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The hydrodynamics and heat transfer in a reactor with a fluidized bed of catalyst particles and an inert material were simulated. The particle bed (the particle density was 2350 kg/m3, and the particle diameter was 1.5 to 4 mm) was located in a distribution device which was a grid of 90 × 90 × 60 mm vertical baffles. The behavior of the liquefying medium (air) was modeled using a realizable k-ε turbulence model. The behavior of particles was modeled using the discrete element method (DEM). In order to reduce the slugging effect, the particles were divided into four separate horizontal layers. It was determined that with the velocity of the liquefying medium close to the minimum fluidization velocity (1 m/s), slugging fluidization is observed. At a velocity of the liquefying medium of 3 m/s, turbulent fluidization in the lowest particle layer and bubbling fluidization on subsequent particle layers are observed. With an increase in the velocity of the liquefying medium over 3 m/s, entrainment of particles is observed. It was shown that a decrease in the density of the liquefying medium from 1.205 kg/m3 to 0.383 kg/m3 when it is heated from 298 K to 923 K would not significantly affect the hydraulic resistance of the bed. Based on the obtained results, it can be stated that the obtained model is optimal for such problems and is suitable for the further description of experimental data. [ABSTRACT FROM AUTHOR]

In this study, we report an easy approach for the production of aqueous dispersions of C60 fullerene with good stability. Maleic acid copolymers, poly(styrene-alt-maleic acid) (SM), poly(N-vinyl-2-pyrrolidone-alt-maleic acid) (VM) and poly(ethylene-alt-maleic acid) (EM) were used to stabilize C60 fullerene molecules in an aqueous environment by forming non-covalent complexes. Polymer conjugates were prepared by mixing a solution of fullerene in N-methylpyrrolidone (NMP) with an aqueous solution of the copolymer, followed by exhaustive dialysis against water. The molar ratios of maleic acid residues in the copolymer and C60 were 5/1 for SM and VM and 10/1 for EM. The volume ratio of NMP and water used was 1:1.2–1.6. Water-soluble complexes (composites) dried lyophilically retained solubility in NMP and water but were practically insoluble in non-polar solvents. The optical and physical properties of the preparations were characterized by UV-Vis spectroscopy, FTIR, DLS, TGA and XPS. The average diameter of the composites in water was 120–200 nm, and the ξ-potential ranged from −16 to −20 mV. The bactericidal properties of the obtained nanostructures were studied. Toxic reagents and time-consuming procedures were not used in the preparation of water-soluble C60 nanocomposites stabilized by the proposed copolymers. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

One-pot synthesis of colloidal Au/ZnO and Ag/ZnO nanohybrid structures was carried out. The copolymers of maleic acid—poly(N-vinyl-2-pyrrolidone-alt-maleic acid), poly(ethylene-alt-maleic acid), or poly(styrene-alt-maleic acid) were used as templates for the sorption of cations of metals-precursors and stabilization of the resulting nanoheterostructures. Simultaneous production of two types of nanoparticles has been implemented under mild conditions in an aqueous alkaline medium and without additional reagents. Equimolar ratios of the metal cations and appropriate load on all copolymers were used: molar ratio of maleic acid monomeric units of copolymer/gold (silver)cations/zinc cations was 1/0.15/0.23 (1/0.3/0.15). The process of obtaining the heterostructures was studied using UV-Vis spectroscopy. The kinetics of the formation of heterostructures was influenced by the nature of the maleic acid copolymer and noble metal cations used. A high reaction rate was observed in the case of using zinc and gold cations-precursors and a copolymer of maleic acid with N-vinylpyrrolidone as a stabilizer of nanoparticles. The structure of the synthesized polymer-stabilized heterostructures was studied using instrumental methods of analysis—XPS, FTIR, PXRD, and TEM. Under the conditions used, stable colloidal solutions of heterodimers were obtained, and such structure can be converted to a solid state and back without loss of properties. [ABSTRACT FROM AUTHOR]

