Tunable Fungal Monofilaments from Food Waste for Textile Applications.

A fungal biorefinery is presented to valorize food waste to fungal monofilaments with tunable properties for different textile applications. Rhizopus delemar is successfully grown on bread waste and the fibrous cell wall is isolated. A spinnable hydrogel is produced from cell wall by protonation of amino groups of chitosan followed by homogenization and concentration. Fungal hydrogel is wet spun to form fungal monofilaments which underwent post-treatments to tune the properties. The highest tensile strength of untreated monofilaments is 65 MPa (and 4% elongation at break). The overall highest tensile strength of 140.9 MPa, is achieved by water post-treatment. Moreover, post-treatment with 3% glycerol resulted in the highest elongation % at break, i.e., 14%. The uniformity of the monofilaments also increased after the post-treatments. The obtained monofilaments are compared with commercial fibers using Ashby's plots and potential applications are discussed. The wet spun monofilaments are located in the category of natural fibers in Ashby's plots. After water and glycerol treatments, the properties shifted toward metals and elastomers, respectively. The compatibility of the monofilaments with human skin cells is supported by a biocompatibility assay. These findings demonstrate fungal monofilaments with tunable properties fitting a wide range of sustainable textiles applications.

Preparation and Characterization of Softwood and Hardwood Nanofibril Hydrogels: Toward Wound Dressing Applications.

Hydrogels of cellulose nanofibrils (CNFs) are promising wound dressing candidates due to their biocompatibility, high water absorption, and transparency. Herein, two different commercially available wood species, softwood and hardwood, were subjected to TEMPO-mediated oxidation to proceed with delignification and oxidation in a one-pot process, and thereafter, nanofibrils were isolated using a high-pressure microfluidizer. Furthermore, transparent nanofibril hydrogel networks were prepared by vacuum filtration. Nanofibril properties and network performance correlated with oxidation were investigated and compared with commercially available TEMPO-oxidized pulp nanofibrils and their networks. Softwood nanofibril hydrogel networks exhibited the best mechanical properties, and in vitro toxicological risk assessment showed no detrimental effect for any of the studied hydrogels on human fibroblast or keratinocyte cells. This study demonstrates a straightforward processing route for direct oxidation of different wood species to obtain nanofibril hydrogels for potential use as wound dressings, with softwood having the most potential.

Self-Assembly of Nanocellulose Hydrogels Mimicking Bacterial Cellulose for Wound Dressing Applications.

The self-assembly of nanocellulose in the form of cellulose nanofibers (CNFs) can be accomplished via hydrogen-bonding assistance into completely bio-based hydrogels. This study aimed to use the intrinsic properties of CNFs, such as their ability to form strong networks and high absorption capacity and exploit them in the sustainable development of effective wound dressing materials. First, TEMPO-oxidized CNFs were separated directly from wood (W-CNFs) and compared with CNFs separated from wood pulp (P-CNFs). Second, two approaches were evaluated for hydrogel self-assembly from W-CNFs, where water was removed from the suspensions via evaporation through suspension casting (SC) or vacuum-assisted filtration (VF). Third, the W-CNF-VF hydrogel was compared to commercial bacterial cellulose (BC). The study demonstrates that the self-assembly via VF of nanocellulose hydrogels from wood was the most promising material as wound dressing and displayed comparable properties to that of BC and strength to that of soft tissue.

Nanocellulose composite wound dressings for real-time pH wound monitoring.

