Cellulose Surface Research Articles

Plant-inspired modification strategy for the large-scale, versatile preparation of cellulose-based products with highly effective and durable UV-protective, antimicrobial, and antiviral performance

Cellulose is a versatile and renewable material used in clinical settings for dressings, masks, and bedding. However, adding functions like UV-shielding, antiviral, and antibacterial properties can be challenging due to its poor adhesion and reduced effectiveness over time. Inspired by the natural structure of plant cell walls, we propose a scalable and versatile strategy by introducing curcumin and lysine to the cellulose surface via the Mannich reaction to achieve a durable antimicrobial and UV-protective cellulose surface. The ensuring chemical configuration was characterized through Nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Additionally, X-ray diffraction analysis confirmed that the modification occurred exclusively at the cellulose surface. We found curcumin-modified sulfated nanocellulose nanofibrils (CL-SCNF) entirely block ultraviolet rays at wavelengths of 200–400 nm (UVA, UVB, and UVC) while providing 82.1 % transparency in the visible spectrum. The resultant silver bonding cellulose products exhibit high antiviral, antibacterial, and antifungal performance against bacterial phage-X174, Escherichia coli, Staphylococcus aureus, and Candida albicans. Furthermore, the strong coordination bonding of silver ions with the β-diketone system endows the final textiles with good washing stability, which can maintain 99 % of antimicrobial activity after repeated washing. This eco-friendly and highly scalable method for fabricating antimicrobial cellulose surfaces will be attractive to manufacturers of protective equipment and textiles, as it offers great potential for applications in a wide range of fields.

Specific ion effects on lignin adsorption and transport through cellulose confinements

The presence of ions in a solution is anticipated to induce distinct effects on macromolecules. Consequently, the tuning of adsorption and mass transfer of lignin molecules can be achieved by incorporating ions with chaotropic or kosmotropic characteristics. This study examines the adsorption and mass transfer behavior of lignin molecules across model cellulose membranes in presence of ions from the Hofmeister series. Experimental investigations encompassed the use of diffusion cells to quantify lignin's mass transfer through the membranes, and quartz crystal microbalance with dissipation (QCM-D) monitoring was used for adsorption studies. Notably, at high ion concentrations, the mass transport rate of lignin was observed to be lower in the presence of highly hydrated (kosmotropic) sulfate ions, conforming to the Hofmeister series. Intriguingly, this relationship was not apparent at lower ion concentrations. Furthermore, QCM-D experiments indicated that lignin displayed higher adsorption onto the cellulose surface when exposed to less hydrated (chaotropic) nitrate anions. This behavior can be rationalized by considering the system's increased entropy gain, facilitated by the release of adsorbed ions and water molecules from the cellulose surface upon lignin adsorption. This study highlights the complexity of ion-specific effects on mass transfer and adsorption processes and their dependency on ion concentrations.

Novel supramolecular deep eutectic solvent-enabled in-situ lignin protection for full valorization of all components of wheat straw

Lignin is usually deemed as an inhibitor to enzymatic hydrolysis of cellulose due to its physical barrier, non-productive adsorption, and steric hindrance. Herein, a novel supramolecular deep eutectic solvent (SUPRADES), comprising ethylene glycol and citric acid in 5:1 M ratio, and β-cyclodextrin (β-CD) in a concentration of 3.5% (w/w), was developed to be efficient for pretreating wheat straw. The delignification rate, cellulose enzymatic digestibility, and hemicellulose removal reached 90.45%, 97.36% and 87.24%, respectively, which may be attributed to the introduction of β-CD with superior ability of both adsorption and in-situ lignin protection to efficiently remove lignin with intact structure from cellulose surface. The mechanisms of high-efficiency lignin extraction/protection were systematically illustrated by adsorption kinetics. Moreover, Trichosporon cutaneum grown on the hemicellulose and cellulose fractions after pretreatment afforded 8.8 g total lipids from 100 g wheat straw. The green SUPARDES pretreatment strategy offers a new avenue for upgrading lignocellulose to biofuels.

