Characterization of Individual Hydrogen Bonds in Crystalline Regenerated Cellulose Using Resolved Polarized FTIR Spectra

[Image: see text] Cellulose nanofibers (CNFs), which are directly isolated as a native form, have drawn considerable attention as eco-friendly and distinctive material to be partly substituted for fossil products. In addition to the increasing attention to the native CNFs, conventional regenerated cellulose having cellulose II crystals also attracts more attention because of its cost-effective method of production in a moderately easy and repeatable fashion. Inter- and intramolecular hydrogen bonds are, in particular, thought to contribute greatly to the physical properties of cellulosic commercial products. More than half century ago, Marchessault et al. attempted to directly assign the hydroxyl (OH) group vibrations related to hydrogen bonding in infrared (IR) spectra. The assignment, however, has not been significantly updated. One reason for the delayed assignments is the difficulty in preparing pure cellulose II. Here, we show successful IR assignments of the interacted OH groups in cellulose II by using the nematic ordered cellulose to prepare a highly oriented regenerated film. The film had anisotropic crystalline domains, which provided a clearly resolved component in the IR spectra. The OH bands were well assigned, and this IR assignment becomes an effective tool to understand the structure–property relationship for engineering advanced regenerated cellulose materials.