The main task of the research is to acquire fundamental knowledge about the effect of polymer structure on the physicochemical properties of films. A novel meta-material that can be used in manufacturing sensor layers was developed as a model. At the first stage, poly(sodium 4-styrenesulfonate) (PNaSS) cross-linked microspheres are synthesized (which are based on strong polyelectrolytes containing sulfo groups in each monomer unit), and at the second stage, PNaSS@PEDOT microspheres are formed. The poly(3,4-ethylenedioxythiophene) (PEDOT) shell was obtained by the acid-assisted self-polymerization of the monomer; this process is biologically safe and thus suitable for biomedical applications. The suitability of electrochemical impedance spectroscopy for E. coli detection was tested; it was revealed that the attached bacterial wall was destroyed upon application of constant oxidation potential (higher than 0.5 V), which makes the PNaSS@PEDOT microsphere particles promising materials for the development of antifouling coatings. Furthermore, under open-circuit conditions, the walls of E. coli bacteria were not destroyed, which opens up the possibility of employing such meta-materials as sensor films. Scanning electron microscopy, X-ray photoelectron spectroscopy, water contact angle, and wide-angle X-ray diffraction methods were applied in order to characterize the PNaSS@PEDOT films.
Polymeric hydrogels based on sulfo-containing comonomers are promising materials for biotechnological application, namely, for use as a system for delivering water and minerals during seed germination in conditions of an unstable moisture zone. In this work, cryogels based on 3-sulfopropyl methacrylate and 2-hydroxyethyl methacrylate copolymers were obtained by the cryotropic gelation method. The morphology, specific surface area, and swelling behaviors of cryogels are found to depend on the total concentration of monomers in the reaction system and the content of the gel fraction in cryogels. Cryogels formed in the presence of nanodiamonds are shown to exhibit high biological activity during the germination of Lepidium sativum L. variety Ajur seeds, which manifests itself by stimulating seed germination and a significant increase in the raw weight of sprouts. These results indicate that sulfonic cryogels have a high potential to improve seed germination and plant growth, proving that such cryogels can be used as environmentally friendly materials for agricultural applications.
Conductive hydrogels are polymeric materials that are promising for bioelectronic applications. In the present study, a complex based on sulfonic cryogels and poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated as an example of a conductive hydrogel. Preparation of polyacrylate cryogels of various morphologies was carried out by cryotropic gelation of 3-sulfopropyl methacrylate and sulfobetaine methacrylate in the presence of functional comonomers (2-hydroxyethyl methacrylate and vinyl acetate). Polymerization of 3,4-ethylenedioxythiophene in the presence of several of the above cryogels occurred throughout the entire volume of each polyelectrolyte cryogel because of its porous structure. Structural features of cryogel@PEDOT complexes in relation to their electrochemical properties were investigated. It was shown that poly(3,4-ethylenedioxythiophene) of a linear conformation was formed in the presence of a cryogel based on sulfobetaine methacrylate, while minimum values of charge-transfer resistance were observed in those complexes, and electrochemical properties of the complexes did not depend on diffusion processes.
This work is devoted to the description of the synthesis of hydrogels in the process of cryotropic gel formation based on copolymerization of synthesized potassium 3-sulfopropyl methacrylate and 2-hydroxyethyl methacrylate (SPMA-co-HEMA) and assessing the potential possibility of their use as substrates for growing plants in intensive light culture in a greenhouse. Gel substrates based on the SPMA-co-HEMA were created in two compositions, differing from each other in the presence of macro- and microelements, and their effects were studied on the plants’ physiological state (content of chlorophylls a and b, activity of catalase and peroxidase enzymes, intensity of lipid peroxidation, elemental compositions) at the vegetative period of their development and on the plants’ growth, productivity and quality of plant production at the final stages of development. Experiments were carried out under controlled microclimate conditions. Modern and standard generally accepted methods of gels were employed (ATR-FTIR and 13C NMR spectral studies, scanning electron microscopy, measurement of specific surface area and pore volume), as well as the methods of the physiological and chemical analysis of plants. The study demonstrated the swelling ability of the created gel substrates. Hydrogels’ structure, their specific surface area, porosity, and pore volume were investigated. Using the example of representatives of leaf, fruit and root vegetable crops, the high biological activity of gel substrates was revealed throughout the vegetation period. Species specificity in the reaction of plants to the presence of gel substrates in the root-inhabited environment was revealed. Lettuce, tomato and cucumber plants were more responsive to the effect of the gel substrate, and radish plants were less responsive. At the same time, more pronounced positive changes in plant growth, quality and productivity were observed in cucumber and lettuce in the variant of gel substrates with macro- and microelements and in tomato plants in both variants of gel substrates. Further research into the mechanisms of the influence of gel substrates on plants, as well as the synthesis of new gel substrates with more pronounced properties to sorb and retain moisture is promising.
Crosslinked cationic particles 200–600 nm in diameter have been synthesized via emulsifier-free copolymerization of methyl methacrylate and 2-aminoethyl methacrylate hydrochloride in the presence of cross-linking agents (N,N'-methylenebisacrylamide, triethylene glycol dimethacrylate, and diethylene glycol dimethacrylate). It has been shown that polymer particles with a maximum concentration of surface functional groups (1.42 µmol/m2) and a stable structure of a surface layer are formed only in the presence of ethanol (20 vol %). The synthesized particles efficiently adsorb biologically active substances, and their dispersions are stable against aggregation in buffer solutions at pH 7.0.
In this work, we investigated the influence of the synthetic conditions of core/shell particles on physico–chemical properties of their shells, the process of self-assembly of particles into 3D-ordered structures, and the sensitivity of films based on these particles to the presence of ethanol and temperature changes. The core/shell particles were prepared by two methods: seed emulsion copolymerization and semi-batch emulsion copolymerization. The cores consisted of polystyrene or its copolymer with methyl methacrylate. Polymer shells of the particles were obtained by copolymerization of methyl methacrylate with several acrylate comonomers: butyl acrylate, butyl methacrylate, propyl acrylate, and ethyl acrylate. The photonic crystal films with the highest sensitivity to ethanol vapors were obtained on the basis of the core/shell particles synthesized by semi-batch emulsion polymerization. It was also established that introducing butyl acrylate or propyl acrylate units into shell copolymers led to an increase in the sensitivity of the resulting photonic crystal films. The films demonstrated a pronounced thermosensitivity only when the corresponding core/shell particles were synthesized as follows: the shell comonomers (methyl methacrylate and butyl acrylate) were introduced into the reaction system during the semi-batch emulsion process in a single step. The intensity of the photonic band gap (PBG) peak for these films decreased by 100% at around 42 °C.