Functional characterization of fungal lytic polysaccharide monooxygenases for cellulose surface oxidation

BackgroundMicrobial lytic polysaccharide monooxygenases (LPMOs) cleave diverse biomass polysaccharides, including cellulose and hemicelluloses, by initial oxidation at C1 or C4 of glycan chains. Within the Carbohydrate-Active Enzymes (CAZy) classification, Auxiliary Activity Family 9 (AA9) comprises the first and largest group of fungal LPMOs, which are often also found in tandem with non-catalytic carbohydrate-binding modules (CBMs). LPMOs originally attracted attention for their ability to potentiate complete biomass deconstruction to monosaccharides. More recently, LPMOs have been applied for selective surface modification of insoluble cellulose and chitin.ResultsTo further explore the catalytic diversity of AA9 LPMOs, over 17,000 sequences were extracted from public databases, filtered, and used to construct a sequence similarity network (SSN) comprising 33 phylogenetically supported clusters. From these, 32 targets were produced successfully in the industrial filamentous fungus Aspergillus niger, 25 of which produced detectable LPMO activity. Detailed biochemical characterization of the eight most highly produced targets revealed individual C1, C4, and mixed C1/C4 regiospecificities of cellulose surface oxidation, different redox co-substrate preferences, and CBM targeting effects. Specifically, the presence of a CBM correlated with increased formation of soluble oxidized products and a more localized pattern of surface oxidation, as indicated by carbonyl-specific fluorescent labeling. On the other hand, LPMOs without native CBMs were associated with minimal release of soluble products and comparatively dispersed oxidation pattern.ConclusionsThis work provides insight into the structural and functional diversity of LPMOs, and highlights the need for further detailed characterization of individual enzymes to identify those best suited for cellulose saccharification versus surface functionalization toward biomaterials applications.

Flexible, high-performance and facile PVA/cellulose/Ag SERS chips for in-situ and rapid detection of thiram pesticide in apple juice

Flexible surface-enhanced Raman scattering (SERS) sensors have gained significant attention for their practical applications in detecting chemical and biological molecules. However, the fabrication of flexible SERS chips is often complex and requires advanced techniques. In this study, we present a simple and rapid method to design a flexible SERS chip based on polyvinyl alcohol (PVA), cellulose, and silver nanoparticles (AgNPs) using mechanical stirring and drying methods. Benefiting from the abundant hydroxide groups on cellulose, AgNPs easily adhere and distribute evenly on the cellulose surface. The combination of PVA and cellulose forms a bendable film-like SERS chip. This chip allows convenient immersion in liquid analyte samples. We demonstrate its effectiveness by using it to detect the thiram pesticide in apple juice using the “dip and dry” method, achieving an outstanding detection limit of 1.01 × 10−8 M. The Raman signals on the SERS chips exhibit high repeatability and reproducibility, with relative standard deviation values below 10%. These findings show that the flexible PVA/cellulose/Ag SERS chips is a strong candidate for real-world analysis.

Research on Water Stability and Crack Resistance of Waste Cellulose Acetate–Reinforced Asphalt Mixtures Based on Response-Surface Methodology

The objective of this study was to explore the engineering application potential of waste cigarette butts and to investigate the effect of waste cellulose acetate (WCA) as reinforcement material on the performance of asphalt mixtures. A performance prediction model was also constructed to explore the optimal mixture preparation scheme. In this study, a scanning electron microscope (SEM) was used to visually characterize the surface morphology of WCA. The elemental composition of the cellulose surface was determined semiquantitatively using an energy dispersive spectrometer (EDS). The experimental design was carried out following the face-centered central composite design (FCCD) of the response-surface methodology (RSM), taking WCA shearing time, WCA content, and asphalt-aggregate ratio as variable factors, and the splitting strength (Rdry), freeze–thaw splitting strength (Rsaturated), and tensile strength ratio (TSR) of the mixtures as response variables. The software Design-Expert was adopted to construct and optimize the model under multiple responses. The road performance was verified by rutting test, low-temperature bending test, and water immersion Marshall test. The results showed that WCA is a kind of organic cellulose with a smooth surface and cloverlike cross section, which can significantly improve the mixture’s crack resistance and water stability. The performance prediction models all achieved a fit of 90% or higher. The best parameters recommended by Design-Expert were WCA content of 0.201%, WCA shearing time of 11.847 min, and asphalt-aggregate ratio of 5.683%, and the WCA-reinforced asphalt mixture Rdry, Rsaturated, and TSR values were 1.38 MPa, 1.24 MPa, and 89.86%, respectively, all of which were within the 95% prediction interval of the model predicted values. In addition, the road performance tests showed that WCA significantly improved the mixture’s flexural strength and water stability, but harmed the high-temperature rutting resistance. WCA has a significant reinforcing effect on asphalt mixture, which has a certain reference value for recycling waste cigarette butts and developing green road materials. In addition, the FCCD model has high accuracy and can effectively guide the road material preparation process.

