Enzymatic polymerization provides an excellent opportunity for the conversion of renewable resources into polymeric materials in an effective and sustainable manner. A series of furan‐based copolyesters was synthesized with up to 35 kg mol⁻¹, by using Novozyme 435 as a biocatalyst and dimethyl 2,5‐furandicarboxylate (DMFDCA), 2,5‐bis(hydroxymethyl)furan (BHMF), aliphatic linear diols, and diacid ethyl esters as monomers. The synthetic mechanism was evaluated by the variation of aliphatic linear monomers and their feed compositions. Interestingly, there was a significant decrease in the molecular weight if the aliphatic monomers were changed from diols to diacid ethyl esters. The obtained copolyesters were thoroughly characterized and compared with their polyester analogs. These findings provide a closer insight into the application of enzymatic polymerization techniques in designing sustainable high‐performance polymers.

2,5-Furandicarboxylic acid (FDCA)-based semi-aromatic polyamides are novel biobased alternatives to petrol-based semi-aromatic polyamides (polyphthalamides), that have a broad commercial interest as engineering thermoplastics and high performance materials. In this study, a series of FDCA-based semi-aromatic polyamides is successfully produced via Novozym®435 (N435, an immobilized form of Candida antarctica lipase b (CALB))-catalyzed polycondensation of (potentially) biobased dimethyl 2,5-furandicarboxylate and aliphatic diamines differing in chain length (C4–C12), using a one-stage method at 90 °C in toluene. The obtained polyamides reach high weight-average molecular weights ranging from 15 800 to 48 300 g mol⁻¹; and N435 shows the highest selectivity towards 1,8-octanediame (C8). MALDI-ToF MS analysis indicates that no byproducts are formed during the enzymatic polymerization. Study of the kinetics of the enzymatic polymerization suggests that phase separation of FDCA-based oligoamides/polyamides takes place in the early stage of polymerization, and the isolated products undergo an enzyme-catalyzed solid-state polymerization. However, the isolation yields of the purified products from the enzymatic polymerizations are less than ∼50% due to the production of a large amount of low molecular weight products that are washed away during the purification steps. Furthermore, the thermal properties of the enzymatic FDCA-based semi-aromatic polyamides are carefully investigated, and compared to those of the FDCA-based and petrol-based counterparts produced via conventional synthesis techniques as reported in literature.

Previously, we have synthesized a diverse range of 2,5-furandicarboxylic acid (FDCA)-based semiaromatic polyamides via enzymatic polymerization. This novel class of polymers are biobased alternatives to polyphthalamides, which are petrol-based semiaromatic polyamides. From a commercial perspective, they have interesting properties as high-performance materials and engineering thermoplastics. It is even more appealing to explore novel FDCA-based polyamides with added functionality, for the development of sustainable functional materials. Here, a set of FDCA-based heteroatom polyamides have been successfully produced via Novozyme 435 (N435)-catalyzed polymerization of biobased dimethyl 2,5-furandicarboxylate with (potentially)heteroatom diamines, namely, 4,9-dioxa-1,12-dodecanediamine (DODA), diethylenetriamine, and 3,3-ethylenediiminopropylamine. We performed the enzymatic polymerization in solution and bulk. The latter approach is more sustainable and results in higher molecular weight products. Among the tested heteroatom diamines, N435 shows the highest catalytic activity toward DODA. Furthermore, we find that all obtained FDCA-based heteroatom polyamides are amorphous materials with a relatively high thermal stability. These heteroatom polyamides display a glass-transition temperature ranging from 41 to 107 °C.

The lipase catalyzed synthesis of furan-comprising polyester oligomer diols (α,ω-telechelic diols) is reported. Oligofuranoate diols with excellent endgroup fidelity and a yield of 95 % were synthesized using a solvent-free two-stage polycondensation of dimethyl furan-2,5-dicarboxylate (DMFDCA) and 1,4-cyclohexanedimethanol (1,4-CHDM) using immobilized Candida Antarctica Lipase B (CalB). Recycling of immobilized CalB to further decrease the production cost is successfully demonstrated. However, it showed limitation in the product yield that decreases ±20% with each additional reuse. The synthetic procedure has been scaled up, easily opening the possibility to use the developed diols in industrial polycondensations utilizing the excellent flame retardancy property and high thermal stability typical for furan-based polymers.

This study reports a facile delignification and natural drying process for synthesizing cellulose films using the unique surface roughness, porosity, and lightness of the hollow stellate cellulose (HSC) united aerenchyma of the wetland weed Juncus effusus L. By controlling the grafted amino/fluorine‐bearing group content of various silane coupling agents, this work successfully manipulates the triboelectric polarities of HSC films after silanization. Subsequently, a layer of Ag nanowire electrodes is coated on one side of the silanized HSC friction layers, resulting in flexible, lightweight, semi‐transparent HSC‐based triboelectric nanogenerators (HSC‐TENGs) featuring both macro‐scale surface roughness and micro‐nano inner pores. These all‐in‐one HSC‐TENGs achieve the highest output voltage of 4.86 V, which is 28 times that of TENGs employing two pristine HSC films as triboelectric layers (PHSC‐TENG). Finally, the HSC‐TENG with the optimum output power is applied as a wearable self‐powered sensor for gait analysis, demonstrating stable and sustainable performances in distinguishing different body motions such as walking, running, jumping, and calf raising. This study not only proposes a new cellulose‐based TENG for future in‐depth body locomotion analysis but also paves the way for converting differently structured aerenchyma from abundant problematic aquatic or wetland weeds into promising structural templates in multifunctional cellulose‐based applications.