The effect of the process temperature and the initial concentration of Mg, Ca, Sr, Ba, Zn, Cd, and Hg 2-ethylhexanoates as catalysts on the productivity and selectivity of the oxidation stage of cumene is studied in the technological chain for the production of polymer composites from cumene; "production of phenol by cumene method (stage 1 is cumene oxidation to cumene hydroperoxide, stage 2 is decomposition of cumene hydroperoxide into phenol and acetone) → production of precursors from phenol → production of polymers from precursors → production of composites from polymers". A criterion has been introduced that reflects the productivity of cumene oxidation at the moment of reaching the maximum concentration of cumene hydroperoxide, which takes into account the cumene conversion and selectivity achieved in this case in the shortest possible time using the selectivity comparable with the selectivity of a non-catalytic process. It has been shown that the achievement of the maximum value of this criterion, among all the considered catalysts, is ensured by Mg 2-ethylhexanoate at its relatively low initial concentration (1 mmol/L) under conditions of moderately-high process temperatures (393–413 K). [ABSTRACT FROM AUTHOR]

A study was made on the effect of Ca, Sr, and Ba chloride complexes with dibenzo-18-crown-6 ether as catalysts on the process criteria of the efficiency of industrial cumene oxidation using kinetic modeling. It is the first stage in the process chain of polymer composite production. The kinetic scheme of the process is made of classical reactions of the radical chain mechanism (reactions of initiation, chain propagation, and chain termination), molecular reactions, reactions of formation of intermediate adducts "component of the reaction mixture—catalyst" and their decomposition, as well as reactions that take into account the specifics of the catalyst used: (1) formation of planar catalyst complexes with various substances; (2) formation of acetophenone along the catalytic path; (3) hydration of the intermediate adduct "α-methylstyrene—catalyst" to the required alcohol. It is shown that the kinetic model fully reproduces the experimental time dependencies of the cumene hydroperoxide concentration in the cumene oxidation and cumene hydroperoxide decomposition. Using the kinetic model, computational experiments were carried out, as a result of which the following conclusions were made: (1) among the considered catalysts, the complex of Sr chloride with dibenzo-18-crown-6 ether should be recognized as the best, provided that it is used at temperatures of 393–413 K and an initial concentration < 2 mmol/L; (2) to ensure selectivity comparable to the selectivity of a non-catalytic process, it is necessary to conduct the catalytic process at a lowest possible initial concentration of any of the considered catalysts. [ABSTRACT FROM AUTHOR]

Application of nanocarriers for drug delivery brings numerous advantages, allowing both minimization of side effects common in systemic drug delivery and improvement in targeting, which has made it the focal point of nanoscience for a number of years. While most of the studies are focused on encapsulation of hydrophobic drugs, delivery of hydrophilic compounds is typically performed via covalent attachment, which often requires chemical modification of the drug and limits the release kinetics. In this paper, we report synthesis of biphilic copolymers of various compositions capable of self-assembly in water with the formation of nanoparticles and suitable for ionic binding of the common anticancer drug doxorubicin. The copolymers are synthesized by radical copolymerization of N-vinyl-2-pyrrolidone and acrylic acid using n-octadecyl-mercaptan as a chain transfer agent. With an increase of the carboxyl group's share in the chain, the role of the electrostatic stabilization factor of the nanoparticles increased as well as the ability of doxorubicin as an ion binder. A mathematical description of the kinetics of doxorubicin binding and release is given and thermodynamic functions for the equilibrium ionic binding of doxorubicin are calculated. [ABSTRACT FROM AUTHOR]

