Noncovalent Dispersion and Functionalization of Cellulose Nanocrystals with Proteins and Polysaccharides

Native cellulose nanocrystals (CNCs) are valuable high quality materials with potential for many applications including the manufacture of high performance materials. In this work, a relatively effortless procedure was introduced for the production of CNCs, which gives a nearly 100% yield of crystalline cellulose. However, the processing of the native CNCs is hindered by the difficulty in dispersing them in water due to the absence of surface charges. To overcome these difficulties, we have developed a one-step procedure for dispersion and functionalization of CNCs with tailored cellulose binding proteins. The process is also applicable for polysaccharides. The tailored cellulose binding proteins are very efficient for the dispersion of CNCs due to the selective interaction with cellulose, and only small fraction of proteins (5–10 wt %, corresponds to about 3 μmol g^–1) could stabilize the CNC suspension. Xyloglucan (XG) enhanced the CNC dispersion above a fraction of 10 wt %. For CNC suspension dispersed with carboxylmethyl cellulose (CMC) we observed the most long-lasting stability, up to 1 month. The cellulose binding proteins could not only enhance the dispersion of the CNCs, but also functionalize the surface. This we demonstrated by attaching gold nanoparticles (GNPs) to the proteins, thus, forming a monolayer of GNPs on the CNC surface. Cryo transmission electron microscopy (Cryo-TEM) imaging confirmed the attachment of the GNPs to CNC solution conditions

Superhydrophobic and Slippery Lubricant-Infused Flexible Transparent Nanocellulose Films by Photoinduced Thiol–Ene Functionalization

Films comprising nanofibrillated cellulose (NFC) are suitable substrates for flexible devices in analytical, sensor, diagnostic, and display technologies. However, some major challenges in such developments include their high moisture sensitivity and the complexity of current methods available for functionalization and patterning. In this work, we present a facile process for tailoring the surface wettability and functionality of NFC films by a fast and versatile approach. First, the NFC films were coated with a layer of reactive nanoporous silicone nanofilament by polycondensation of trichlorovinylsilane (TCVS). The TCVS afforded reactive vinyl groups, thereby enabling simple UV-induced functionalization of NFC films with various thiol-containing molecules via the photo “click” thiol–ene reaction. Modification with perfluoroalkyl thiols resulted in robust superhydrophobic surfaces, which could then be further transformed into transparent slippery lubricant-infused NFC films that displayed repellency against both aqueous and organic liquids with surface tensions as low as 18 mN·m^–1. Finally, transparent and flexible NFC films incorporated hydrophilic micropatterns by modification with OH, NH₂, or COOH surface groups, enabling space-resolved superhydrophobic–hydrophilic domains. Flexibility, transparency, patternability, and perfect superhydrophobicity of the produced nanocellulose substrates warrants their application in biosensing, display protection, and biomedical and diagnostics devices

Contribution of Residual Proteins to the Thermomechanical Performance of Cellulosic Nanofibrils Isolated from Green Macroalgae

Cellulosic nanofibrils (CNFs) were isolated from one of the most widespread freshwater macroalgae, Aegagropila linnaei. The algae were first carboxylated with a recyclable dicarboxylic acid, which facilitated deconstruction into CNFs via microfluidization while preserving the protein component. For comparison, cellulosic fibrils were also isolated by chemical treatment of the algae with sodium chlorite. Compared with the energy demanded for deconstruction of wood fibers, algal biomass required substantially lower levels. Nevertheless, the resultant nanofibrils were more crystalline (crystallinity index > 90%) and had a higher degree of polymerization (DP > 2500). Taking advantage of these properties, algal CNFs were used to produce films or nanopapers (tensile strength of up to 120 MPa), the strength of which resulted from protein-enhanced interfibrillar adhesion. Besides being translucent and flexible, the nanopapers displayed unusually high thermal stability (up to 349 °C). Overall, we demonstrate a high-end utilization of a renewable bioresource that is available in large volumes, for example, in the form of algal blooms