Self-Assembling Oligo(2-oxazoline) Organogelators for the Encapsulation and Slow Release of Bioactive Volatiles

Abstract

Herein, we report a class of distinctive supramolecular nanostructures in situ-generated from the cationic ring-opening polymerization of a particular 2-oxazoline monomer, i.e., 2-( N - tert -butyloxycarbonylaminomethyl)-2-oxazoline (Ox1). Driven by side-chain hydrogen bonding between neighboring molecules and van der Waals interactions, the growing oligomers of Ox1 precipitate in the form of macroscopic platelets when the degree of polymerization reaches 5–7. A similar self-assembly occurred in the block copolymerization of 2-ethyl-2-oxazoline (EtOx) or 2-pentyl-2-oxazoline (PeOx) and Ox1 as the second monomer. These polymeric aggregates were found to disassemble into rod-like nanoparticles under appropriate conditions, and to form stable organogels in some polar solvents like dimethylformamide as well as in natural liquid fragrances such as ( R )-carvone, citronellal, and ( R )-limonene. Scanning electron microscopy revealed that the morphology of their xerogels was solvent-dependent, mainly with a lamellar or fibrous structure. The rheology measurements confirmed the as-obtained organogels feature an obvious thixotropic character. The storage modulus was about 7–10 times higher than the loss modulus, indicating the physical crosslinking in the gel. The fragrance release profiles showed that the presented supramolecular gel system exhibits good sustained-release effect for the loaded bioactive volatiles.

Controlled Lactonization of o-Coumaric Esters Mediated by Supramolecular Gels

“…Their chemical structure is easily tuneable, they can respond to different stimuli (triggers) to form/disrupt the gel network, and they are often biocompatible and biodegradable [ 17 , 18 , 19 , 20 , 21 ]. The controlled release of fragrances from gel media has been reported by us [ 22 ] and other research groups [ 6 , 8 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 ].…”