The skin is the largest organ of the human body. Wounds disrupt the functions of the skin and can have catastrophic consequences for an individual resulting in significant morbidity and mortality. Wound infections are common and can substantially delay healing and can result in non-healing wounds and sepsis. Early diagnosis and treatment of infection reduce risk of complications and support wound healing. Methods for monitoring of wound pH can facilitate early detection of infection. Here we show a novel strategy for integrating pH sensing capabilities in state-of-the-art hydrogel-based wound dressings fabricated from bacterial nanocellulose (BC). A high surface area material was developed by self-assembly of mesoporous silica nanoparticles (MSNs) in BC. By encapsulating a pH-responsive dye in the MSNs, wound dressings for continuous pH sensing with spatiotemporal resolution were developed. The pH responsive BC-based nanocomposites demonstrated excellent wound dressing properties, with respect to conformability, mechanical properties, and water vapor transmission rate. In addition to facilitating rapid colorimetric assessment of wound pH, this strategy for generating functional BC-MSN nanocomposites can be further be adapted for encapsulation and release of bioactive compounds for treatment of hard-to-heal wounds, enabling development of novel wound care materials.

Characteristics of Cellulose Nanofibrils from Transgenic Trees with Reduced Expression of Cellulose Synthase Interacting 1.

Cellulose nanofibrils can be derived from the native load-bearing cellulose microfibrils in wood. These microfibrils are synthesized by a cellulose synthase enzyme complex that resides in the plasma membrane of developing wood cells. It was previously shown that transgenic hybrid aspen trees with reduced expression of CSI1 have different wood mechanics and cellulose microfibril properties. We hypothesized that these changes in the native cellulose may affect the quality of the corresponding nanofibrils. To test this hypothesis, wood from wild-type and transgenic trees with reduced expression of CSI1 was subjected to oxidative nanofibril isolation. The transgenic wood-extracted nanofibrils exhibited a significantly lower suspension viscosity and estimated surface area than the wild-type nanofibrils. Furthermore, the nanofibril networks manufactured from the transgenics exhibited high stiffness, as well as reduced water uptake, tensile strength, strain-to-break, and degree of polymerization. Presumably, the difference in wood properties caused by the decreased expression of CSI1 resulted in nanofibrils with distinctive qualities. The observed changes in the physicochemical properties suggest that the differences were caused by changes in the apparent nanofibril aspect ratio and surface accessibility. This study demonstrates the possibility of influencing wood-derived nanofibril quality through the genetic engineering of trees.

Thermal Conductivity of Cellulose Fibers in Different Size Scales and Densities.

Considering the growing use of cellulose in various applications, knowledge and understanding of its physical properties become increasingly important. Thermal conductivity is a key property, but its variation with porosity and density is unknown, and it is not known if such a variation is affected by fiber size and temperature. Here, we determine the relationships by measurements of the thermal conductivity of cellulose fibers (CFs) and cellulose nanofibers (CNFs) derived from commercial birch pulp as a function of pressure and temperature. The results show that the thermal conductivity varies relatively weakly with density (ρsample = 1340-1560 kg m-3) and that its temperature dependence is independent of density, porosity, and fiber size for temperatures in the range 80-380 K. The universal temperature and density dependencies of the thermal conductivity of a random network of CNFs are described by a third-order polynomial function (SI-units): κCNF = (0.0787 + 2.73 × 10-3·T - 7.6749 × 10-6·T2 + 8.4637 × 10-9·T3)·(ρsample/ρ0)2, where ρ0 = 1340 kg m-3 and κCF = 1.065·κCNF. Despite a relatively high degree of crystallinity, both CF and CNF samples show amorphous-like thermal conductivity, that is, it increases with increasing temperature. This appears to be due to the nano-sized elementary fibrils of cellulose, which explains that the thermal conductivity of CNFs and CFs shows identical behavior and differs by only ca. 6%. The nano-sized fibrils effectively limit the phonon mean free path to a few nanometers for heat conduction across fibers, and it is only significantly longer for highly directed heat conduction along fibers. This feature of cellulose makes it easier to apply in applications that require low thermal conductivity combined with high strength; the weak density dependence of the thermal conductivity is a particularly useful property when the material is subjected to high loads. The results for thermal conductivity also suggest that the crystalline structures of cellulose remain stable up to at least 0.7 GPa.

