ABSTRACT
Stimuli-responsive copolymers are of great interest for targeted drug delivery. This study reports on a controllable post-polymerization quaternization with 2-bromomethyl-4-fluorophenylboronic acid of the poly(4-vinyl pyridine) (P4VP) block of a common poly(styrene)-b-poly(4-vinyl pyridine)-b-poly(ethylene oxide) (SVE) triblock terpolymer in order to achieve a selective responsivity to various diols. For this purpose, a reproducible method was established for P4VP block quaternization at a defined ratio, confirming the reaction yield by 11B, 1H NMR. Then, a reproducible self-assembly protocol is designed for preparing stable micelles from functionalized stimuli-responsive triblock terpolymers, which are characterized by light scattering and by cryogenic transmission electron microscopy. In addition, UV-Vis spectroscopy is used to monitor the boron-ester bonding and hydrolysis with alizarin as a model drug and to study encapsulation and release of this drug, induced by sensing with three geminal diols: fructose, galactose and ascorbic acid. The obtained results show that only the latter, with the vicinal diol group on sp2-hybridized carbons, was efficient for alizarin release. Therefore, the post-polymerization method for triblock terpolymer functionalization presented in this study allows for preparation of specific stimuli-responsive systems with a high potential for targeted drug delivery, especially for cancer treatment.
ABSTRACT
Novel solvent-free ultra-extensible, tough, and self-healing nanocomposite elastomers were synthesized. The self-assembled materials were based on the copolymer matrix poly(methoxyethyl acrylate-co-sodium methacrylate) physically crosslinked by clay nano-platelets ('poly[MEA-co-SMA]/clay'). Depending on the content of SMA, the super-elastomers were predominantly hydrophobic, water-swelling, or fully water-soluble, and hence repeatedly processible. The SMA co-monomer introduces a tremendous increase in tensile strength, an increase in toughness, while ultra-extensibility is preserved. By tuning the contents of nano-clay and SMA co-monomer, a very wide range of product properties was achieved, including extreme ultra-extensibility, or high stiffness combined with more moderate super-extensibility, or very different values of tensile strength. There was very attractive, great improvement in autonomous self-healing ability induced by SMA, combined with tremendously enhanced self-recovery of internal mechanical damage: even complete self-recovery could be achieved. The ionic SMA repeat units were found to assemble to multiplets, which are phase-separated in the hydrophobic polyMEA matrix. The dynamics of SMA-units-hopping between these aggregates was of key importance for the mechanical, visco-elastic, tensile, and self-healing properties. The studied super-elastomers are attractive as advanced self-healing materials in engineering, soft robotics, and in medical or implant applications.
ABSTRACT
Novel stiff, tough, highly transparent and ultra-extensible self-assembled nanocomposite elastomers based on poly(2-methoxyethylacrylate) (polyMEA) were synthesized. The materials are physically crosslinked by small in-situ-formed silica nanospheres, sized 3-5 nm, which proved to be a very efficient macro-crosslinker in the self-assembled network architecture. Very high values of yield stress (2.3 MPa), tensile strength (3.0 MPa), and modulus (typically 10 MPa), were achieved in combination with ultra-extensibility: the stiffest sample was breaking at 1610% of elongation. Related nanocomposites doubly filled with nano-silica and clay nano-platelets were also prepared, which displayed interesting synergy effects of the fillers at some compositions. All the nanocomposites exhibit 'plasto-elastic' tensile behaviour in the 'as prepared' state: they display considerable energy absorption (and also 'necking' like plastics), but at the same time a large but not complete (50%) retraction of deformation. However, after the first large tensile deformation, the materials irreversibly switch to 'real elastomeric' tensile behaviour (with some creep). The initial 'plasto-elastic' stretching thus causes an internal rearrangement. The studied materials, which additionally are valuable due to their high transparency, could be of application interest as advanced structural materials in soft robotics, in implant technology, or in regenerative medicine. The presented study focuses on structure-property relationships, and on their effects on physical properties, especially on the complex tensile, elastic and viscoelastic behaviour of the polyMEA nanocomposites.