Cellulose Dissolution, Modification, and the Derived Hydrogel: A Review.

The cellulose-based hydrogel has occupied a pivotal position in almost all walks of life. However, the native cellulose can not be directly used for preparing hydrogel due to the complex non-covalent interactions. Some literature has discussed the dissolution and modification of cellulose but has yet to address the influence of the pretreatment on the as-prepared hydrogels. Firstly, the "touching" of cellulose by derived and non-derived solvents was introduced, namely, the dissolution of cellulose. Secondly, the "conversion" of functional groups on the cellulose surface by special routes, which is the modification of cellulose. The above-mentioned two parts were intended to explain the changes in physicochemical properties of cellulose by these routes and their influences on the subsequent hydrogel preparation. Finally, the "reinforcement" of cellulose-based hydrogels by physical and chemical techniques was summarized, viz., improving the mechanical properties of cellulose-based hydrogels and the changes in the multi-level structure of the interior of cellulose-based hydrogels.

Heterogeneous Hierarchical Self-Assembly Forming Crystalline Nanocellulose–CaCO3 Hybrid Nanoparticle Biocomposites

Nanocellulose is increasingly proposed as a sustainable raw material having strong interparticle bonding. However, cellulose alone has limited bending and impact resistance. We newly observe self-assembly between crystalline nanocellulose (CNC) and ultrafine ground chemical-free calcium carbonate nanoparticles (UGCC). The suspension displays an intrinsic gel-like state, and heterogeneous adsorption occurs under the specific conditions where Brownian motion of both species is arrested by application of ultralow shear (0.01 s−1). In contrast, simple static aging of the mixture leads to autoflocculation of each species independently. The heterogeneous adsorption results in compound particle self-assembly leading to multi-level hierarchical structures depending on relative species size and concentration ratio. Fine particles from species 1 adsorb onto the coarser complementary particles of species 2 and vice versa. Depending also on whether CNC or UGCC particles are in excess, the structural assembly occurs primarily through either CNC–CNC hydrogen bonding or CaCO3–CaCO3 autogenous flocculation, respectively. Controlling the hierarchical composite structure bonding in this way, the resulting morphology can express dual or predominantly single either mineralic or cellulosic surface properties. Novel complex hybrid biocomposite materials can therefore be produced having designable compatibility across a broad range of both natural and oil-based polymeric materials. Both CNC and UGCC are exemplified here via commercial products.

Influence of Different Treatments on the Structure and Conversion of Silicon Species in Rice Straw to Tetraethyl Orthosilicate (TEOS).

The production of tetraethyl orthosilicate (TEOS) from biomass provides a new way for TEOS production and biomass valorization. In this study, rice straw was treated using different fractionation methods, and the content, state, and reactivity of Si in the treated samples were investigated. It was found that acid treatment and ethanol extraction kept most Si in the biomass, while alkali treatment caused significant Si loss. Si was mainly present in the SiOx , Si-O-C, and Si-O-Si states in the surface of raw rice straw, cellulose and Klason lignin. The results showed that the Si-O-Si state in rice straw was beneficial for the formation of TEOS. The removal of lipids from rice straw facilitated the production of TEOS, giving the highest TEOS yield of 76.2 %. In contrast, the production of TEOS from other samples became difficult; the simultaneous conversion of the three organic components of rice straw also facilitated the production of TEOS.

Dispersion of Cellulose Nanofibers in Methacrylate-Based Nanocomposites.