Functional Nanocomposite Films of Poly(Lactic Acid) with Well-Dispersed Chitin Nanocrystals Achieved Using a Dispersing Agent and Liquid-Assisted Extrusion Process.

The development of bio-based nanocomposites is of high scientific and industrial interest, since they offer excellent advantages in creating functional materials. However, dispersion and distribution of the nanomaterials inside the polymer matrix is a key challenge to achieve high-performance functional nanocomposites. In this context, for better dispersion, biobased triethyl citrate (TEC) as a dispersing agent in a liquid-assisted extrusion process was used to prepare the nanocomposites of poly (lactic acid) (PLA) and chitin nanocrystals (ChNCs). The aim was to identify the effect of the TEC content on the dispersion of ChNCs in the PLA matrix and the manufacturing of a functional nanocomposite. The nanocomposite film's optical properties; microstructure; migration of the additive and nanocomposites' thermal, mechanical and rheological properties, all influenced by the ChNC dispersion, were studied. The microscopy study confirmed that the dispersion of the ChNCs was improved with the increasing TEC content, and the best dispersion was found in the nanocomposite prepared with 15 wt% TEC. Additionally, the nanocomposite with the highest TEC content (15 wt%) resembled the mechanical properties of commonly used polymers like polyethylene and polypropylene. The addition of ChNCs in PLA-TEC15 enhanced the melt viscosity, as well as melt strength, of the polymer and demonstrated antibacterial activity.

Multifunctional Ginger Nanofiber Hydrogels with Tunable Absorption: The Potential for Advanced Wound Dressing Applications.

In this study, ginger residue from juice production was evaluated as a raw material resource for preparation of nanofiber hydrogels with multifunctional properties for advanced wound dressing applications. Alkali treatment was applied to adjust the chemical composition of ginger fibers followed by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation prior to nanofiber isolation. The effect of alkali treatment on hydrogel properties assembled through vacuum filtration without addition of any chemical cross-linker was evaluated. An outstanding absorption ability of 6200% combined with excellent mechanical properties, tensile strength of 2.1 ± 0.2 MPa, elastic modulus of 15.3 ± 0.3 MPa, and elongation at break of 25.1%, was achieved without alkali treatment. Furthermore, the absorption capacity was tunable by applying alkali treatment at different concentrations and by adjusting the hydrogel grammage. Cytocompatibility evaluation of the hydrogels showed no significant effect on human fibroblast proliferation in vitro. Ginger essential oil was used to functionalize the hydrogels by providing antimicrobial activity, furthering their potential as a multifunctional wound dressing.

Seaweed-Derived Alginate-Cellulose Nanofiber Aerogel for Insulation Applications.

The next generation of green insulation materials is being developed to provide safer and more sustainable alternatives to conventional materials. Bio-based cellulose nanofiber (CNF) aerogels offer excellent thermal insulation properties; however, their high flammability restricts their application. In this study, the design concept for the development of a multifunctional and non-toxic insulation material is inspired by the natural composition of seaweed, comprising both alginate and cellulose. The approach includes three steps: first, CNFs were separated from alginate-rich seaweed to obtain a resource-efficient, fully bio-based, and inherently flame-retardant material; second, ice-templating, followed by freeze-drying, was employed to form an anisotropic aerogel for effective insulation; and finally, a simple crosslinking approach was applied to improve the flame-retardant behavior and stability. At a density of 0.015 g cm-3, the lightweight anisotropic aerogels displayed favorable mechanical properties, including a compressive modulus of 370 kPa, high thermal stability, low thermal conductivity (31.5 mW m-1 K-1), considerable flame retardancy (0.053 mm s-1), and self-extinguishing behavior, where the inherent characteristics were considerably improved by crosslinking. Different concentrations of the crosslinker altered the mechanical properties, while the anisotropic structure influenced the mechanical properties, combustion velocity, and to some extent thermal conductivity. Seaweed-derived aerogels possess intrinsic characteristics that could serve as a template for the future development of sustainable high-performance insulation materials.

