Ákos Szabó

Synthesis of Poly(poly(ethylene glycol) methacrylate)–Polyisobutylene ABA Block Copolymers by the Combination of Quasiliving Carbocationic and Atom Transfer Radical Polymerizations

Systematic investigations are carried out on the synthesis of a series of new, unique ABA-type triblock copolymers consisting of the hydrophobic and chemically inert polyisobutylene (PIB) inner and the hydrophilic comb-shaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer as an outer block. Telechelic PIB macroinitiators with narrow molecular weight distributions (MWD) are synthesized by quasiliving carbocationic polymerization of isobutylene with a bifunctional initiator followed by quantitative chain end derivatizations. Atom transfer radical polymerization (ATRP) of PEGMAs with various molecular weights is investigated by using these macroinitiators. It is found that CuBr is an inefficient ATRP catalyst, while CuCl leads to high, nearly complete conversions of the PEGMA macromonomers. Gel permeation chromatography (GPC) analyses reveal slow initiation of PEGMA at relatively high PIB/PEGMA ratios or with PEGMAs of higher molecular weights due to steric hindrance between the macroinitiator and macromonomer. The occurrence of slow initiation, and not permanent termination, is proven by highly efficient ATRP of a low-molecular-weight monomer, methyl methacrylate, with the block copolymers as macroinitiators. Successful synthesis of PPEGMA-PIB-PPEGMA ABA block copolymers is obtained by using either low-molecular-weight PEGMA or relatively low macroinitiator/macromonomer ratios. Differential scanning calorimetry (DSC) indicates phase separation and significant suppression of the crystallinity of the pendant poly(ethylene glycol) (PEG) chains in these new block copolymers.

Synthesis of Poly(methyl methacrylate)-poly(poly(ethylene glycol) methacrylate)-polyisobutylene ABCBA Pentablock Copolymers by Combining Quasiliving Carbocationic and Atom Transfer Radical Polymerizations and Characterization Thereof

Novel, unique amphiphilic pentablock terpolymers consisting of the highly hydrophobic polyisobutylene (PIB) mid-segment attached to the hydrophilic combshaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer chains, which are coupled to poly(methyl methacrylate) (PMMA) outer segments were synthesized by the combination of quasiliving carbocationic polymerization and atom transfer radical polymerization (ATRP). First, a bifunctional PIB macroinitiator was prepared by quasiliving carbocationic polymerization and subsequent quantitative chain end derivatizations. Quasiliving ATRP of PEGMAs with different molecular weights (Mn = 188, 300 and 475 g/mol) led to triblock copolymers which were further reacted with MMA under ATRP conditions to obtain PMMA-PPEGMA-PIB-PPEGMA-PMMA ABCBA-type pentablock copolymers. It was found that slow initiation takes place between the PIB macroinitiator and PEGMA macromonomers with higher molecular weights via ATRP. ATRP of MMA with the resulting block copolymers composed of PIB and PPEGMA chain segments led to the desired block copolymers with high initiating efficiency. Investigations of the resulting pentablock copolymers by DSC, SAXS and phase mode AFM revealed that nanophase separation occurs in these new macromolecular structures with average domain distances of 11-14 nm, and local lamellar self-assembly takes place in the pentablocks with PPEGMA polymacromonomer segments of PEGMAs with Mn of 118 g/mol and 300 g/mol, while disordered nanophases are observed in the block copolymer with PEGMA having molecular weight of 475 g/mol. These new amphiphilic block copolymers composed of biocompatible chain segments can find applications in a variety of advanced fields.

PEGylation of Superparamagnetic Iron Oxide Nanoparticles with Self-Organizing Polyacrylate-PEG Brushes for Contrast Enhancement in MRI Diagnosis

For biomedical applications, superparamagnetic nanoparticles (MNPs) have to be coated with a stealth layer that provides colloidal stability in biological media, long enough persistence and circulation times for reaching the expected medical aims, and anchor sites for further attachment of bioactive agents. One of such stealth molecules designed and synthesized by us, poly(polyethylene glycol methacrylate-co-acrylic acid) referred to as P(PEGMA-AA), was demonstrated to make MNPs reasonably resistant to cell internalization, and be an excellent candidate for magnetic hyperthermia treatments in addition to possessing the necessary colloidal stability under physiological conditions (Illés et al. J. Magn. Magn. Mater. 2018, 451, 710–720). In the present work, we elaborated on the molecular background of the formation of the P(PEGMA-AA)-coated MNPs, and of their remarkable colloidal stability and salt tolerance by using potentiometric acid–base titration, adsorption isotherm determination, infrared spectroscopy (FT-IR ATR), dynamic light scattering, and electrokinetic potential determination methods. The P(PEGMA-AA)@MNPs have excellent blood compatibility as demonstrated in blood sedimentation, smears, and white blood cell viability experiments. In addition, blood serum proteins formed a protein corona, protecting the particles against aggregation (found in dynamic light scattering and electrokinetic potential measurements). Our novel particles also proved to be promising candidates for MRI diagnosis, exhibiting one of the highest values of r2 relaxivity (451 mM−1s−1) found in literature.