Poly(methylmethacrylate-co-methacrylic acid) (PMMA-co-MAA) polymers were prepared via cobalt-mediated free radical copolymerization and were characterized after synthesis. The synthesis led to a 98.5% conversion and a final ratio between the two units, MMA/MAA, was equal to 63:37 mol%. PMMA-co-MAA was then used as a matrix for cellulose-based nanocomposites to tailor filler compatibility, thanks to the presence of carboxylic groups capable of generating strong H-bonds with the cellulose surface. Cellulose nanofibers (CNFs) were dispersed using a solution with a mixture of two solvents to tailor compatibility of both the components. For this purpose, CNFs were successfully re-dispersed in methanol using the solvent exchange method and tetrahydrofuran/methanol mixtures at different ratios were used for the preparation of the films. Fully transparent films of PMMA-co-MAA + CNF were prepared up to 15 wt% of CNF with a good dispersion in the matrix. This dispersion state leads to the reinforcement of the polymethacrylate matrix, increasing its tensile strength whilst preserving optical transparency.

Cellulose-Supported Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides.

Herein, we describe efficient nanogold-catalyzed cycloisomerization reactions of alkynoic acids and allenynamides to enol lactones and dihydropyrroles, respectively (the latter via an Alder-ene reaction). The gold nanoparticles were immobilized on thiol-functionalized microcrystalline cellulose and characterized by electron microscopy (HAADF-STEM) and by XPS. The thiol-stabilized gold nanoparticles (Au0) were obtained in the size range 1.5-6 nm at the cellulose surface. The robust and sustainable cellulose-supported gold nanocatalyst can be recycled for multiple cycles without losing activity.

Optimized Lytic Polysaccharide Monooxygenase Action Increases Fiber Accessibility and Fibrillation by Releasing Tension Stress in Cellulose Cotton Fibers.

Lytic polysaccharide monooxygenase (LPMO) enzymes have recently shaken up our knowledge of the enzymatic degradation of biopolymers and cellulose in particular. This unique class of metalloenzymes cleaves cellulose and other recalcitrant polysaccharides using an oxidative mechanism. Despite their potential in biomass saccharification and cellulose fibrillation, the detailed mode of action of LPMOs at the surface of cellulose fibers still remains poorly understood and highly challenging to investigate. In this study, we first determined the optimal parameters (temperature, pH, enzyme concentration, and pulp consistency) of LPMO action on the cellulose fibers by analyzing the changes in molar mass distribution of solubilized fibers using high performance size exclusion chromatography (HPSEC). Using an experimental design approach with a fungal LPMO from the AA9 family (PaLPMO9H) and cotton fibers, we revealed a maximum decrease in molar mass at 26.6 °C and pH 5.5, with 1.6% w/w enzyme loading in dilute cellulose dispersions (100 mg of cellulose at 0.5% w/v). These optimal conditions were used to further investigate the effect of PaLPMO9H on the cellulosic fiber structure. Direct visualization of the fiber surface by scanning electron microscopy (SEM) revealed that PaLPMO9H created cracks on the cellulose surface while it attacked tension regions that triggered the rearrangement of cellulose chains. Solid-state NMR indicated that PaLPMO9H increased the lateral fibril dimension and created novel accessible surfaces. This study confirms the LPMO-driven disruption of cellulose fibers and extends our knowledge of the mechanism underlying such modifications. We hypothesize that the oxidative cleavage at the surface of the fibers releases the tension stress with loosening of the fiber structure and peeling of the surface, thereby increasing the accessibility and facilitating fibrillation.

Tuning the water interactions of cellulose nanofibril hydrogels using willow bark extract

Cellulose nanofibrils (CNFs) are increasingly used as precursors for foams, films and composites, where water interactions are of great importance. In this study, we used willow bark extract (WBE), an underrated natural source of bioactive phenolic compounds, as a plant-based modifier for CNF hydrogels, without compromising their mechanical properties. We found that the introduction of WBE into both native, mechanically fibrillated CNFs and TEMPO-oxidized CNFs increased considerably the storage modulus of the hydrogels and reduced their swelling ratio in water up to 5–7 times. A detailed chemical analysis revealed that WBE is composed of several phenolic compounds in addition to potassium salts. Whereas the salt ions reduced the repulsion between fibrils and created denser CNF networks, the phenolic compounds - which adsorbed readily on the cellulose surfaces - played an important role in assisting the flowability of the hydrogels at high shear strains by reducing the flocculation tendency, often observed in pure and salt-containing CNFs, and contributed to the structural integrity of the CNF network in aqueous environment. Surprisingly, the willow bark extract exhibited hemolysis activity, which highlights the importance of more thorough investigations of biocompatibility of natural materials. WBE shows great potential for managing the water interactions of CNF-based products.

