The interaction of commercial polyethyleneglycol monomethyl ethers of various molecular weights and ethyl-2-cyanoacrylate yields adducts that, under the action of nucleophiles, release ethyl 2-cyanoacrylate, which immediately polymerizes by an anionic mechanism. This leads to the formation of a series of amphiphilic block copolymers with different lengths of the hydrophilic and hydrophobic blocks. The synthesized amphiphilic block copolymers were characterized by MALDI-TOF, XPS, TEM, 1H NMR, and IR spectroscopy, as well as gel permeation chromatography. The possibility of micelle-like aggregates formation in aqueous media as a result of self-assembly of amphiphilic copolymers of poly(ethyleneglycol)-block-poly(ethyl-2-cyanoacrylate) with number-average and intensity-averaged diameters of 115-140 nm and 190-240 nm, respectively, which vary relatively little with a change in the length of the hydrophilic and hydrophobic blocks, is shown. It was found that nanoparticles formed on the basis of poly(ethyleneglycol)-block-poly(ethyl-2-cyanoacrylate) do not exert a noticeable cytotoxic effect up to a concentration of 0.55 mg mL-1 in vitro experiments on the MCF-7 cell line and exhibit pronounced antitumor activity after loading with doxorubicin. Nanoparticles based on amphiphilic PEGylated poly(ethyl-2-cyanoacrylate) are technologically advanced and easy to obtain and have a suitable size and low cytotoxicity, which makes them promising candidates as carriers of antitumor drugs.
The development of new methods for obtaining nitrogen-containing sorbents to bind carbon dioxide is an important task to combat climate change, minimize a carbon trace and obtain industrially valuable products in heterogeneous catalytic processes. In this regard, the effect of the temperature of pyrolysis of polyphenylenepyridines on the chemical composition and sorption. The X-ray photoelectron spectroscopy (XPS) method was used to demonstrate the formation of nitrogen-containing products of high-temperature (800 - 1000 degrees C) carbonization of polyphenylenepyridines and polybiphenylenepyridines containing surface hydroxyl, ether, and carboxyl functional groups. According to the study of carbon dioxide adsorption-desorption isotherms, the new materials have a specific surface area of about 1000 m(2)g(-1) and a micropore diameter of up to 0.48 nm (Non-Local Density Functional Theory (NLDFT)). The resulting carbon materials had a high adsorption capacity for carbon dioxide, as well as the ability to cooperatively desorb it in accordance with the second-order kinetic equation. It was shown that the rate of carbon dioxide desorption decreased with increasing pyrolysis temperature used to form nitrogen-containing carbon material. Simultaneously with increasing pyrolysis temperature, a decrease in the mass fraction of nitrogen in the samples was observed with an increase in the adsorption capacity of the formed adsorbents with respect to carbon dioxide. Thus, the increase in the specific surface had a greater effect on the amount of carbon dioxide adsorption than the N/C value ratio did.
On the basis ofp-diacetylbenzene and 4,4'-diacetylbi phenyl, polyphenylenepyridines with a ratio of pyridine to phenylene rings of 1 : 5-6.5 were synthesized. Their heating in argon at 450, 800 and 1000 degrees C afforded porous polymers with a specific surface area up to 1146 m2 g-1. X-ray photoelectron spectroscopy of these substances showed that nitrogen atoms in them exist mainly in the form of graphite-and pyridine-like systems. Intensity (arbitrary units) 2 1 0 406 404 402 400 398 396 Binding energy/eV N N N N
Nitrogen-containing polyphenylene type polymers containing pyridine rings were synthesized. The polymer-forming reaction is based on the interaction of diacetylarylene and triethylorthoformate with the formation of a pyrylium salt and subsequent treatment of the intermediate product with ammonia. The optimal ratios of the reagents for the formation of the pyridine fragment were determined. The mechanism of the main reaction is discussed. The formation of the pyridine ring and phentriyl (1,3,5-triphenylsubstituted benzene) fragments was confirmed using 1H NMR data of the example of model reactions. After heating at a temperature of 450 °C, when a more complete polycondensation process occurs, the polymers reach high values of thermal characteristics—10% weight loss in an inert atmosphere corresponds to 600 °C. The structure of the synthesized polymers was confirmed using elemental analysis, IR, XPS, and EPR spectroscopy. The conjugation length in cross-linked polyphenylene pyridines can be controlled by varying the arylene bridge groups between the phentriyl fragments, which opens up opportunities for the development of new composite materials for electrical applications.