A method was developed for the conjugation of aminopropyl spacer-bearing carbohydrates with epoxy groups on the crown of nanoparticles consisting of a copolymer of N-vinyl-2-pyrrolidone and allyl glycidyl ether in basic buffer, opening prospects for the design of vectorized nanocomposite drug forms. A conjugate of the above copolymer and trisaccharide A, a synthetic blood group antigen, was synthesized. Meglumine was used to bind any unreacted epoxide groups of the allyl glycidyl fragment. One- and two-dimensional NMR spectroscopy showed quantitative opening of the epoxide ring as a result of carbohydrate immobilization. By integrating the characteristic signals in the 1H NMR spectrum, we determined the molar ratio of the immobilized vector and meglumine, as well as the composition and number-average molecular weight of the carrier copolymer. The results obtained point to the interesting possibilities in the further study of the polymer–carbohydrate ligand system as a platform for the development of several drug carriers and theranostics based on them. [ABSTRACT FROM AUTHOR]

This paper deals with the development of polymeric nanocarriers based on amphiphilic copolymers of N‐vinyl‐2‐pyrrolidone and acrylic acid of various molecular weights synthesized through the AIBN‐initiated radical copolymerization of N‐vinyl‐2‐pyrrolidone and acrylic acid in the presence of n‐octadecyl mercaptan. The structure of the copolymers is characterized by 1Н NMR, 13С NMR, IR and MALDI‐TOF MS spectroscopy. It is shown that the length of the hydrophilic block defines the size of the nanoaggregates while impacting the steric stabilization efficiency and the probability of the interchain hydrogen bond formation. The hydrogen bonds formation between the residues of N‐vinyl‐2‐pyrrolidone and acrylic acid is in agreement with the reduction of the ζ‐potential of the nanoaggregates and the critical aggregation concentrations upon increasing the molecular weight. The presence of acrylic acid residues in the amphiphilic macromolecules leads to a higher affinity for doxorubicin and slow partial release of doxorubicin bonded with the aggregates' corona, which is helpful for reducing its cardiac toxicity. Nanoaggregates with a paclitaxel‐loaded hydrophobic core are obtained, showing the possibility of dual loading. The amphiphilic copolymers of N‐vinyl‐2‐pyrrolidone and acrylic acid containing an n‐octadecyl thio end group are thus promising candidates for combination cancer therapy with immobilized anti‐cancer drugs, paclitaxel, and doxorubicin. [ABSTRACT FROM AUTHOR]

An epoxy‐containing copolymer was synthesized by radical copolymerization of N‐vinyl‐2‐pyrrolidone and allyl glycidyl ether. Further, the obtained copolymer was used to immobilize dopamine. It was found that immobilization of dopamine follows an equation of second general order and is accompanied by opening of the epoxy cycle. The synthesized dopamine‐containing copolymer was used to produce hydrogels that are formed during the treatment thereof with solutions of iron(III) chloride and sodium periodate. The gel formed upon treatment with iron(III) chloride was found to be pH sensitive. It was shown that the hydrogel obtained through oxidation with sodium periodate is capable of complete slow degradation in a saline phosphate buffer at pH 7.5. © 2020 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

The kinetic curves for oxidation of dopamine hydrochloride in aqueous solution in the presence of ammonium peroxydisulfate were obtained by UV–vis spectroscopy and potentiometry. It was shown that the reaction follows the first‐order kinetic equation and proceeds at a low rate. The values for the activation energy and the preexponential factor were determined as 75 kJ × mol−1 and 4 × 108 s−1, respectively. The activation entropy was found having a negative value of −89 J × mol−1 × K−1. The first reaction order, the low preexponential factor and the negative activation entropy value for the reaction between the 2‐(3,4‐dihydroxyphenyl)ethanammonium cation and the peroxydisulfate anion were explained by the formation of ionic associates, which slowly enter into the internal redox reaction. [ABSTRACT FROM AUTHOR]

