Stimuli-responsive nanoparticles from ionic cellulose derivatives

Abstract

Stimuli-responsive nanoparticles (NPs) based on sustainable polymeric feedstock still need more exploration in comparison with NPs based on synthetic polymers. In this report, stimuli-responsive NPs from novel ionic cellulose derivatives were prepared via a facile nanoprecipitation. Cellulose 10-undecenoyl ester (CUE) with a degree of substitution (DS) of 3 was synthesized by esterification of cellulose with 10-undecenoyl chloride. Then, CUE was modified by photo-induced thiol-ene reactions, in order to obtain organo-soluble ionic cellulose derivatives with DSs of ∼3, namely cellulose 11-((3-carboxyl)ethylthio)undecanoate (CUE-MPA), cellulose 11-((2-aminoethyl)thio)undecanoate (CUE-CA), cellulose 11-(2-(2-(diethylamino)ethyl)thio)undecanoate (CUE-DEAET) and cellulose 11-(2-(2-(dimethylamino)ethyl)thio)undecanoate (CUE-DMAET). CUE-MPA could be transformed into NPs with average diameters in the range of 80-330 nm, but these NPs did not show particular stimuli-responsive properties. Moreover, the dropping technique resulted in smaller NPs than a dialysis technique. Stable NPs with average diameters in the range of 90-180 nm showing pH-responsive and switchable sizes were obtained from CUE-DEAET and CUE-DMAET possessing tertiary amines using nanoprecipitation. Thus, altering the terminal functional groups will be a new approach to prepare stimuli-responsive cellulose-derived polymeric NPs.

Incorporation of Hydrophobic Dyes within Cellulose Acetate and Acetate Phthalate Based Nanoparticles

“…They are easy to prepare and taken up by cells without showing cytotoxicity . In order to introduce specific functionalities (e.g., sensoring, drug delivery, antigen detection, and stimuli responsiveness), different active molecules (e.g., dyes, drugs, antibodies, and ionic substituents) have been attached covalently either directly to the particles or to the hydrophobic polysaccharide derivatives prior to the self‐assembling process …”

“…Hydrophobic polysaccharide derivatives, such as esters of monocarboxcylic acids, alkyl-and phenyl carbonates, and acetals derived from cellulose, dextran, and xylan, are capable of forming well-defi ned spherical nanoparticles polysaccharide derivatives prior to the self-assembling process. [10][11][12][13] Physical entrapment is a highly desired and facile alternative for loading polysaccharide based NP with a broad variety of active substances. It would enable higher loading capacities compared to covalent immobilization.…”

Functional nanomaterials through esterification of cellulose: a review of chemistry and application

“…Composite films with 0-80 wt% of such modified CNCs within a poly(butadiene) rubber matrix were prepared via cross-linking by UV-light initiated thiol-ene click reaction to mimic biological nanocomposites involving self-assembled and spacefiled structures of hard reinforcing and soft toughening domains. Furthermore, pH-responsive NPs with switchable sizes using a modified nanoprecipitation method were prepared using cellulose 10-undecenoyl ester (CUE) as precursor (Wang et al 2016c). The CUE with a DS of 3 was synthesized after the esterification of cellulose with 10-undecenoyl chloride under heterogenous condition.…”

Thiol–ene click reaction on cellulose sponge and its application for oil/water separation

“…Tingaut et al 24 prepared three functional cellulose lms using thiol-ene click reactions. Zhang et al 25 prepared different pH-responsive nanoparticles from novel ionic cellulose derivatives made by thiol-ene click reactions. Levkin et al 26 prepared functional nanocellulose lms using photo-induced thiol-ene reactions.…”