(E)-2-Сyano-5-phenylpent-2-en-4-ynoic acid esters and N-substituted amides were synthesized by the Knoevenagel condensation of 3-phenylpropiolaldehyde with the corresponding cyanoacetates or cyanoacetamides in the presence of basic alumina used as a catalyst. The IR and Raman spectra of the resulting compounds show strong absorption bands in the range of 1565–1580 cm–1 which are attributed to the vibrations of the C=C bond in the enyl moiety.
Using the condensation of acetophenone under the action of triethyl orthoformate as an example, the effect of ratios of solvents (CH(OEt) 3 and toluene) and the starting re-actants on the composition and yields of aromatic products was studied. After treatment of reaction mixtures with ammonia, 1,3,5-triphenylbenzene, m -terphenyl, and 2,6-diphen-ylpyridine were isolated.
Cationic copolymers based on 2-(N,N-dimethylamino)ethyl methacrylate and polyethylene glycol monomethyl ether (pDMAEMA-co-PEO) with different molecular weights have been synthesized. Their physicochemical properties were studied by NMR spectroscopy, sedimentation, and potentiometric titration. According to the data of potentiometric titration for the synthesized pegylated cationic copolymers, the apparent dissociation constants were determined in the pH range from 4.5 to 8.5. The physicochemical properties of interpolyelectrolyte complexes of these polycations with circular DNA (IPEC DNA) were also studied by dynamic light scattering, electrophoretic mobility, and TEM methods. It has been established that the diameter and electrokinetic potential (ζ-potential) of interpolyelectrolyte complexes can be varied over a wide range (from 200 nm to 1.5 μm and from −25 mV to +30 mV) by changing the ratio of oppositely charged ionizable groups in pegylated cationic copolymers and DNA, as well as by regulating medium pH. The resistance of the IPEC DNA/polycation complex to the action of nucleases was studied by electrophoresis in agarose gel; the cytotoxic effect of the polymers in vitro, and the efficiency of penetration (transfection) of IPEC DNA with PDMAEMA-co-PEO-polycations into eukaryotic cells of a cell line derived from human embryonic kidneys HEK 293 in vitro.
A network porous polyphenylene and fullerene-containing branched oligophenylenes have been synthesized to produce the polyphenylenes impregnated with the fullerene-containing compounds for CO2 adsorption. The resulting compounds were studied by IR spectroscopy and X-ray photoelectron spectroscopy (XPS). The analysis of the specific surface area was performed using the Brunauer–Emmett–Teller (BET) theory. The samples were tested tested for the efficiency of carbon dioxide adsorption. The most effective carbon dioxide adsorbent is found to be the polyphenylene impregnated with a triphenylamine-containing fullerene derivative.
Ethyl 3-alkoxy-2-cyanopropanoates were prepared by the reaction of ethyl 2-cyanoacrylate with the corresponding linear alkanols C6–C12 in acidic medium. Their treatment with water as a weak nucleophile resulted in elimination of the alkanol and the formation of oligocyanoacrylate terminated with the alkoxy group. The oligomers were studied by NMR spectroscopy, IR spectroscopy, MALDI-TOF mass-spectrometry and dynamic light scattering.
Three-dimensional polymers are synthesized by polycondensation of triacetylarenes with the formation of 1,3,5-phentriyl and dimeric diphenylpropenone fragments. Microporous polyphenylenes with an intrinsic surface area of 650-690 m2 g-1 were obtained by additional heating at 450 degrees C. The values of the intrinsic surface area of polyphenylenes with rigid-chain rod-shaped inter-nodal fragments significantly exceed those of polyphenylenes with a flexible-chain inter-nodal fragments.
