Lignin nanoparticle-decorated nanocellulose cryogels as adsorbents for pharmaceutical pollutants

Adsorption is a relatively simple wastewater treatment method that has the potential to mitigate the impacts of pharmaceutical pollution. This requires the development of reusable adsorbents that can simultaneously remove pharmaceuticals of varying chemical structure and properties. Here, the adsorption potential of nanostructured wood-based adsorbents towards different pharmaceuticals in a multi-component system was investigated. The adsorbents in the form of macroporous cryogels were prepared by anchoring lignin nanoparticles (LNPs) to the nanocellulose network via electrostatic attraction. The naturally anionic LNPs were anchored to cationic cellulose nanofibrils (cCNF) and the cationic LNPs (cLNPs) were combined with anionic TEMPO-oxidized CNF (TCNF), producing two sets of nanocellulose-based cryogels that also differed in their overall surface charge density. The cryogels, prepared by freeze-drying, showed layered cellulosic sheets randomly decorated with spherical lignin on the surface. They exhibited varying selectivity and efficiency in removing pharmaceuticals with differing aromaticity, polarity and ionic characters. Their adsorption potential was also affected by the type (unmodified or cationic), amount and morphology of the lignin nanomaterials, as well as the pH of the pharmaceutical solution. Overall, the findings revealed that LNPs or cLNPs can act as functionalizing and crosslinking agents to nanocellulose-based cryogels. Despite the decrease in the overall positive surface charge, the addition of LNPs to the cCNF-based cryogels showed enhanced adsorption, not only towards the anionic aromatic pharmaceutical diclofenac but also towards the aromatic cationic metoprolol (MPL) and tramadol (TRA) and neutral aromatic carbamazepine. The addition of cLNPs to TCNF-based cryogels improved the adsorption of MPL and TRA despite the decrease in the net negative surface charge. The improved adsorption was attributed to modes of removal other than electrostatic attraction, and they could be 7C-7C aromatic ring or hydrophobic interactions brought by the addition of LNPs or cLNPs. However, significant improvement was only found if the ratio of LNPs or cLNPs to nanocellulose was 0.6:1 or higher and with spherical lignin nanomaterials. As crosslinking agents, the LNPs or cLNPs affected the rheological behavior of the gels, and increased the firmness and decreased the water holding capacity of the corresponding cryogels. The resistance of the cryogels towards disintegration with exposure to water also improved with crosslinking, which eventually enabled the cryogels, especially the TCNF-based one, to be regenerated and reused for five cycles of adsorption-desorption experiment for the model pharmaceutical MPL. Thus, this study opened new opportunities to utilize LNPs in providing nanocellulose-based adsorbents with additional functional groups, which were otherwise often achieved by rigorous chemical modifications, at the same time, crosslinking the nanocellulose network.Peer reviewe

Lignocellulose Biocomposites– A Comparison of Wood Fibers and Microfibrillated Lignocellulose

All-lignocellulose composites, meaning densified fiber or fibril materials without added binder, show interesting mechanical properties and can be eco-friendly. Composites based on hot-pressed microfibrillated lignocellulose (MFLC) and lignocellulosic wood fiber (WF) reinforcements are compared with respect to processing, structure, mechanical properties, and eco-indicators. Also, these reinforcements are compared in hot-pressed degradable lignocellulosic crosslinked polycaprolactone (c-PCL) biocomposites based on in-situ polymerization of new caprolactone oligomers. The intermediate lignin content (≈11%) was favorable for MFLC preparation, although the cumulative energy demand was high for mechanical disintegration from unbleached softwood kraft pulp. The mechanical properties were much better for random-in-plane MFLC compared with WF composites due to lower porosity, better interfiber bonding, and smaller-scale defects. Data for strain-field development during tensile tests was in support of these findings. For c-PCL biocomposites, much higher ultimate strength was obtained for the c-PCL/MFLC composites compared with c-PCL/WF. The most important reason was the strainhardening behavior combined with higher strain to failure, since the scale of developing defects was much smaller with MFLC reinforcement.Kompositer baserade på enbart lignocellulosa, dvs pressade fiber- eller fibrillmaterial utan tillsatt bindemedel, har intressanta mekaniska egenskaper och är ofta miljövänliga material. Varmpressad mikrofibrillerad lignocellulosa (MFLC) och varmpressade träfibrer (WF) jämförs med avseende på process, struktur, mekaniska egenskaper och ekoindikatorer. De jämförs också i varmpressade nedbrytbara c-PCL-biokompositer baserade på in-situ polymerisation av nya kaprolakton-oligomerer.  Ett optimum i ligninhalt (≈11%) var gynnsamt för MFLC-framställning, även om det kumulativa energibehovet var högt för mekanisk sönderdelning till MFLC från oblekt barrvedsmassa. De mekaniska egenskaperna var mycket bättre för MFLC jämfört med WF-kompositer för slumpmässig fiberorientering i planet. Orsakerna är lägre porositet, bättre bindning mellan fibrer och att storleken på materialdefekterna är små för MFLC. Data för töjningsfältsutveckling under dragförsök gav stöd för dessa förklaringar. För biokompositer baserade på c-PCL var hållfastheten mycket högre för c-PCL/MFLC-kompositer jämfört med cPCL/WF. Den viktigaste orsaken var starkt töjningshårdnande i kombination med högre töjning till brott, vilket troligen beror på att defekterna som utvecklas under mekanisk belastning av c-PCL/MFLC är mycket mindre än för c-PCL/WF, vid jämförbar töjning.QC 2022-05-17</p

