Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities

Abstract

Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2-methylene-1,3-dioxepane (MDO) using a macro-xanthate CTA, poly(N-vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)-b-poly(MDO-co-VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self-assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro-CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and "click" chemistry as postpolymerization tools to create fluorescently labeled nanoparticles.

Degradable vinyl copolymers through thiocarbonyl addition–ring-opening (TARO) polymerization

“…However, these systems are not without drawbacks. Cyclic ketene acetals generally show low reactivity during radical copolymerizations with (meth)acrylic and styrenic monomers (meaning that only small quantities of the feed are incorporated into the product) 8 although recent work has demonstrated high incorporation of cyclic ketene acetals during copolymerizations with vinyl ethers, 13 vinyl esters, 14 N-vinyl pyrrolidone, 15 and maleimides. 16,17 The cyclic allyl sulfide monomer family, while allowing additional in-ring functionality, 11,18 installs a methylene group into the product which remains reactive toward radicals and can lead to unwanted crosslinking.…”

Amphiphilic block copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene: synthesis and self‐assembly

“…3(c), :1 water/toluene). Because the solvent composition plays an important role in controlling the morphology of the self‐assembled structures, it is necessary to choose a suitable solvent for the self‐assembly of the block copolymer. Thus, the solubility parameters of various solvents and of the individual blocks in the copolymer were calculated.…”

Molecular bionics – engineering biomaterials at the molecular level using biological principles

“…Its main drawback is represented by the need of using peculiar monomers (e.g., high-strain rings [212] such as cyclic ketene acetals (CKA) [212,213] which are difficult to synthesise/purify and store. Nevertheless, a number of reports of supramolecular assemblies (spherical/worm-like micelles and vesicles) bearing copolymers produced using this technique are starting to appear in literature for drug delivery applications [214][215][216][217][218][219].…”