Compound based on star-shaped oligophenylene and modified with l-valine fullerene C60 has been synthesized and characterized. For characterization, X-ray photoelectron spectroscopy was used.
Polycondensation of rigid-chain di- and triacetylarenes and their copolycondensation has afforded three-dimensional polymers via the formation of 1,3,5-phentriyl and dipnone moieties. The influence of the monomers structure on the polymers properties has been analyzed. Additional thermal treatment at 450оC has afforded microporous polyphenylenes with phentriyl branching fragments exhibiting intrinsic surface area of 650–690 m2/g.
A second generation phenylene dendrimer, viz. 1,3,5-tris[4-(3,5-diphenylphenyl)phenyl]benzene, was synthesized by cyclocondensation of 4-acetyl-3′,5′-diphenyl(biphenyl). This compound on heating to 600°C is transformed into substance possessing extremely heat-stable secondary structure. It retains the aromatic structure at this temperature and when heated to 1000°C is converted into material with graphite-like structure.
Homocondensation of 1,3-di(5-acenaphthenyl)but-2-en-1-one obtained by dimerization of 5-acetylacenaphthene leads to 1,3,5-tri(5-acenaphthenyl)benzene. No alternative product, 1,3,5,7-tetra(5-acenaphthenyl)cyclooctatetraene, was formed.
Microporous three-dimensional polyphenylenes with phentriyl branching moieties are synthesized by the trimerization polycyclocondensation of p-diacetylbenzene followed by additional heat treatment at 450°C. The structure of the polymers is studied by IR spectroscopy and the methods of thermal desorption of argon and low-temperature sorption of nitrogen. The volume of micropores amounts to more than 70% of the total pore volume. Calculations of the parameters of the microporous structure using the Dubinin–Radushkevich and Dubinin–Astakhov methods show that the average micropore size in the test sample is 1 nm. The surface of all pores, as calculated by various methods, is in the range from 470 to 980 m2/g. According to the TGA data, the polymer shows high heat resistance: when heated in an inert medium, its mass losses does not exceed 20% in the range of 200–900°C.
A series of porous polyphenylenes has been synthesized from diacetyl aromatic compounds via two step trimerization–cyclocondensation. The monomer structure influences the value of the polymer porosity. The polyphenylene networks have BET surface up to 760 m2 g−1
A model compound, as well as linear and cross-linked polymers polyazomethine and polyphenylene, were synthesized based on 1,2-bis(4-acetylbenzyl)-o-carborane. The thermal stability of polymers was investigated. The structure of polymers was studied by X-ray photoelectron spectroscopy (XPS).
Two branched oligophenylenethynylenes with phenylene or biphenylene moieties as inter-nodal fragments are synthesized by the Sonogashira reaction for optoelectronic applications. The branching of polyphenylenethynylenes influences the electro-optical properties, but cannot be precisely controlled, while its determination is often hardly addressed. The optical investigation, supported by nuclear magnetic resonance (NMR) studies, of oligophenylenethynylenes and the properly synthesized model compounds is performed to get insights on the branching and related effect on the material performance. The proposed branched oligophenylenethynylenes are good ultraviolet emitters in solution, while in solid-state aggregation phenomena strongly affect emission properties. However, the interactions between pi-electrons on phenylene and ethynylene of neighboring molecules in films enhance intermolecular charge transport (hole mobility = 3.2 x 10(-3) cm(2) V(-1)s(-1)) making them optimal candidates as hole transport materials in optoelectronic devices. The insertion of the oligophenylenethynylene film as a hole transporting layer in multilayered solution processes blue, green, and red electroluminescent diodes, enhances OLEDs electro-optical properties.
A series of branched oligophenylenes containing the dioctylfluorene and octylphenothiazine moieties was synthesized using the Suzuki reaction applied within the framework of the A(2) + B-2 + B-3 approach. 1,3,5-tris(7-Bromo-9,9-di-n-octylfluoren-2-yl)benzene and 1,3,5-tris- (4-bromophenyl)benzene were used as the branching co-monomers. It was shown that the fluorescence spectra of co-oligomers containing phenothiazine moieties are shifted to the longwavelength region as compared to the spectra of that without such moieties.