POLYMER CHEMISTRY, cilt.16, ss.3619-3631, 2025 (SCI-Expanded)
Boron-based asymmetrically structured poly(substituted glycolide) homopolymers (BF2I-PASG) were prepared from a library of asymmetric substituted glycolide (ASG, I-VI) monomers (linear alkyl (propyl methyl-I and propyl ethyl-II) or branched (isobutyl methyl-III, isobutyl ethyl-IV, isoleucine methyl-V, and isoleucine ethyl-VI) glycolide), which have an analogous structure to lactide (LA) and glycolide (GA), using BF2dbmOEtOH (BF2I) as the initiator in the presence of the Sn(Oct)2 catalyst in a solvent-free environment. The presence of amorphous BF2I-PASG, with a glass transition temperature (Tg) ranging from 4.1 to 31.9 degrees C determined by DSC analysis, suggested its suitability for short-term drug release. This amorphous character is attributed to the asymmetric structure of monomers I-VI, which incorporate various substituted side groups on the GA rings. The thermal stability (i.e., Td) of BF2I-PASG was examined by TGA analysis, revealing a single-step degradation that shifted towards higher Td values, from 346 degrees C to 377 degrees C, as the length of the alkyl side group on the polymer backbone increased. BF2I-PASGs exhibit high extinction coefficients of up to 53 750 M-1 cm-1, demonstrating strong pi-pi* transitions and intense blue fluorescence, with fluorescence lifetimes following a single-exponential decay as high as 1.96 ns and good quantum yields of up to 75%. Moreover, the nanoparticles (NPs) of these polymers possess a smooth surface and regular spherical shape, with average diameters as small as 236 nm, low and narrow polydispersity indices (PDI) ranging from 0.062 to 0.136, and a drug loading capacity of approximately >= 5%. For example, the NPs exhibited a rapid release profile for the anticancer drug paclitaxel, with around 82.1-96.2 of the drug released within approximately 5 days, depending on the NP composition.