2-norbornene) were synthesized via ring opening metathesis and addition polymerization. The polymers sulfonation reaction under homogeneous conditions resulted in ionomer with high sulfonation degree up to 79% (IEC 3.36 meq/g). The prepared ionomer was characterized by DSC, GPC, 1H NMR and FT-IR. Polymers for electromecha...

Addition polymerization of substituted norbornene derivatives is a powerful tool for macromolecular design of high-performance materials. Being required for polymerization of functionalized monomers bearing bulky or polar substituents, Pd-based catalysts are known as active species providing the way to a series of high molecular weight products. He...

Exo-5-norbornene-2,3-dicarboxyanhydride (exo-NDA) is an attractive precursor for creating optically active polymers due to its symmetrical structure. Monomers based on exo-NDA have such important advantage as the possibility of polymerization exists by two mechanisms - ROMP and addition polymerization. This paper presents a simple and accessible me...

Polynorbornenes are known as materials demonstrating low values of dielectric constant. Dielectric properties of substituted polynorbornenes with different structure of the main chain bearing F-containing substituents in the side chains are discussed. The incorporation of bulky fluoroorganic groups in polynorbornene structure was found to be an eff...

Herein, we report the synthesis of a racemic monomer (1r,2r,6s,7s)-4-(1-phenylethyl)-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione and its metathesis polymerization. The desired monomer was successfully prepared from exo-5-norbornene-2,3-dicarboxyanhydride (exo-NDA) and 1-phenylethylamine. The obtained monomer exhibited a good reactivity in ROMP pol...

The molecular dynamics of addition-type poly(tricyclononenes) with Si-substituted bulky side groups has been investigated by a combination of neutron time-of-flight and neutron backscattering spectroscopy on a time scale from 0.1 ps to ca. 3 ns. The investigated poly(tricyclononenes) PTCNSi1 and PTCNSi2g both bear a high microporosity which makes t...

Polymers with rigid main chains and flexible long side substituents combine membrane properties of both glassy and rubbery polymers. Such polymers exhibit high selectivity for CO2/N2 and light hydrocarbon separations. Herein we report synthesis and gas transport properties of two sets of addition and metathesis polynorbornenes bearing flexible ethe...

The construction of highly ordered nanostructure plays an important role in realizing the specific functions of organic materials. However, it remains challenging to design photoelectric materials with sub-10-nm nanostructures. Herein, a novel tetraphenylethylene derivative tethered with polyhedral oligosilsesquioxane nanocages (TPE-BPOSS) was desi...

High-energy-density (HED) liquid fuels are required for modern and perspective volume-limited aircrafts to extend the flight distance and to increase the speed. In this work, we report on the synthesis of a new set of HED liquid polycyclic norbornane-containing hydrocarbons and on the study of their key physico-chemical characteristics. A facile ro...

POSS-containing polynorbornene with pendant perylene diimide (PPDI-POSS) has been synthesized, with alkyl-containing polynorbornene (PPDI-C10C8) as reference. the supermolecular structure and photoluminescence property were elucidated using UV-Vis absorption spectra, one- and...

Polymers derived from norbornenes with polar groups are of interest as modular templates and materials for membrane processes and microelectronic applications due to the attractive combination of their properties. However, the synthesis of high-molecular weight homopolymers from norbornenes containing polar groups is still a challenge. Herein, we r...

Here, we present a new lux-biosensor based on Bacillus subtilis for detecting of DNA-tropic and oxidative stress-causing agents. Hybrid plasmids pNK-DinC, pNK-AlkA, and pNK-MrgA have been constructed, in which the Photorhabdus luminescens reporter genes luxABCDE are transcribed from the stress-inducible promoters of B. subtilis: the SOS promoter Pd...

A series of vinyl-addition poly(5-alkyl-2-norbornenes) with varied alkyl side group from methyl to tetradecyl was synthesized and systematically studied in terms of pure and mixed gas permeability. It was found that the length of the side group plays a key role in the gas separation performance. For instance, the permeability of permanent gases thr...

The paper describes the synthesis of novel strained hydrocarbons based on a diene of the norbornene series, namely 5-methylene-2-norbornene, using catalytic cyclopropanation with diazomethane. The study demonstrated the possibility of selective cyclopropanation solely along the endocyclic double bond. The physicochemical properties of the hydrocarb...

New methylpalladium chloride complex with bulky N,N'-bis(1,2,3,4-tetrahydro-1-naphthyl)-substituted glyoxal diimine ligand was obtained. This complex was found to be an efficient catalyst for vinyl-addition polymerization of norbornene derivative and for polymerization of a diazoacetate, giving polycarbenes with side polar functionalities.

