Modular Adjustment of Swelling Behaviors of Surface-Modified Solvent-Responsive Polymeric Nanoparticles Based on Cellulose 10-Undecenoyl Ester

Abstract

Functional polymeric nanoparticles (NPs) have attracted intense interest because of their broad applications. However, most of them focused on characteristics, behaviors, properties, or functionalities of the NPs, while neglecting the interaction between NPs and solvents and thus the influence of solvents on the physical−chemical properties of NPs. In this paper, NPs based on cellulose 10-undecenoyl ester with total substitution of hydroxyl groups by undecenoyl moieties were prepared in various organic dispersants via nanoprecipitation. These NPs were further surface-modified with diverse functionalities via thiol−ene reactions on the terminal vinyl groups of undecenoyl moieties. The swelling behaviors of the resultant surface-modified NPs were systematically investigated via adding corresponding swelling solvents to the dispersions, fitting the swelling modes to different types of functions, and analyzing the factors influencing the swelling processes. It is concluded that different interactions including hydrogen bond interaction between swelling solvents and surface-modified outer layers as well as nonmodified interior parts of NPs are essential for different swelling trends. The swelling extents and tolerant capacities for swelling solvents in dispersant could be affected by the characters of dispersants, the surface functionalities of NPs, and the interaction between them. Thus, our investigation provides a general understanding of the swelling behaviors of surface-modified solvent-responsive NPs derived from polymeric cellulose derivatives.

Multifunctional Reversible Self‐Assembled Structures of Cellulose‐Derived Phase‐Change Nanocrystals

“…[ 5 ] To prepare C18‐UCNCs as phase‐change nanocrystals with phase‐change properties, 1‐octadecanethiol was grafted in the shell layer of UCNCs containing terminal vinyl groups via thiol–ene reaction (Figure 1a). [ 20 ] Compared with those of UCNCs, the peaks related to vinyl groups at 113.9 and 138.2 ppm in the 13 C NMR spectrum of C18‐UCNCs disappeared after the thiol–ene reaction, while a new signal attributed to the CH 3 ‐group appeared at 15.0 ppm (Figure 1e). These results confirmed the successful introduction of 1‐octadecanethiol groups.…”

pH-responsive polymeric nanoparticles with tunable sizes for targeted drug delivery

“…NPs were further prepared via the nanoprecipitation dropping technique using these DAC derivatives. 36 Generally, 1 mL DMF solution of each DAC derivative (10 mg mL À1 ) was added to 10 mL of water by using a syringe pump at a rate of 0.2 mL min À1 under agitation at 800 rpm. The opalescent color of the resulting dispersions indicated the formation of NPs from DAC derivatives.…”

Covalent surface functionalization of nonwoven fabrics with controlled hydrophobicity, water absorption, and pH regulation properties

“…[29][30][31][32][33] Furthermore, the reactive alkene end-groups of 10-undecenoate cellulose can be covalently linked to functional molecules via thiol-ene click and thiol-Michael addition reactions. [34][35][36][37] To the best of our knowledge, UC has not been employed on textiles yet. Due to efficiency of the esterification reaction of UC with hydroxyl groups present on the surface of the fabrics and the availability of the free double-bond end-group for further facile modification with functional materials, this compound could potentially serve as an efficient linker molecule for covalent functionalization of textile.…”

“…A small bifunctional molecule, 10‐undecenoyl chloride (UC), was previously reported by us and others as a grafting molecule for various types of cellulose‐based materials from bran, olive, and eucalyptus as well as neat cellulose and cellulose esters 29–33 . Furthermore, the reactive alkene end‐groups of 10‐undecenoate cellulose can be covalently linked to functional molecules via thiol‐ene click and thiol‐Michael addition reactions 34–37 . To the best of our knowledge, UC has not been employed on textiles yet.…”