The Effect of High Lignin Content on Oxidative Nanofibrillation of Wood Cell Wall.

Wood from field-grown poplars with different genotypes and varying lignin content (17.4 wt % to 30.0 wt %) were subjected to one-pot 2,2,6,6-Tetramethylpiperidin-1-yl)oxyl catalyzed oxidation and high-pressure homogenization in order to investigate nanofibrillation following simultaneous delignification and cellulose oxidation. When comparing low and high lignin wood it was found that the high lignin wood was more easily fibrillated as indicated by a higher nanofibril yield (68% and 45%) and suspension viscosity (27 and 15 mPa·s). The nanofibrils were monodisperse with diameter ranging between 1.2 and 2.0 nm as measured using atomic force microscopy. Slightly less cellulose oxidation (0.44 and 0.68 mmol·g-1) together with a reduced process yield (36% and 44%) was also found which showed that the removal of a larger amount of lignin increased the efficiency of the homogenization step despite slightly reduced oxidation of the nanofibril surfaces. The surface area of oxidized high lignin wood was also higher than low lignin wood (114 m2·g-1 and 76 m2·g-1) which implicates porosity as a factor that can influence cellulose nanofibril isolation from wood in a beneficial manner.

Biorefinery Approach for Aerogels.

According to the International Energy Agency, biorefinery is "the sustainable processing of biomass into a spectrum of marketable bio-based products (chemicals, materials) and bioenergy (fuels, power, heat)". In this review, we survey how the biorefinery approach can be applied to highly porous and nanostructured materials, namely aerogels. Historically, aerogels were first developed using inorganic matter. Subsequently, synthetic polymers were also employed. At the beginning of the 21st century, new aerogels were created based on biomass. Which sources of biomass can be used to make aerogels and how? This review answers these questions, paying special attention to bio-aerogels' environmental and biomedical applications. The article is a result of fruitful exchanges in the frame of the European project COST Action "CA 18125 AERoGELS: Advanced Engineering and Research of aeroGels for Environment and Life Sciences".

Water purification ultrafiltration membranes using nanofibers from unbleached and bleached rice straw.

There has been an increasing interest in recent years in isolating cellulose nanofibers from unbleached cellulose pulps for economic, environmental, and functional reasons. In the current work, cellulose nanofibers isolated from high-lignin unbleached neutral sulfite pulp were compared to those isolated from bleached rice straw pulp in making thin-film ultrafiltration membranes by vacuum filtration on hardened filter paper. The prepared membranes were characterized in terms of their microscopic structure, hydrophilicity, pure water flux, protein fouling, and ability to remove lime nanoparticles and purify papermaking wastewater effluent. Using cellulose nanofibers isolated from unbleached pulp facilitated the formation of a thin-film membrane (with a shorter filtration time for thin-film formation) and resulted in higher water flux than that obtained using nanofibers isolated from bleached fibers, without sacrificing its ability to remove the different pollutants.

Utilizing the Natural Composition of Brown Seaweed for the Preparation of Hybrid Ink for 3D Printing of Hydrogels.

This study aims to utilize the natural composition of brown seaweed by deriving alginate and cellulose concurrently from the stipe (stem-like) and blade (leaf-like) structures of the seaweed; further, this is followed by fibrillation for the direct and resource-efficient preparation of alginate/cellulose nanofiber (CNF) hybrid inks for three-dimensional (3D) printing of hydrogels. The efficiency of the fibrillation process was evaluated, and the obtained gels were further studied with regard to their rheological behavior. As a proof of concept, the inks were 3D printed into discs, followed by cross-linking with CaCl2 to form biomimetic hydrogels. It was shown that the nanofibrillation process from both seaweed structures is very energy-efficient, with an energy demand lower than 1.5 kW h/kg, and with CNF dimensions below 15 nm. The inks displayed excellent shear-thinning behavior and cytocompatibility and were successfully printed into 3D discs that, after cross-linking, exhibited an interconnected network structure with favorable mechanical properties, and a cell viability of 71%. The designed 3D biomimetic hydrogels offers an environmentally benign, cost-efficient, and biocompatible material platform with a favorable structure for the development of biomedical devices, such as 3D bio printing of soft tissues.