Cellulosic surfaces endowed with chemical reactivity by physical adsorption of functionalized polysaccharides

Cellulosic surfaces endowed with chemical reactivity by physical adsorption of functionalized polysaccharides

Inhibition of α-amylase and amyloglucosidase by cellulose nanofibrils with different surface charge and spectroscopic analysis of their interaction mechanism

We investigated the inhibition effect of carboxymethylated cellulose nanofibrils with four different surface chargeon α-amylase and amyloglucosidase via enzyme activity inhibition assay, fluorescence spectra and secondary structure change analysis. These results revealed that cellulose nanofibril with lowest surface charge displayed the greatest inhibition effects against α-amylase (9.81 mg/mL) and amyloglucosidase (13.16 mg/mL). All cellulose nanofibrils in starch model significantly (p < 0.05) inhibited the starch digestion, where the inhibition effect was negatively correlated with the magnitude of particle surface charge. Cellulose nanofibrils could bind α-amylase or amyloglucosidase to form new complex in the manner of static quenching. The thermodynamic parameters demonstrated that the cellulose nanofibrils-starch hydrolase (α-amylase or amyloglucosidase) complexes were formed spontaneously via hydrophobic effects. Additionally, Fourier transform Infrared spectra exhibited the changes in the fraction of secondary structures of starch hydrolase after the interactions with carboxymethylated cellulose nanofibrils. These data provide a convenient and simple method tailor gastrointestinal digestion of starch by changing cellulose surface charge, to control postprandial serum glucose upsurge.

Biofilm-Mediated Fragmentation and Degradation of Microcrystalline Cellulose by Cellulomonas flavigena KU (ATCC 53703).

Cellulomonas flavigena KU (ATCC 53703) produces an extracellular matrix involved in the degradation of microcrystalline cellulose. This extracellular material is primarily composed of the gel-forming, β-1,3-glucan known as curdlan and associated, cellulose-degrading enzymes. In this study, the effects of various forms of nutrient limitation on cellulose attachment, cellular aggregation, curdlan production, and biofilm formation were investigated throughout a 7-day incubation period by using phase-contrast microscopy. Compared to cultures grown in non-limiting media, nitrogen-limitation promoted early attachment of C. flavigena KU cells to the cellulose surface, and cellulose attachment was congruent with cellular aggregation and curdlan production. Over the course of the experiment, microcolonies of attached cells grew into curdlan-producing biofilms on the cellulose. By contrast, bacterial cells grown on cellulose in non-limiting media remained unattached and unaggregated throughout most of the incubation period. By 7days of incubation, bacterial aggregation was ninefold greater in N-limited cultures compared to nutritionally complete cultures. In a similar way, phosphorus- and vitamin-limitation (i.e., yeast extract-limitation) also resulted in early cellulose attachment and biofilm formation. Furthermore, nutrient limitation promoted more rapid and efficient fragmentation and degradation of cellulose, with cellulose fragments in low-N media averaging half the size of those in high-N media after 7days. Two modes of cellulose degradation are proposed for C. flavigena KU, a "planktonic mode" and a "biofilm mode". Similar observations have been reported for other curdlan-producing cellulomonads, and these differing cellulose degradation strategies may ultimately prove to reflect sequential stages of a multifaceted biofilm cycle important in the bioconversion of this abundant and renewable natural resource.

Water Influence on the Physico-Chemical Properties and 3D Printability of Choline Acrylate-Bacterial Cellulose Inks.

