Co-delivery of chemotherapeutics in cancer treatment has been proven essential for overcoming multidrug resistance and improving the outcome of therapy. We report the synthesis of amphiphilic copolymers of N-vinyl-2-pyrrolidone and allyl glycidyl ether of various compositions and demonstrate that they can form nanoaggregates capable of simultaneous covalent immobilization of doxorubicin by the epoxy groups in the shell and hydrophobic-driven incorporation of paclitaxel into the core of nanoparticles. The structure of the obtained copolymers was characterized by ¹³C NMR, IR, and MALDI spectroscopy, as well as adsorption at the water/toluene interface. A linear increase in the number-average molecular weight of amphiphilic copolymers and a decrease in the number-average diameter of macromolecular aggregates with an increase in the ratio N-vinyl-2-pyrrolidone/allyl glycidyl ether were observed. The assembled nanocarriers were characterized by DLS. The reported novel nanocarriers can be of interest for delivery and co-delivery of a wide range of pharmacological preparations and combined therapy for cancer and other deceases.

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.

The combination of biocompatibility, biodegradability, and high mechanical strength has provided a steady growth in interest in the synthesis and application of lactic acid-based polyesters for the creation of implants. On the other hand, the hydrophobicity of polylactide limits the possibilities of its use in biomedical fields. The ring-opening polymerization of L-lactide, catalyzed by tin (II) 2-ethylhexanoate in the presence of 2,2-bis(hydroxymethyl)propionic acid, and an ester of polyethylene glycol monomethyl ester and 2,2-bis(hydroxymethyl)propionic acid accompanied by the introduction of a pool of hydrophilic groups, that reduce the contact angle, were considered. The structures of the synthesized amphiphilic branched pegylated copolylactides were characterized by ¹H NMR spectroscopy and gel permeation chromatography. The resulting amphiphilic copolylactides, with a narrow MWD (1.14–1.22) and molecular weight of 5000–13,000, were used to prepare interpolymer mixtures with PLLA. Already, with the introduction of 10 wt% branched pegylated copolylactides, PLLA-based films had reduced brittleness, hydrophilicity, with a water contact angle of 71.9–88.5°, and increased water absorption. An additional decrease in the water contact angle, of 66.1°, was achieved by filling the mixed polylactide films with 20 wt% hydroxyapatite, which also led to a moderate decrease in strength and ultimate tensile elongation. At the same time, the PLLA modification did not have a significant effect on the melting point and the glass transition temperature; however, the filling with hydroxyapatite increased the thermal stability.

The effects of the molecular architecture of water-insoluble organosilicon polymerizable surfactant macromers (SAMs) on their colloidal-chemical characteristics and on their efficiency in heterophase radical polymerization of styrene and methyl methacrylate were studied. It was shown that despite considerable differences in the structure of three synthesized oligomers (linear α,ω-dipropylmethacrylatepolydimethylsiloxane with a number of repeated siloxane units n = 20—l-SAM; branched γ-methacryloxypropyl containing dimethylsiloxane oligomer—b-SAM; and “spherical” oligo-(γ-methacryloxypropyl)silsesquioxane—s-SAM), the colloidal-chemical characteristics (interfacial tension, layer thickness, adsorption, etc.) were rather similar. In particular, they all form “thick” multimolecular adsorption layers on the toluene–water interphase. All three SAMs were shown to act as effective colloidal stabilizers in heterophase radical polymerization of styrene and methyl methacrylate, which resulted in one-step preparation of large (0.5–1.5 µm) polymer particles with narrow particle size distribution. The obtained results are consistent with the published data on the use of water-insoluble polymerizable oligomers of various chemical structures on the heterophase radical polymerization. The use of these colloidal stabilizers may be considered as an effective way to obtain stable suspensions with large particles and narrow particle size distribution.

