ABSTRACT
The thermo- and pH-responsive polymer brushes based on methoxy[oligo(propyleneglycol)8-block-oligo(ethyleneglycol)8]methacrylate with different concentrations of N-[3-(dimethylamino)propyl]methacrylamide (from 0% to 20%) were synthesized via RAFT polymerization. The "grafting-through" approach was used to prepare the low-molar-mass dispersion samples (Mw/Mn ≈ 1.3). Molar masses and hydrodynamic characteristics were obtained using static and dynamic light scattering and viscometry. The solvents used were acetonitrile, DMFA, and water. The molar masses of the prepared samples ranged from 40,000 to 60,000 g·mol-1. The macromolecules of these polymer brushes were modeled using a prolate revolution ellipsoid or a cylinder with spherical ends. In water, micelle-like aggregates were formed. Critical micelle concentrations decreased with the content of N-[3-(dimethylamino)propyl]methacrylamide. Molecular brushes demonstrated thermo- and pH-responsiveness in water-salt solutions. It was shown that at a given molecular mass and at close pH values, the increase in the number of N-[3-(dimethylamino)propyl]methacrylamide units led to an increase in phase separation temperatures.
ABSTRACT
Herein, a series of ternary amphiphilic amide-containing bottlebrushes were synthesized by photoiniferter (PI-RAFT) polymerization of macromonomers in continuous-flow mode using trithiocarbonate as a chain transfer agent. Visible light-mediated polymerization of macromonomers under mild conditions enabled the preparation of thermoresponsive copolymers with low dispersity and high yields in a very short time, which is not typical for the classical reversible addition-fragmentation chain transfer process. Methoxy oligo(ethylene glycol) methacrylate and alkoxy(C12-C14) oligo(ethylene glycol) methacrylate were used as the basic monomers providing amphiphilic and thermoresponsive properties. The study investigated how modifying comonomers, acrylamide (AAm), methacrylamide (MAAm), and N-methylacrylamide (-MeAAm) affect the features of bottlebrush micelle formation, their critical micelle concentration, and loading capacity for pyrene, a hydrophobic drug model. The results showed that the process is scalable and can produce tens of grams of pure copolymer per day. The unmodified copolymer formed unimolecular micelles at temperatures below the LCST in aqueous solutions, as revealed by DLS and SLS data. The incorporation of AAm, MAAm, and N-MeAAm units resulted in an increase in micelle aggregation numbers. The resulting bottlebrushes formed uni- or bimolecular micelles at extremely low concentrations. These micelles possess a high capacity for loading pyrene, making them a promising choice for targeted drug delivery.
ABSTRACT
The properties of polymer brushes based on three macromonomers were investigated in aqueous and organic solutions. Methacrylic monomers with different compositions of the oligo(oxyalkylene) substituents and arrangements of the oligo(ethylene glycol) and oligo(propylene glycol) blocks were used for the synthesis of polymers. There were methoxy [oligo(ethylene glycol)10.3-block-oligo(propylene glycol)4.7] methacrylate, methoxy [oligo(propylene glycol)8.3-block-oligo(ethylene glycol)6.6] methacrylate, and methoxy oligo(propylene glycol)4.2 methacrylate. Molecular brushes were investigated by the methods of molecular hydrodynamics and optics in dilute solutions in acetonitrile, chloroform, and water. The peculiarities of behavior of poly[oligo(oxyalkylene) methacrylates] in aqueous solutions and water-toluene systems have been found; in particular, the solubility of the polymers in water and organic solvents, the polymers equilibrium distribution between the phases, and the surface activity in the water-toluene system have been established. The thermo-responsibility in aqueous solutions and values of a critical concentration of micelle formation were shown. Depending on the arrangement of blocks in the side chains of molecular brushes, they are characterized by different intramolecular density.
ABSTRACT
The synthesis of two new copolymer conjugates of methoxyoligo(ethylene glycol)methacrylate MPEGMA and betulin methacrylate BM was developed via RAFT polymerization. The molar content of BM units was equal to 9-10 and 13-16 mol%, respectively (HPLC, 1H and 13C NMR); molar weights were equal to 75000-115000. CeO2 NPs as a component of the hybrid material were synthesized for the preparation of the composition with copolymer conjugates of MPEGMA and BM. We showed a significant increase in G6PDH and GR activities by 21-51% and 9-132%, respectively, which was due to the increase in NADPH concentration under the action of copolymers in vitro. The actions of copolymers and CeO2 NPs combination were stronger than those of the individual components: the SOD activity increased by more than 30%, the catalase activity increased dose-dependently from 13 to 45%, and the GR activity increased to 49%. The maximum increase in enzyme activity was observed for the G6PDH from 54% to 151%. The MDA level dose-dependently increased by 3-15% under the action of copolymers compared with the control, and dose-dependently decreased by 3-12% in samples containing CeO2 NPs only. CeO2 NP-copolymer compositions can be used for the design of new biomimetic medical products with controlled antioxidant properties.