Effect of Unbleached Rice Straw Cellulose Nanofibers on the Properties of Polysulfone Membranes.

In addition to their lower cost and more environmentally friendly nature, cellulose nanofibers isolated from unbleached pulps offer different surface properties and functionality than those isolated from bleached pulps. At the same time, nanofibers isolated from unbleached pulps keep interesting properties such as hydrophilicity and mechanical strength, close to those isolated from bleached pulps. In the current work, rice straw nanofibers (RSNF) isolated from unbleached neutral sulfite pulp (lignin content 14%) were used with polysulfone (PSF) polymer to make membrane via phase inversion. The effect of RSNF on microstructure, porosity, hydrophilicity, mechanical properties, water flux, and fouling of PSF membranes was studied. In addition, the prepared membranes were tested to remove lime nanoparticles, an example of medium-size nanoparticles. The results showed that using RSNF at loadings from 0.5 to 2 wt.% can significantly increase hydrophilicity, porosity, water flux, and antifouling properties of PSF. RSNF also brought about an increase in rejection of lime nanoparticles (up to 98% rejection) from their aqueous suspension, and at the same time, with increasing flux across the membranes. Tensile strength of the membranes improved by ~29% with addition of RSNF and the maximum improvement was obtained on using 0.5% of RSNF, while Young's modulus improved by ~40% at the same RSNF loading. As compared to previous published results on using cellulose nanofibers isolated from bleached pulps, the obtained results in the current work showed potential application of nanofibers isolated from unbleached pulps for improving important properties of PSF membranes, such as hydrophilicity, water flux, rejection, and antifouling properties.

Nanocomposite Film Based on Cellulose Acetate and Lignin-Rich Rice Straw Nanofibers.

Nanofibers isolated from unbleached neutral sulfite rice straw pulp were used to prepare transparent films without the need to modify the isolated rice straw nanofibers (RSNF). RSNF with loading from 1.25 to 10 wt.% were mixed with cellulose acetate (CA) solution in acetone and films were formed by casting. The films were characterized regarding their transparency and light transmittance, microstructure, mechanical properties, crystallinity, water contact angle, porosity, water vapor permeability, and thermal properties. The results showed good dispersion of RSNF in CA matrix and films with good transparency and homogeneity could be prepared at RSNF loadings of less than 5%. As shown from contact angle and atomic force microscopy (AFM) measurements, the RSNF resulted in increased hydrophilic nature and roughness of the films. No significant improvement in tensile strength and Young's modulus was recorded as a result of adding RSNF to CA. Addition of the RSNF did not significantly affect the porosity, crystallinity and melting temperature of CA, but slightly increased its glass transition temperature.

Potential of municipal solid waste paper as raw material for production of cellulose nanofibres.

When aiming for higher resource efficiency, greater utilization of waste streams is needed. In this work, waste paper separated from mixed municipal solid waste (MSW) was studied as a potential starting material for the production of cellulose nanofibres (CNFs). The waste paper was treated using three different techniques, namely pulping, flotation and washing, after which it was subjected to an ultrafine grinding process to produce CNFs. The energy consumption of the nanofibrillation and nanofibre morphology, as well as properties of the prepared nanofibers, were analysed. Despite the varying amounts of impurities in the waste fibres, all samples could be fibrillated into nanoscale fibres. The tensile strengths of the CNF networks ranged from 70 to 100 MPa, while the stiffness was ∼7 GPa; thus, their mechanical strength can be adequate for applications in which high purity is not required. The contact angles of the CNF networks varied depending on the used treatment method: the flotation-treated networks were more hydrophilic (contact angle 52.5°) and the washed networks were more hydrophobic (contact angle 72.6°).