Silicon-substituted polynorbornenes are an unusual class of polymeric membrane materials, combining the properties of both glassy and rubbery polymers. They exhibit an attractive performance for CO2/N2 separation and for separation of gaseous hydrocarbons. However, addition polynorbornenes with Si-groups (for examples, having Si–O–C, or Si–O–Si-spa...

The interest in porous organic materials derived from norbornenes is driven by versatile chemistry of norbornenes, fine-tunable structure of these polymers, high accessible surface area, and large free volume of polynorbornenes for technical applications in adsorption, membrane separation, gas storage, and heterogeneous catalysis. This comprehensiv...

The chromatographic properties and thermal stability are investigated for the polymeric stationary phase based on the norbornene polymer. It was shown that without additional cross-linking, poly(3-(tributoxysilyl)tricyclononene-7) demonstrates properties similar to liquid chromatographic stationary phases. It was also found to be more thermally sta...

Polynorbornenes are ideal materials for systematic structure-property investigations designed to correlate gas-transport properties to polymer structure. The modular nature of norbornene-based systems provides a facile route towards the synthesis of diverse polymeric materials. Though many valuable correlations between gas-permeability and polynorb...

An efficient method of activating Pd-complexes without the use of additives such as Lewis acids for addition polymerization of norbornene and its derivatives has been developed. Readily available organic compounds...

[This corrects the article DOI: 10.1371/journal.pone.0228525.].

5-(Methoxymethyl)norbornene is synthesized from the commercial 5-norbornene-2-methanol via the Williamson reaction. Its addition polymerization is studied, and conditions for formation of a high molecular weight product with a high yield are determined. The gas-transport properties of the synthesized addition polynorbornene for a wide set of gases...

Based on positron annihilation and low-temperature gas (CO2) sorption data, we discuss the nature of size distribution of micropores in a number of polynorbornenes with various substituent groups in the side chain. The local stiffness of highly permeable glassy polymers suggests that they are microheterogeneous. In this case, distributions that are...

A norbornane derivative, exo-tetrahydrodicyclopentadiene, is the main component of the high-density liquid fuel called JP-10. In the current communication we describe the preparation of some related norbornane-containing hydrocarbons and their energetic properties. The desired hydrocarbons were readily obtained in high yields using Diels-Alder and/...

A novel perylene diimide derivative bearing siloxane moieties (PDI-TTMSS) was synthesized by a simple one-step reaction. By the combination of spectroscopic, microscopic and scattering experiments, we have demonstrated that PDI-TTMSS...

The main physico-chemical features, as well as gasoline blending features of eight diol derivatives (1,3-diisopropyl and 1,3-di-tert-butyl glycerol ethers – di-GIPE and di-GTBE; O-isopropyl and O-tert-butyl solketal ethers – SIPE and STBE; isopropylidene ketals of ethylene and propylene glycol – DMD and TMD; cyclic ketals of glycerol with the methy...

A series of heterogeneous catalysts based on different metal chlorides (AlCl3, NbCl5, ZnCl2) immobilized on silica gel have been prepared. The catalytic activity of obtained catalysts for the isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) to its exo-isomer (exo-THDCPD, the main component of JP-10 fuel) has been investigated in deta...

Borylation of arenes with bis(pinacolato)diboron catalyzed by sterically encumbered NHC platinum complexes proceeds predominantly at ortho-position even in the absence of a directing group (o : m : p ratio up to 10: 3: 1). The similar borylation with pinacolborane would proceed less selectively.

For the first time, dielectric and calorimetric investigations of a homologous series of Janus polynorbornenes with rigid main backbones and flexible −Si(OR)3 side groups of differing length alkyl chains (R = propyl, butyl, hexyl, octyl, and decyl) is reported. Generally, this class of polymers has some potential for applications in the field of ga...

The toxic effect of strained hydrocarbon 2,2'—bis (bicyclo[2.2.1]heptane) (BBH) was studied using whole-cell bacterial lux-biosensors based on Escherichia coli cells in which luciferase genes are transcriptionally fused with stress-inducible promoters. It was shown that BBH has the genotoxic effect causing bacterial SOS response however no alkylati...

Inelastic incoherent neutron time-of flight scattering was employed to measure the low frequency density of states for a series of addition polymerized polynorbornenes with bulky side groups. The rigid main chain in combination with the bulky side groups give rise to a microporosity of these polymers in the solid state. The microporosity characteri...