The article presents data on the study of the polymerization temperature effect on the properties of polymer suspensions (particle diameter, particle size distribution and aggregate stability) obtained in the presence of water-insoluble organosilicon surfactants. The effect of temperature was studied during heterophase polymerization of styrene and methyl methacrylate in the presence of organosilicon surfactants of various structures with terminal amino and glycidoxy groups (alpha, omega-bis (trimethylsiloxy-oligodimethylmethyl (3-aminopropyl) siloxane (PMADMS(1)) and alpha, omega-bis [3-glycidoxypropyll poly-dimethylsiloxane (PDMS (CHOCH2)). Polymerization was carried out in different temperature conditions. The dependence of the polymerization rate and particle diameter on the synthesis temperature was revealed. With increasing temperature, the rate increases, and the particle diameter decreases (from 1.1 mu m to 0.4 mu m). It was shown that the activation energy of styrene polymerization in the presence of organosilicon surfactants of various structures is 25.4 and 33.4 J/mol, which is close to the values usually observed during radical heterophase polymerization. A decrease in the polymerization temperature leads to an increase in the induction period on the conversion/time kinetic curves. A detailed study of the initial stage of polymerization of methyl methacrylate at different temperatures showed that the particle diameter is determined at the initial stage of polymerization and depends significantly on the temperature of the process. In the case of the synthesis of polymer suspensions at a constant temperature throughout the entire polymerization process, the temperature value does not significantly affect the aggregate stability of the obtained polymer particles. In this case, the aggregate stability of polymer suspensions is influenced by the rate of an interfacial adsorption layer formation from molecules of an organosilicon surfactant and polymer, which is formed at the initial stage of the polymerization process.

Полимерные микросферы с глицидокси-группами на поверхности могут быть использованы в качестве носителей биолигандов в диагностических тест-системах. Однако возможность синтеза агрегативно устойчивых функциональных полимерных микросфер в широком диапазоне диаметров является актуальной проблемой современной полимерной химии. Данная статья посвящена систематическим исследованиям кинетических закономерностей полимеризации стирола и метилметакрилата в присутствии кремнийорганического ПАВ с концевыми глицидокси-группами – α,ω бис[3 глицидоксипроопил]-полидиметилсилоксана, ПДМС(СНОСН₂). В статье показано влияние объемного соотношения фаз, концентрации инициатора, ПАВ, температуры синтеза и рН исходной среды на свойства полимерных суспензий (их агрегативную устойчивость, монодисперсность, диаметр частиц). Исследовано формирование полимерно-мономерных частиц в процессе полимеризации и показано, что полимерные суспензии сохраняют высокую агрегативную устойчивость с ранних конверсий мономера, а диаметр частиц изменяется до 30% конверсии мономера. Благодаря высокой поверхностной активности используемого кремнийорганического ПАВ и его несовместимости с образующимся полимером, одностадийным синтезом были получены агрегативно устойчивые функциональные полимерные суспензии с диаметрами от 0,09 до 1,1 мкм. Исследования степени гидратации полимерных микросфер показали, что наличие на их поверхности функциональных глицидокси-групп обеспечивает образование гидратной оболочки, которая увеличивает стабильность полимерных частиц, а также позволяет использовать полученные микросферы в качестве носителей биолигандов. Таким образом, использование нерастворимых в воде кремнийорганических ПАВ в качестве стабилизаторов гетерофазной полимеризации виниловых мономеров позволяет синтезировать агрегативно устойчивые функциональные полимерные суспензии в широком интервале диаметров. Использование кремнийорганических ПАВ с различными функциональными группами расширяет ассортимент функциональных полимерных микросфер, используемых в различных областях деятельности. Для цитирования: Грицкова И.А., Ежова А.А., Гусев С.А., Лобанова Н.А., Чвалун С.Н. Синтез и свойства полимерных суспензий, полученных гетерофазной полимеризацией в присутствии α,ω–бис[3-глицидоксипропил]-полидиметилсилоксана. Изв. вузов. Химия и хим. технология. 2023. Т. 66. Вып. 4. С. 43-51. DOI: 10.6060/ivkkt.20236604.6741.