Lignocellulose Biocomposites– A Comparison of Wood Fibers and Microfibrillated Lignocellulose

All-lignocellulose composites, meaning densified fiber or fibril materials without added binder, show interesting mechanical properties and can be eco-friendly. Composites based on hot-pressed microfibrillated lignocellulose (MFLC) and lignocellulosic wood fiber (WF) reinforcements are compared with respect to processing, structure, mechanical properties, and eco-indicators. Also, these reinforcements are compared in hot-pressed degradable lignocellulosic crosslinked polycaprolactone (c-PCL) biocomposites based on in-situ polymerization of new caprolactone oligomers. The intermediate lignin content (≈11%) was favorable for MFLC preparation, although the cumulative energy demand was high for mechanical disintegration from unbleached softwood kraft pulp. The mechanical properties were much better for random-in-plane MFLC compared with WF composites due to lower porosity, better interfiber bonding, and smaller-scale defects. Data for strain-field development during tensile tests was in support of these findings. For c-PCL biocomposites, much higher ultimate strength was obtained for the c-PCL/MFLC composites compared with c-PCL/WF. The most important reason was the strainhardening behavior combined with higher strain to failure, since the scale of developing defects was much smaller with MFLC reinforcement.Kompositer baserade på enbart lignocellulosa, dvs pressade fiber- eller fibrillmaterial utan tillsatt bindemedel, har intressanta mekaniska egenskaper och är ofta miljövänliga material. Varmpressad mikrofibrillerad lignocellulosa (MFLC) och varmpressade träfibrer (WF) jämförs med avseende på process, struktur, mekaniska egenskaper och ekoindikatorer. De jämförs också i varmpressade nedbrytbara c-PCL-biokompositer baserade på in-situ polymerisation av nya kaprolakton-oligomerer.  Ett optimum i ligninhalt (≈11%) var gynnsamt för MFLC-framställning, även om det kumulativa energibehovet var högt för mekanisk sönderdelning till MFLC från oblekt barrvedsmassa. De mekaniska egenskaperna var mycket bättre för MFLC jämfört med WF-kompositer för slumpmässig fiberorientering i planet. Orsakerna är lägre porositet, bättre bindning mellan fibrer och att storleken på materialdefekterna är små för MFLC. Data för töjningsfältsutveckling under dragförsök gav stöd för dessa förklaringar. För biokompositer baserade på c-PCL var hållfastheten mycket högre för c-PCL/MFLC-kompositer jämfört med cPCL/WF. Den viktigaste orsaken var starkt töjningshårdnande i kombination med högre töjning till brott, vilket troligen beror på att defekterna som utvecklas under mekanisk belastning av c-PCL/MFLC är mycket mindre än för c-PCL/WF, vid jämförbar töjning.QC 2022-05-17</p

Enzymatic crosslinking of lignin nanoparticles and nanocellulose in cryogels improves adsorption of pharmaceutical pollutants