Subject(s)
Cerium , Nanoparticles , Antioxidants/pharmacology , Catalase , Cerium/chemistry , Cerium/pharmacology , Ethylene Glycol , Methacrylates/chemistry , NADP , Nanoparticles/chemistry , Polymers/chemistry , Superoxide Dismutase , TriterpenesABSTRACT
Thermo- and pH-responsive poly(N-[3-(diethylamino)propyl]methacrylamide)s were synthesized by free radical polymerization and RAFT polymerization. The molar masses of the samples were 33,000-35,000 gâmol-1. Investigations of the dilute solutions showed that the prepared samples were flexible chain polymers. The behavior of the synthesized polymers in the buffer solutions was analyzed by turbidity and light scattering at a pH range of 7-13 and a concentration range of 0.0002-0.008 g·cm-3. When the concentrated solutions were at a low temperature, there were macromolecules and aggregates, which were formed due to the interaction of hydrophobic units. For the investigated samples, the lower critical solution temperatures were equal. The phase separation temperatures decreased as pH increased. The influence of polydispersity index on the characteristics of the samples in the solutions was analyzed. The radii of molecules of poly(N-[3-(diethylamino)propyl]methacrylamide) obtained by RAFT polymerization at this temperature at the onset and end of the phase separation interval were lower than ones for samples synthesized by conventional free radical polymerization.
ABSTRACT
Polymethacrylic molecular brushes with oligo(ethylene glycol)-block-oligo(propylene glycol) side chains were investigated by static and dynamic light scattering and viscometry. The solvents used were acetonitrile, tetrahydrofuran, chloroform, and water. The grafted copolymers were molecularly dispersed and dissolved in tetrahydrofuran and acetonitrile. In these solvents, the molar masses of copolymers were determined. In thermodynamically good solvents, namely tetrahydrofuran and acetonitrile, investigated copolymers have a high intramolecular density and the shape of their molecules resembles a star-shaped macromolecule. In chloroform and water, the micelle-like aggregates were formed. Critical micelle concentrations decreased with the lengthening of the hydrophobic block. Molecular brushes demonstrated thermosensitive behavior in aqueous solutions. The phase separation temperatures reduced with an increase in the content of the oligo(propylene glycol) block.
ABSTRACT
Amphiphilic random and diblock thermoresponsive oligo(ethylene glycol)-based (co)polymers were synthesized via photoiniferter polymerization under visible light using trithiocarbonate as a chain transfer agent. The effect of solvent, light intensity and wavelength on the rate of the process was investigated. It was shown that blue and green LED light could initiate RAFT polymerization of macromonomers without an exogenous initiator at room temperature, giving bottlebrush polymers with low dispersity at sufficiently high conversions achieved in 1-2 h. The pseudo-living mechanism of polymerization and high chain-end fidelity were confirmed by successful chain extension. Thermoresponsive properties of the copolymers in aqueous solutions were studied via turbidimetry and laser light scattering. Random copolymers of methoxy- and alkoxy oligo(ethylene glycol) methacrylates of a specified length formed unimolecular micelles in water with a hydrophobic core consisting of a polymer backbone and alkyl groups and a hydrophilic oligo(ethylene glycol) shell. In contrast, the diblock copolymer formed huge multimolecular micelles.
ABSTRACT
Concentration effects in the base-catalyzed hydrolysis of water-soluble methacrylates (3-(N,N-dimethylaminoethyl) methacrylate (DMAEMA), 2-hydroxyethyl methacrylate (HEMA) and oligo(ethylene glycol) methacrylates (OEGMAs)) have been studied. These monomers are rapidly hydrolyzed in the presence of bases at the room temperature in dilute aqueous solutions, but the reaction rate decreases sharply in highly concentrated solutions. A clear correlation was found between a form of the viscosity isotherm for DMAEMA solutions and the concentration dependence of the autocatalytic hydrolysis rate which indicates the connection of process kinetics with the structure of solutions. These data should be considered when carrying out homo- and copolymerization of the previously mentioned monomers in aqueous solutions.