Promoted hydrogel formation of lignin-containing arabinoxylan aerogel using cellulose nanofibers as a functional biomaterial.

In this work, three-dimensional (3D) aerogels and hydrogels based on lignin-containing arabinoxylan (AX) and cellulose nanofibers (CNF) were prepared. The effects of the CNF and the crosslinking with citric acid (CA) of various contents (1, 3, 5 wt%) were evaluated. All the aerogels possessed highly porous (above 98%) and lightweight structures. The AX-CNF hydrogel with a CA content of 1 wt% revealed a favorable network structure with respect to the swelling ratio; nanofiber addition resulted in a five-fold increase in the degree of swelling (68 g of water per g). The compressive properties were improved when the higher CA content (5 wt%) was used; when combined with CNF, there was a seven-fold enhancement in the compressive strength. The AX-CNF hydrogels were prepared using a green and straightforward method that utilizes sustainable resources efficiently. Therefore, such natural hydrogels could find application potential, for example in the field of soft tissue engineering.

Use of Bacterial Cellulose and Crosslinked Cellulose Nanofibers Membranes for Removal of Oil from Oil-in-Water Emulsions.

Abstract: Never-dried bacterial cellulose (BC) and crosslinked cellulose nanofibers (CNF) were used for the removal of oil from stabilized and non-stabilized oil-in-water emulsions with droplet sizes less than 1 µm. The CNF membranes were exchanged with isopropyl alcohol before drying. The microscopic structure of the prepared membranes was evaluated using scanning electron microscopy (SEM); the water flux and the rejection of oil were evaluated using a dead-end filtration cell. BC harvested after different incubation time periods (2 to 10 days) did not show a change in the width of the nanofibers, but only the thickness of the membranes was increased. Pure water flux was not affected as a result of increasing thicknesses of BC membranes harvested after 4⁻10 days while BC harvested after two days had significantly higher water flux than the others. BC showed a higher flux and efficiency in removing oil from oil emulsions than CNF membranes. Removal of oil by the different membranes from the non-stabilized oil emulsion was more efficient than from the stabilized one.

Membranes Based on Cellulose Nanofibers and Activated Carbon for Removal of Escherichia coli Bacteria from Water.

Cellulosic nanomaterials are potential candidates in different areas, especially in water treatment. In the current work, palm fruit stalks cellulose nanofibers (CNF), TEMPO-oxidized CNF (OCNF), and activated carbon (AC) were used to make thin film membranes for removal of E. coli bacteria from water. Two types of layered membranes were produced: a single layer setup of crosslinked CNF and a two-layer setup of AC/OCNF (bottom) and crosslinked CNF (up) on hardened filter paper. The prepared membranes were evaluated regarding their microstructure and layers thickness using scanning electron microscopy (SEM). Water flux and rejection of E. coli bacteria was tested using dead end stirred cells at 1 MPa pressure. Thickness of the cosslinked CNF layer in both types of membranes was about 0.75 micron. The results showed that exchanging water by isopropyl alcohol before drying increased porosity of membranes, and thus resulted in increasing pure water flux and flux of bacteria suspension. The two-layer AC/OCNF/CNF membrane had much higher water flux than the single layer CNF due to higher porosity seen on the surface of the former. Both types of membranes showed high capability of removing E. coli bacteria (rejection ~96⁻99%) with slightly higher efficiency for the AC/OCNF/CNF membrane than CNF membrane. AC/OCNF/CNF membrane also showed resistance against growth of E. coli and S. aureus bacteria on the upper CNF surface while the single layer CNF membrane did not show resistance against growth of the aforementioned bacteria.