The aim of this work was to study the influence of water as a co-solvent on the interaction between a polymerizable ionic liquid-choline acrylate (ChA)-and bacterial cellulose. Bacterial cellulose dispersed in ChA is a new type of UV-curable biopolymer-based ink that is a prospective material for the 3D printing of green composite ion-gels. Higher cellulose content in inks is beneficial for the ecological and mechanical properties of materials, and leads to increased viscosity and the yield stress of such systems and hampers printability. It was found that the addition of water results in (1) a decrease in the solvent viscosity and yield stress; and (2) a decrease in the stability of dispersion toward phase separation under stress. In this work, an optimal composition in the range of 30-40 wt% water content demonstrating 97-160 Pa of yield stress was found that ensures the printability and stability of inks. The rheological properties of inks and mechanical characteristics (0.7-0.8 MPa strength and 1.1-1.2 MPa Young's modulus) were obtained. The mechanism of influence of the ratio ChA/water on the properties of ink was revealed with atomic force microscopy, wide-angle X-ray diffraction studies of bacterial cellulose after regeneration from solvent, and computer simulation of ChA/water mixtures and their interaction with the cellulose surface.

Ultrasound-assisted extraction and characteristics of maize polysaccharides from different sites

Antitumor, antioxidant, hypoglycemic, and immunomodulatory properties are all exhibited by maize polysaccharides. With the increasing sophistication of maize polysaccharide extraction methods, enzymatic method is no longer limited to a single enzyme to extract polysaccharides, and is more often used in combination with ultrasound or microwave, or combination with different enzymes. Ultrasound has a good cell wall-breaking effect, making it easier to dislodge lignin and hemicellulose from the cellulose surface of the maize husk. The “water extraction and alcohol precipitation” method is the simplest but most resource- and time-consuming process. However, the “ultrasound-assisted extraction” and “microwave-assisted extraction” methods not only compensate for the shortcoming, but also increase the extraction rate. Herein, the preparation, structural analysis, and activities of maize polysaccharides were analyzed and discussed.

Hornification in commercial chemical pulps: Dependence on water removal and hornification mechanisms

Understanding cellulose hornification provides crucial information regarding drying of pulp, paper, and other cellulosic materials as well as recycling them. By measuring drainage, fiber width, and water retention value of hardwood and softwood pulps before and after sheet forming and after different drying procedures at different achieved levels of solids, the hornification was evaluated. The water retention value was also measured for the pulps when dried from acetone to observe what happens when hydrogen bonds are not available in the liquid phase. The drainage and fiber width decreased with increasing solids content; the fibers became increasingly stiff with increased water removal. Water retention measurements indicated that hornification is a stepwise process with large drops in fiber flexibility as soon as the fibers are being processed and later after a certain amount of water has been removed. In sum, the fibers must achieve a certain solids content to show hornification, and hydrogen bonds in water draw the cellulose surfaces together to create hornification. The mechanism of hornification is believed to be driven by hydrogen bonds and related to the distance between cellulose chains inside the fiber wall. Other types of bonds are probably also present and help with the irreversibility of hornification.

On the chemical fate of propyl gallate as stabilizer in Lyocell spinning dopes

Propyl gallate (PG, gallic acid propyl ester, Tenox®) is a very frequently used stabilizer and antioxidant in food and material applications, also used on large scale in the Lyocell process to stabilize the cellulose spinning dopes. In the present study we have investigated the fate of PG under classical Lyocell conditions (cellulose dissolved in N-methylmorpholine-N-oxide monohydrate at temperatures above 80 °C) by means of multiple analytical techniques, including NMR, GPC, and MS-hyphenated chromatography. It is demonstrated that propyl gallate is quickly hydrolyzed to gallate or, as a side reaction, aminolyzed to gallic acid morpholide. The products of the antioxidative action of gallic acid and propyl gallate, namely ellagic acid and its bis(ortho-quinone), are very easily adsorbed to cellulosic surfaces and are chiefly responsible for the discoloration of Lyocell spinning dopes and the resulting fibers. However, gallic acid morpholide and its parent compound gallic amide, while both having good antioxidant activity similar to propyl gallate itself, do neither form ellagic acid nor the bis(ortho-quinone) and are thus significantly superior to the conventionally used propyl gallate with regard to chromophore generation and resulting brightness loss. Also gallate moieties in tannins can be converted into the amide or morpholide to be further used as Lyocell stabilizers, which might open the way both to new Lyocell stabilizers and to a niche utilization for tannins.Graphical abstract