The oligomer of acrylic acid with a thiooctadecyl end-group was obtained by using octadecyl mercaptan as the chain-transfer agent. The resulting oligomer was characterized by 1H NMR and 13C NMR spectroscopy and critical micelle concentration was determined in aqueous solution. The order with respect to the initiator concentration was 0.5 and 1.6 with respect to the monomer concentration. The abnormal reaction order with respect to the monomer concentration was explained by participation in the chain propagation of unassociated and associated forms of acrylic acid, which were stabilized by formation of hydrogen bonds. The kinetic parameters of telomerization were determined. Telomerization with acrylic acid in the non-associated form had lower activation energy and lower pre-exponential factor than in the case of associated forms. The synthesis of the acrylic acid oligomer with a thiooctadecyl end-group having a low critical micelle concentration in water was carried out in one stage and corresponds to the concept of atom economy. [ABSTRACT FROM AUTHOR]

Aim: Ability to deliver drugs into the cell nuclei can significantly increase the efficacy of cancer therapies, in particular in the case of multidrug-resistant cancer Results: Polymer nanocarriers based on amphiphilic thiooctadecyl-terminated poly-N-vinyl-2-pyrrolidone were produced and loaded with a model hydrophobic drug, curcumin. Two commonly used loading approaches - emulsification and ultrasonic dispersion - were found to lead to two different size distributions with distinctively different biological effect. While nanocarriers produced via the emulsion method penetrated cells by dynamin-dependent endocytic mechanisms, sub-100 nm dispersion-produced nanocarriers were capable of crossing the membranes via biologically independent mechanisms. Conclusion: This finding opens an intriguing possibility of intranuclear delivery by merely tailoring the size of polymeric carriers, thus promising a new approach for cancer therapies. [ABSTRACT FROM AUTHOR]

Global enhancement of crop yield is achieved using chemical fertilizers; however, agro-economy is affected due to poor nutrient uptake efficacy (NUE), which also causes environmental pollution. Encapsulating urea granules with hydrophobic material can be one solution. Additionally, the inverse vulcanized copolymer obtained from vegetable oils are a new class of green sulfur-enriched polymer with good biodegradation and better sulfur oxidation potential, but they possess unreacted sulfur, which leads to void generations. In this study, inverse vulcanization reaction conditions to minimize the amount of unreacted sulfur through response surface methodology (RSM) is optimized. The copolymer obtained was then characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). FTIR confirmed the formation of the copolymer, TGA demonstrated that copolymer is thermally stable up to 200 °C temperature, and DSC revealed the sulfur conversion of 82.2% (predicted conversion of 82.37%), which shows the goodness of the model developed to predict the sulfur conversion. To further maximize the sulfur conversion, 5 wt% diisopropenyl benzene (DIB) as a crosslinker is added during synthesis to produce terpolymer. The urea granule is then coated using terpolymer, and the nutrient release longevity of the coated urea is tested in distilled water, which revealed that only 65% of its total nutrient is released after 40 days of incubation. The soil burial of the terpolymer demonstrated its biodegradability, as 26% weight loss happens in 52 days of incubation. Thus, inverse vulcanized terpolymer as a coating material for urea demonstrated far better nutrient release longevity compared with other biopolymers with improved biodegradation; moreover, these copolymers also have potential to improve sulfur oxidation. [ABSTRACT FROM AUTHOR]

Development of nanocarrier-based drug delivery systems is a major breakthrough in pharmacology, promising targeted delivery and reduction in drug toxicity. On the cellular level, encapsulation of a drug substantially affects the endocytic processes due to nanocarrier–membrane interaction. In this study we synthesized and characterized nanocarriers assembled from amphiphilic oligomers of N-vinyl-2-pyrrolidone with a terminal thiooctadecyl group (PVP-OD). It was found that the dissolution free energy of PVP-OD depends linearly on the molecular mass of its hydrophilic part up to M ¯ n = 2 × 104, leading to an exponential dependence of critical aggregation concentration (CAC) on the molar mass. A model hydrophobic compound (DiI dye) was loaded into the nanocarriers and exhibited slow release into the aqueous phase on a scale of 18 h. Cellular uptake of the loaded nanocarriers and that of free DiI were compared in vitro using glioblastoma (U87) and fibroblast (CRL2429) cells. While the uptake of both DiI/PVP-OD nanocarriers and free DiI was inhibited by dynasore, indicating a dynamin-dependent endocytic pathway as a major mechanism, a decrease in the uptake rate of free DiI was observed in the presence of wortmannin. This suggests that while macropinocytosis plays a role in the uptake of low-molecular components, this pathway might be circumvented by incorporation of DiI into nanocarriers. [ABSTRACT FROM AUTHOR]