Structure-property study of polynorbornenes for low dielectric permittivity materials was performed. Dielectric properties of various polynorbornenes bearing F-, Si- and alkenyl-side groups were investigated. The incorporation of both fluoroorganic- and Me3Si-groups as side substituents was found to be a fruitful tool to tune dielectric properties...

A novel perylene diimide material (perylene diimide tetracid- dihexadecyldimethylammonium bromide, PDTA-DHAB) with unique hierarchical structure was designed and prepared by ionic self-assembly (ISA) method. The self-assembly behavior and aggregated structure of the complex were then studied by a variety of techniques such as UV-Vis absorption spec...

Polynorbornenes represent a fruitful class of polymers for structure–property study. Recently, vinyl-addition polynorbornenes bearing side groups of different natures were observed to exhibit excellent gas permeation ability, along with attractive C4H10/CH4 and CO2/N2 separation selectivities. However, to date, the gas transport properties of fluor...

In this study approaches for chemical conversions of the renewable compounds 1,2-propanediol (1,2-PD) and 2,3-butanediol (2,3-BD) that yield the corresponding cyclic ketals and glycol ethers have been investigated experimentally. The characterization of the obtained products as potential green solvents and gasoline components is discussed. Cyclic k...

The synthesis and structural characterization of a series of novel platinum(0) complexes were reported. A number of (NHC)Pt(dvtms) (dvtms = 1,3-divinyl-1,1,3,3-tetramethyldisiloxane) complexes were investigated in catalytic addition of B2Pin2 to terminal alkenes. The novel expanded ring N-heterocyclic carbene complex (7-Dipp)Pt(dvtms) showed highes...

Herein four modified polymers were prepared from readily available addition poly(5-vinyl-2-norbornene) (PVNB) and their gas-transport properties were studied in detail. Hydrogenation, epoxidation, cyclopropanation and thiol-en reactions were chosen for the modifications of PVNB. Hydrogenation of PVNB was performed using p-toluenesulfonyl hydrazide....

A new method is developed for the production of composite fibers based on cellulose and vinyltriethoxysilane and formed from N-methylmorpholine-N-oxide solutions. Introduction of the organosilicon additive promotes the activation of cellulose pyrolysis processes, and its choice relies on the presence of a double bond in vinyltriethoxysilane, which...

Here we present the study of the genotoxic effect of a 2,2'-bis(bicyclo[2.2.1]heptane) (BBH), which is promising as a fuel component for liquid rocket engines. The use of Escherichia coli lux -biosensors showed that in addition to DNA damage causing SOS-response, there is also an oxidative effect on cells. The greatest toxicity is determined by the...

We studied the addition polymerization of readily available bifunctional norbornene derivatives, 5-alkylidene-2-norbornenes, in the presence of modified Pd complexes with N-heterocyclic carbene ligands activated by borates. The Pd–N-heterocyclic carbene complex/phosphine/borate systems selectively catalyze the addition polymerization of 5-methylene...

The correlations between two structure factors of polymers from mono-silicon-substituted norbornenes are considered. The first of them is the nature of central atom in Me3X-substituent (X = C, Si, Ge). It is shown that silicon is the most optimal atom for gas-transport properties. The second factor is the nature of group bonded with silicon atom in...

Sorption and membrane properties of metathesis and addition polymers based on 5-(2’-norbornanyl)- norbornene were studied. The desired monomer was prepared from 5-vinyl-2-norbornene by its selective hydrogenation to 2-vinylnorbornane followed by Diels-Alder reaction with dicyclopentadiene. Metathesis polymer was prepared in the presence of the firs...

The synthesis and structure of 2,4,6,-tricyclobutyl-1,3,5-trioxane, C 15 H 24 O 31 , is described. It was formed in 39% yield during the work-up of the Swern oxidation of cyclobutylmethanol and may serve as a stable precursor of the cyclobutane carbaldehyde. The molecule of 1 occupies a special position (3. m ) located at the center of its 1,3,5-tr...

In the paper porous polymeric materials recently obtained from norbornene derivatives are presented. Up to now three groups of polynorbornenes exhibited the presence of micro-either mesopores and large surface area are considered. The first one is the group of Me3Si-containing addition polynorbornenes. These polymers are microporous and possess Bru...

Correction for ‘The selective hydrosilylation of norbornadiene-2,5 by monohydrosiloxanes’ by Marina A. Guseva et al. , RSC Adv. , 2019, 9 , 33029–33037.

A simple one-step approach for the selective synthesis of exo-norbornenes with organosilicon substituents is suggested through the direct hydrosilylation of norbornadiene-2,5 with chlorine-free silanes. Using the example of norbornadiene-2,5 hydrosilylation with pentamethyldisiloxane and 1,1,1,3,5,5,5-heptamethyltrisiloxane, the possibility of obta...

