Thiol-based chemistry as versatile routes for the effective functionalization of cellulose nanofibers

Sol An; Bokyoung Jeon; Jong Hyuk Bae; Ick Soo Kim; Keewook Paeng; Myungwoong Kim; Hoik Lee

doi:10.1016/j.carbpol.2019.115259

Thiol-based chemistry as versatile routes for the effective functionalization of cellulose nanofibers

Carbohydr Polym. 2019 Dec 15:226:115259. doi: 10.1016/j.carbpol.2019.115259. Epub 2019 Aug 27.

Authors

Sol An¹, Bokyoung Jeon¹, Jong Hyuk Bae², Ick Soo Kim³, Keewook Paeng⁴, Myungwoong Kim⁵, Hoik Lee⁶

Affiliations

¹ Department of Chemistry and Chemical Engineering, Inha University, Incheon, 22212, Republic of Korea.
² Research Institute of Industrial Technology Convergence, Smart Textiles R&D Groups, Korea Institute of Industrial Technology, Ansan, 15588, Republic of Korea; Department of Organic and Nano Engineering, Hanyang University, Seoul, Republic of Korea.
³ Nano Fusion Technology Research Group, Division of Frontier Fibers, Institute for Fiber Engineering (IFES), Interdisciplinary Cluster for Cutting Edge Research (ICCER), Shinshu University, Tokida 3-15-1, Ueda, Nagano, 386-8567, Japan.
⁴ Department of Chemistry, Sungkyunkwan University, Suwon, 16419, Republic of Korea. Electronic address: paeng@skku.edu.
⁵ Department of Chemistry and Chemical Engineering, Inha University, Incheon, 22212, Republic of Korea. Electronic address: mkim233@inha.ac.kr.
⁶ Research Institute of Industrial Technology Convergence, Smart Textiles R&D Groups, Korea Institute of Industrial Technology, Ansan, 15588, Republic of Korea. Electronic address: hoik@kitech.re.kr.

PMID: 31582070
DOI: 10.1016/j.carbpol.2019.115259

Abstract

We demonstrate effective functionalization chemistry for cellulose nanofiber modification using thiol functionality. Electrospun cellulose acetate nanofibers were deacetylated to obtain cellulose nanofibers, which were modified further to incorporate thiol on their surface by the esterification of hydroxyl groups with 3,3'-dithiodipropionic acid and further reductive cleavage of the disulfide bond. The thiol functionality was highly versatile to bring simple and efficient chemical reactions to attain (i) Ag nanoparticle-adsorbed cellulose nanofibers by Ag ion reduction at surface, (ii) various amine (primary amine and quaternary amine) functionalized cellulose nanofibers by Michael addition, and (iii) complex polymer functionalized cellulose nanofibers by a radical-based thiol-ene reaction, under mild conditions, i.e. in any reaction media, at room temperature, and under ambient atmosphere, evidenced by a variety of characterization methods including a quantitative analysis with X-ray photoemission spectroscopy. These scalable thiol-based chemistries should offer a new generation of well-tailored cellulose nanofiber materials with complex inorganic, organic, and polymeric functionalities, potentially expanding to functionalized surfaces of other carbohydrate-based materials to achieve the desired properties.

Keywords: Cellulose nanofiber; Metal adsorption; Thiol functionalization; Thiol-ene click reactions.