Pharmaceuticals, designed for treating diseases, ironically endanger humans and aquatic ecosystems as pollutants. Adsorption-based wastewater treatment could address this problem, however, creating efficient adsorbents remains a challenge. Recent efforts have shifted towards sustainable bio-based adsorbents. Here, cryogels from lignin-containing cellulose nanofibrils (LCNF) and lignin nanoparticles (LNPs) were explored as pharmaceuticals adsorbents. An enzyme-based approach using laccase was used for crosslinking instead of fossil-based chemical modification. The impact of laccase treatment on LNPs alone produced surface-crosslinked water-insoluble LNPs with preserved morphology and a hemicellulose-rich, water-soluble LNP fraction. The water-insoluble LNPs displayed a significant increase in adsorption capacity, up to 140 % and 400 % for neutral and cationic drugs, respectively. The crosslinked cryogel prepared by one-pot incubation of LNPs, LCNF and laccase showed significantly higher adsorption capacities for various pharmaceuticals in a multi-component system than pure LCNF or unmodified cryogels. The crosslinking minimized the leaching of LNPs in water, signifying enhanced binding between LNPs and LCNF. In real wastewater, the laccase-modified cryogel displayed 8–44 % removal for cationic pharmaceuticals. Overall, laccase treatment facilitated the production of bio-based adsorbents by improving the deposition of LNPs to LCNF. Finally, this work introduces a sustainable approach for engineering adsorbents, while aligning with global sustainability goals.Peer reviewe

Lignin nanoparticles as co-stabilizers and modifiers of nanocellulose-based Pickering emulsions and foams

Nanocellulose is very hydrophilic, preventing interactions with the oil phase in Pickering emulsions. This limitation is herein addressed by incorporating lignin nanoparticles (LNPs) as co-stabilizers of nanocellulose-based Pickering emulsions. LNP addition decreases the oil droplet size and slows creaming at pH 5 and 8 and with increasing LNP content. Emulsification at pH 3 and LNP cationization lead to droplet flocculation and rapid creaming. LNP application for emulsification, prior or simultaneously with nanocellulose, favors stability given the improved interactions with the oil phase. The Pickering emulsions can be freeze–dried, enabling the recovery of a solid macroporous foam that can act as adsorbent for pharmaceutical pollutants. Overall, the properties of nanocellulose-based Pickering emulsions and foams can be tailored by LNP addition. This strategy offers a unique, green approach to stabilize biphasic systems using bio-based nanomaterials without tedious and costly modification procedures.</p

Sulfated carboxymethyl cellulose and carboxymethyl κ-carrageenan immobilization on 3D-printed poly-ε-caprolactone scaffolds differentially promote pre-osteoblast proliferation and osteogenic activity

The lack of bioactivity in three-dimensional (3D)-printing of poly-є-caprolactone (PCL) scaffolds limits cell-material interactions in bone tissue engineering. This constraint can be overcome by surface-functionalization using glycosaminoglycan-like anionic polysaccharides, e.g., carboxymethyl cellulose (CMC), a plant-based carboxymethylated, unsulfated polysaccharide, and κ-carrageenan, a seaweed-derived sulfated, non-carboxymethylated polysaccharide. The sulfation of CMC and carboxymethylation of κ-carrageenan critically improve their bioactivity. However, whether sulfated carboxymethyl cellulose (SCMC) and carboxymethyl κ-carrageenan (CM-κ-Car) affect the osteogenic differentiation potential of pre-osteoblasts on 3D-scaffolds is still unknown. Here, we aimed to assess the effects of surface-functionalization by SCMC or CM-κ-Car on the physicochemical and mechanical properties of 3D-printed PCL scaffolds, as well as the osteogenic response of pre-osteoblasts. MC3T3-E1 pre-osteoblasts were seeded on 3D-printed PCL scaffolds that were functionalized by CM-κ-Car (PCL/CM-κ-Car) or SCMC (PCL/SCMC), cultured up to 28 days. The scaffolds’ physicochemical and mechanical properties and pre-osteoblast function were assessed experimentally and by finite element (FE) modeling. We found that the surface-functionalization by SCMC and CM-κ-Car did not change the scaffold geometry and structure but decreased the elastic modulus. Furthermore, the scaffold surface roughness and hardness increased and the scaffold became more hydrophilic. The FE modeling results implied resilience up to 2% compression strain, which was below the yield stress for all scaffolds. Surface-functionalization by SCMC decreased Runx2 and Dmp1 expression, while surface-functionalization by CM-κ-Car increased Cox2 expression at day 1. Surface-functionalization by SCMC most strongly enhanced pre-osteoblast proliferation and collagen production, while CM-κ-Car most significantly increased alkaline phosphatase activity and mineralization after 28 days. In conclusion, surface-functionalization by SCMC or CM-κ-Car of 3D-printed PCL-scaffolds enhanced pre-osteoblast proliferation and osteogenic activity, likely due to increased surface roughness and hydrophilicity. Surface-functionalization by SCMC most strongly enhanced cell proliferation, while CM-κ-Car most significantly promoted osteogenic activity, suggesting that surface-functionalization by CM-κ-Car may be more promising, especially in the short-term, for in vivo bone formation