This article describes data on preparation of sulfonated hydrogenated poly(phenylnorbornene) with different cations synthesized via sequential ring-opening metathesis polymerization, reduction, homogeneous sulfonation and cation exchange reactions. The data of the characterization of new polymers by nuclear magnetic resonance (1H NMR) spectroscopy,...

Solid–state dissolution in N–methylmorpholine N–oxide was used to obtain solutions of mixtures derived from cellulose and various organosilicon additives, namely, tetraethoxysilane, vinyltriethoxysilane, and bis (trimethylsilyl)acetylene. Optical study of the phase composition and morphology of these solutions showed that they are two–phase emulsio...

A one-step selective method based on the hydrosilylation of 2,5-norbornadiene with commercially available silanes in the presence of a Pd-catalyst and bulky ligand R-MOP is developed for the synthesis of exo-isomers of silicon-containing norbornenes. This approach leads to the formation of exclusively exo-isomers. The absence of the steps of alkyla...

A simple two-stage scheme is proposed for the synthesis of a new porous polymeric material based on dicyclopentadiene, an industrial product and one of the most accessible derivatives of norbornene. The selective addition polymerization of dicyclopentadiene, a bifunctional monomer, proceeds via opening of only one endocyclic double bond and the sub...

Theoretical analysis was made on the composition and thermodynamic parameters of combustion products of 2,2'-bis(bicyclo[2.2.1]heptane) in oxygen in a wide range of temperatures and pressures. 2,2'-Bis(bicyclo[2.2.1]heptane) can potentially be used as a fuel component in combustion chambers of liquid rocket engines for the first-stage launch vehicl...

Nanoporous glassy polymers are perspective materials for the fabrication of gas separation membranes, especially for the application of gaseous hydrocarbon separation. However, the drawback of such materials is the pronounced physical aging resulting in the dramatic drop of gas transport properties due to relaxation of high‐free‐volume fraction in...

The nature of micropore size distribution in a number of amorphous polymer glasses (membrane materials and sorbents) has been discussed on the basis of data on positron annihilation lifetime spectroscopy (PALS) and low-temperature CO2 gas sorption (LTGS). The LTGS (CO2) technique in combination with mathematical processing by the density functional...

One-step and selective approach to the synthesis of Si-containing exo-norbornenes has been developed based on hydrosilylation reaction of norbornadiene-2,5 with unactivated silanes using Pd-complexes in the presence of bulky ligands. This approach leads to only exo-isomers of norbornene derivatives. The absence of alkylation step by organometallic...

Here, we report the synthesis and the study of gas‐transport properties of crosslinked highly permeable copolymers from Si‐containing norbornene derivatives. The initial high‐molecular‐weight copolymers were prepared via addition copolymerization of 3‐trimethylsilyltricyclo[4.2.1.02,5]non‐7‐ene (TCNSi1) with 3‐triethoxysilyltricyclo[4.2.1.02,5]non‐...

A one-step selective method for the synthesis of exo isomers of silicon-containing norbornenes by hydrosilylation of norbornadiene-2,5 with non-activated silanes in the presence of a Pd catalyst and bulky ligands has been developed. This approach leads to the formation of exo isomers only. The absence of stages of alkylation with organometallic rea...

Previously undescribed norbornene monomer 3,3,4-trifluoro-4-perfluorohexyltricyclononene-7 is synthesized by the [2+2+2] cycloaddition reaction. The monomer is involved in the ring-opening polymerization metathesis in the presence of the first-generation Grubbs catalyst to give rise to the amorphous, glassy unsaturated polymer. The gas-transport pr...

Two metathesis homopolymers with tri(n-propoxy)silyl and tri(n-butoxy)silyl side substituents are synthesized, and their adhesive properties are investigated. High-molecular-weight polymers are prepared in the presence of the first-generation Grubbs catalyst in a good yield. Adhesive properties are studied by the probe tack method at different temp...

Two‐stage [2π+2σ+2σ]‐cycloaddition of quadricyclane (2) with 2,3‐dicyano‐1,4‐benzoquinone (1) with a huge difference in the activity of two reaction centers has been studied. In the first stage (kinetic control), the cycloaddition of 2 takes place on the activated С2=С3 bond of 1 to form the monoadduct 3, and in the second stage the cycloaddition o...

Superglassy polymers with large fractional free volume emerge as novel materials with a broad range of applications, especially in the field of membrane separations. Highly permeable addition-type substituted polynorbornenes with high thermal resistance and chemical stability are among the most promising materials. The major obstacle for extending...