Bio-based composites that mimic the plant cell wall

Abstract

Nature creates high performance materials under modest conditions, i.e., neutral pH and ambient temperature and pressure. One of the most significant materials is the plant cell wall. The plant cell wall is a composite of oriented cellulose microfibrils reinforcing a lignin/hemicellulose matrix. In principle, the plant cell wall composite is designed much like a synthetic fiber-reinforced polymer composite. Unlike synthetic composites, the plant cell wall has an excellent combination of high modulus, strength, toughness and low density that originates in the optimal interactions between the biopolymers. Therefore, to produce high performance composites, a unique route may be to mimic a biological system like the plant cell wall. The present work focuses on understanding the thermodynamics of biopolymer assembly to exploit the process in vitro. In our system, we use an already polymerized nanocellulose template and polymerize phenolic monomers on the template using a peroxidase enzyme. In the first part, we have polymerized phenol using horseradish peroxidase (HRP) in the presence of TEMPO-oxidized nanocellulose. Similar to native plant cell wall structures, the polyphenol-nanocellulose composite had intimate mixing of polyphenol and cellulose at the nanoscale with the presence of cellulose promoting a uniquely organized structure. The obtained composite material showed synergy that enhanced the thermal stability, hydrophobicity, and possibly mechanical properties. In the second part, monolignol coniferyl alcohol was polymerized in the presence of nanocellulose by the same procedure. A comparison between the polyphenol composite and poly(coniferyl alcohol) (PCA) composite revealed that the propanyl substitution imparted flexibility to the PCA molecules so that they could bend and form a hollow globule structure to envelope nanocellulose inside. Polyphenol could not do this because of its rigidity.