It was found that sulfanylethanoic and 3-sulfanylpropanoic acids are effective regulators of molecular weight with chain transfer constants of 0.441 and 0.317, respectively, and show an unexpected acceleration effect on the radical polymerization of N-vinyl-2-pyrrolidone, initiated by 2,2'-azobisisobutyronitrile. It was determined for the first time that the thiolate anions of mercapto acids form a high-temperature redox initiating system with 2,2'-azobisisobutyronitrile during the radical polymerization of N-vinyl-2-pyrrolidone in 1,4-dioxane. Considering the peculiarities of initiation, a kinetic model of the polymerization of N-vinyl-2-pyrrolidone is proposed, and it is shown that the theoretical orders of the reaction rate, with respect to the monomer, initiator, and chain transfer agent, are 1, 0.75, 0.25, and are close to their experimentally determined values. Carboxyl-containing techelics of N-vinyl-2-pyrrolidone were synthesized so that it can slow down the release of the anticancer drug, doxorubicin, from aqueous solutions, which can find its application in the pharmacological field. [ABSTRACT FROM AUTHOR]

The kinetic regularities of the initial stage of chemical oxidative polymerization of methylene blue under the action of ammonium peroxodisulfate in an aqueous medium have been established by the method of potentiometry. It was shown that the methylene blue polymerization mechanism includes the stages of chain initiation and growth. It was found that the rate of the initial stage of the reaction obeys the kinetic equation of the first order with the activation energy 49 kJ · mol−1. Based on the proposed mechanism of oxidative polymerization of methylene blue and the data of MALDI, EPR, and IR spectroscopy methods, the structure of the polymethylene blue chain is proposed. It has been shown that polymethylene blue has a metallic luster, and its electrical conductivity is probably the result of conjugation over extended chain sections and the formation of charge transfer complexes. It was found that polymethylene blue is resistant to heating up to a temperature of 440 K and then enters into exothermic transformations without significant weight loss. When the temperature rises above 480 K, polymethylene blue is subject to endothermic degradation and retains 75% of its mass up to 1000 K. [ABSTRACT FROM AUTHOR]

Microbubbles are routinely used ultrasound contrast agents in the clinic. While a soft protein shell is commercially preferable for imaging purposes, a rigid polymer shell demonstrates prolonged agent stability. Hence, combining polymers and proteins in one shell composition can advance microbubble properties. We formulated the hybrid "protein-copolymer" microbubble shell with a complex of bovine serum albumin and an amphiphilic copolymer of N -vinyl-2-pyrrolidone and acrylic acid. The resulting microbubbles demonstrated advanced physicochemical and acoustic properties, preserving in vitro biocompatibility. Adjusting the mass ratio between protein and copolymer allowed fine tuning of the microbubble properties of concentration (by two orders, up to 10 10 MBs/mL), mean size (from 0.8 to 5 μm), and shell thickness (from 28 to 50 nm). In addition, the minimum air-liquid surface tension for the "protein-copolymer" solution enabled the highest bubble concentration. At the same time, a higher copolymer amount in the bubble shell increased the bubble size and tuned duration and intensity of the contrast during an ultrasound procedure. Demonstrated results exemplify the potential of the hybrid "protein-polymer" microbubble shell, allowing tailoring of microbubble properties for image-guided applications, combining advances of each material involved in the formulation.