The development of advanced composite biomaterials combining the versatility and biodegradability of polymers and the unique characteristics of metal oxide nanoparticles unveils new horizons in emerging biomedical applications, including tissue regeneration, drug delivery and gene therapy, theranostics and medical imaging. Nanocrystalline cerium(IV) oxide, or nanoceria, stands out from a crowd of other metal oxides as being a truly unique material, showing great potential in biomedicine due to its low systemic toxicity and numerous beneficial effects on living systems. The combination of nanoceria with new generations of biomedical polymers, such as PolyHEMA (poly(2-hydroxyethyl methacrylate)-based hydrogels, electrospun nanofibrous polycaprolactone or natural-based chitosan or cellulose, helps to expand the prospective area of applications by facilitating their bioavailability and averting potential negative effects. This review describes recent advances in biomedical polymeric material practices, highlights up-to-the-minute cerium oxide nanoparticle applications, as well as polymer-nanoceria composites, and aims to address the question: how can nanoceria enhance the biomedical potential of modern polymeric materials?
The structure of LiCl in tetrahydrofuran (THF) solution and its effect on the structure and stability of active sites of the anionic polymerization of methyl methacrylate (MMA) and styrene (St) was studied using the quantum-chemical density functional theory (DFT) approach. In the case of MMA anionic polymerization, it was found that LiCl forms stable mixed aggregates with ester enolates which model the PMMA living chain ends, thus preventing them from self-aggregation. They may even stabilize more reactive zwitterionic structures of these chain ends. The dissociation of solvated LiCl dimers to form Li + (THF)4 cations is slightly endothermic in THF, while scavenging of Li + (THF)4 by LiCl dimers to produce more stable quintuple cations [(THF)3Li-Cl-Li(THF)2-Cl-Li(THF)3] + is even exothermic. Therefore, if the concentration of LiCl exceeds a certain threshold value, Li + (THF)4 cations should effectively be scavenged by LiCl dimers. Thus, increasing LiCl concentration below the threshold concentration should lead to an increase in the concentration of free Li + (THF)4 cations. In the anionic polymerization of styrene in the presence of LiCl this results in the suppression of PSt-Li chain end dissociation due to the common ion effect, slowing down the polymerization. Further addition of LiCl above the threshold concentration should decrease the concentration of free Li + (THF)4 cations, leading to enhanced PSt-Li chain end dissociation, thus increasing the polymerization rate, in agreement with kinetic data reported in the literature.
To design novel polymer materials with optimal properties relevant to industrial usage, it would seem logical to modify polymers with reportedly good functionality, such as polyimides (PIs). We have created a set of PI-based nanocomposites containing binary blends of CeO2 with carbon nanoparticles (nanocones/discs or nanofibres), to improve a number of functional characteristics of the PIs. The prime novelty of this study is in a search for a synergistic effect amidst the nanofiller moieties regarding the thermal and the mechanical properties of PIs. In this paper, we report on the structure, thermal, and mechanical characteristics of the PI-based nanocomposites with binary fillers. We have found that, with a certain composition, the functional performance of a material can be substantially improved. For example, a PI containing SO2-groups in its macrochains not only had its thermal stability enhanced (by ~20 °C, 10% weight loss up to 533 °C) but also had its stiffness increased by more than 10% (Young’s modulus as high as 2.9–3.0 GPa) in comparison with the matrix PI. In the case of a PI with no sulfonic groups, binary fillers increased stiffness of the polymer above its glass transition temperature, thereby widening its working temperature range. The mechanisms of these phenomena are discussed. Thus, this study could contribute to the design of new composite materials with controllable and improved functionality.
The unusual effect of selective enhancement of the thermal stability of aromatic polyimide materials was established through the introduction of cerium dioxide nanoparticles into these polymers as nanofiller. Depending on the chemical structure of the polymers, a marked increase or a substantial decrease in the thermal stability of the nanocomposite material was registered by thermal analysis, as compared with that of unfilled polymer material. The positive effect was registered only for the composite materials based on the matrix polyimides containing the sulfur atoms located in the sulfonic groups arranged in the elementary units. The results of the thermogravimetric examination are compared with the data obtained during the mechanical tests of the same samples. The possible reasons for the alteration of the thermal stability of polymers by ceria nanoparticles are discussed. The effect above can be of substantial practical interest providing new options for the design of polyimide nanocomposite materials with enhanced thermal stability.
A technique for the fabrication of bacterial cellulose-based films with CeO2 nanofiller has been developed. The structural and morphological characteristics of the materials have been studied, their thermal and mechanical properties in dry and swollen states having been determined. The preparation methodology makes it possible to obtain composites with a uniform distribution of nanoparticles. The catalytic effect of ceria, regarding the thermal oxidative destruction of cellulose, has been confirmed by TGA and DTA methods. An increase in CeO2 content led to an increase in the elastic modulus (a 1.27-fold increase caused by the introduction of 5 wt.% of the nanofiller into the polymer) and strength of the films. This effect is explained by the formation of additional links between polymer macro-chains via the nanoparticles’ surface. The materials fabricated were characterized by a limited ability to swell in water. Swelling caused a 20- to 30-fold reduction in the stiffness of the material, the mechanical properties of the films in a swollen state remaining germane to their practical use. The application of the composite films in cell engineering as substrates for the stem cells’ proliferation has been studied. The increase in CeO2 content in the films enhanced the proliferative activity of embryonic mouse stem cells. The cells cultured on the scaffold containing 5 wt.% of ceria demonstrated increased cell survival and migration activity. An analysis of gene expression confirmed improved cultivation conditions on CeO2-containing scaffolds.
Poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) membranes are attractive due to high permeability for gases; however, the selectivity of these membranes is insufficient. In this work, the gas selectivity was improved without significant loss of the permeability. For this purpose, PPO was modified via incorporation of the branched copolyimide filler–grafted copolyimide (PI‐g‐PMMA) with polymethyl methacrylate (PMMA) side chains. Two series of mixed self‐supporting PPO/PI‐g‐PMMA films (with variation of the filler content) were prepared and studied as gas separation membranes. The length of the polymide (PI) chain and the density of PMMA grafting were the same in both series, however, in one series the grafted chains contained 50 MMA units, and in the other 150 units. The intermolecular interactions between the PPO matrix and the PI‐g‐PMMA fillers were investigated using viscometry, infrared (IR) spectroscopy, and scanning electron microscopy. The compatibility of the polymer components is limited; however, for both series, the contents of the respective filler are found, which ensures phase segregation only in a microscale. Therefore, the mechanical properties of the films allow their use as gas separation membranes. It is shown that the degree of the segregation as well as the mechanical and gas transport properties of the membranes depend on the length of the PMMA chains, and the membranes with filler‐containing shorter branches (50 MMA units) show better selectivity.
Multicomponent molecular brushes containing amphiphilic polymer moieties are promising objects of research of macromolecular chemistry. The development of stimulus-responsive systems sensitive to changes in environmental parameters, based on the molecular brushes, opens up new possibilities for their applications in medicine, biochemistry and microelectronics. The review presents the current understanding of the structures of main types of amphiphilic multicomponent brushes, depending on the chemical nature and type of coupling of the backbone and side chains. The approaches to the controlled synthesis of multicomponent molecular brushes of different architecture are analyzed. Self-assembly processes of multicomponent molecular brushes in selective solvents are considered. The bibliography includes 259 references.
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