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In recent times, cellulose, an abundant and renewable biopolymer, has attracted considerable interest due to its potential applications in nanotechnology. This review explores the latest developments in cellulose-based nanomaterial synthesis, functionalization, and commercial applications. Beginning with an overview of the diverse sources of cellulose and the methods employed for its isolation and purification, the review delves into the various techniques used for the synthesis of cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs), highlighting their unique properties and potential applications. Furthermore, the functionalization strategies employed to enhance the properties and tailor the functionalities of cellulose-based nanomaterials were discussed. The review also provides insights into the emerging commercial applications of cellulose-based nanomaterials across diverse sectors, including packaging, biomedical engineering, textiles, and environmental remediation. Finally, challenges and prospects for the widespread adoption of cellulose-based nanomaterials are outlined, emphasizing the need for further research and development to unlock their full potential in sustainable and innovative applications.
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Here, biogenic and multifunctional active food coatings and packaging with UV shielding and antimicrobial properties were structured from the aqueous dispersion of an industrial byproduct, suberin, which was stabilized with amphiphilic cellulose nanofibers (CNF). The dual-functioning CNF, synthesized in a deep eutectic solvent, functioned as an efficient suberin dispersant and reinforcing agent in the packaging design. The nanofibrillar percolation network of CNF provided a steric hindrance against the coalescence of the suberin particles. The low CNF dosage of 0.5 wt% resulted in dispersion with optimal viscosity (208.70 Pa.s), enhanced stability (instability index of <0.001), and reduced particle size (9.37 ± 2.43 µm). The dispersion of suberin and CNF was further converted into self-standing films with superior UV-blocking capability, good thermal stability, improved hydrophobicity (increase in water contact angle from 61° ± 0.15 to 83° ± 5.11), and antimicrobial properties against gram-negative bacteria. Finally, the synergistic bicomponent dispersions were demonstrated as fruit coatings for bananas and packaging for strawberries to promote their self-life. The coatings and packaging considerably mitigated fruit deterioration and improved their freshness by preventing moisture loss and microbial attack. This sustainable approach is expected to pave the way toward advanced, biogenic, and active food packaging based on widely available bioresources.
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Celulose , Embalagem de Alimentos , Lipídeos , Nanofibras , Madeira , Nanofibras/química , Celulose/química , Embalagem de Alimentos/métodos , Madeira/química , Lipídeos/química , Interações Hidrofóbicas e Hidrofílicas , Antibacterianos/química , Antibacterianos/farmacologia , Viscosidade , Musa/química , Água/química , Bactérias Gram-Negativas/efeitos dos fármacos , Frutas/químicaRESUMO
Ionogels have grabbed significant interest in various applications, from sensors and actuators to wearable electronics and energy storage devices. However, current ionogels suffer from low strength and poor ionic conductivity, limiting their performance in practical applications. Here, inspired by the mechanical reinforcement of natural biomacromolecules through noncovalent aggregates, a strategy is proposed to construct nanofibril-based ionogels through complex coacervation-induced assembly. Cellulose nanofibrils (CNFs) can bundle together with poly(ionic liquid) (PIL) to form a superstrong nanofibrous network, in which the ionic liquid (IL) can be retained to form ionogels with high liquid inclusion and ionic conductivity. The strength of the CNF-PIL-IL ionogels can be tuned by the IL content over a wide range of up to 78 MPa. The optical transparency, high strength, and hygroscopicity enabled them to be promising candidates in moist-electricity generation and applications such as energy harvesting windows and wearable power generators. In addition, the ionogels are degradable and the ionogel-based generators can be recycled through dehydration. Our strategy suggests perspectives for the fabrication of high-strength and multifunctional ionogels for sustainable applications.
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The potential applications of cellulose nanofibril-based foam materials can be expanded by their enhanced water durability. This study proposes two crosslinking methods to improve the water durability of the oven-dried carboxymethylated cellulose nanofibril (CMCNF) foam. The first method involves the addition of a crosslinker, polyamideamine epichlorohydrin. The second method is the self-crosslinking of CMCNFs via heat treatment at 140 °C for less than an hour, which is a simple way to crosslink CMCNF-based materials. Both crosslinking methods resulted in excellent water durability and wet resilience of the foams, which also exhibited high water absorbency. Furthermore, neither method affected the structural nor mechanical properties of the oven-dried CMCNF foams. In particular, self-crosslinking by heat treatment proved to be as effective as using a crosslinking agent. Compared to the freeze-dried foam, the oven-dried foam exhibited slower methylene blue (MB) dye adsorption but a higher maximum adsorption capacity (238-250 mg/g), attributed to the closed pore structure and a larger specific surface area. In addition, the isotherm and reusability of the foam for MB adsorption were investigated. These crosslinking processes expanded the potential use of oven-dried CMCNF foams as adsorbents for cationic dyes.
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Celulose , Corantes , Reagentes de Ligações Cruzadas , Azul de Metileno , Nanofibras , Água , Nanofibras/química , Adsorção , Água/química , Celulose/química , Celulose/análogos & derivados , Corantes/química , Azul de Metileno/química , Reagentes de Ligações Cruzadas/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Epicloroidrina/químicaRESUMO
Electromagnetic sensors with flexible antennas as sensing elements have attracted increasing attention in noninvasive continuous glucose monitoring for diabetic patients. The significant radiation performance loss of flexible antennas during mechanical deformation impairs the reliability of glucose monitoring. Here, we present flexible ultrawideband monopole antennas composed of Ti3C2 MXene and cellulose nanofibril (CNF) composite films for continuous glucose monitoring. The flexible MXene/CNF antenna with 20% CNF content can obtain a gain of up to 3.33 dBi and a radiation efficiency of up to 65.40% at a frequency range from 2.3 to 6.0 GHz. Compared with the pure MXene antenna, this antenna offers a comparable radiation performance and a lower performance loss in mechanical bending deformation. Moreover, the MXene/CNF antenna shows a stable response to fetal bovine serum/glucose, with a correlation of >0.9 at the reference glucose levels, and responds sensitively to the variations in blood glucose levels during human trials. The proposed strategy enhancing the mechanical robustness of MXene-based flexible antennas makes metallic two-dimensional nanomaterials more promising in wearable electromagnetic sensors.
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Glicemia , Celulose , Titânio , Celulose/química , Titânio/química , Humanos , Glicemia/análise , Nanocompostos/química , Técnicas Biossensoriais/métodos , Dispositivos Eletrônicos Vestíveis , Animais , Nanofibras/química , Glucose/análiseRESUMO
Improving interface connectivity of magnetic nanoparticles in carbon aerogels is crucial, yet challenging for assembling lightweight, elastic, high-performance, and multifunctional carbon architectures. Here, an in situ growth strategy to achieve high dispersion of metal-organic frameworks (MOFs)-anchored cellulose nanofibrils to enhance the interface connection quality is proposed. Followed by a facile freeze-casting and carbonization treatment, sustainable biomimetic porous carbon aerogels with highly dispersed and closely connected MOF-derived magnetic nano-capsules are fabricated. Thanks to the tight interface bonding of nano-capsule microstructure, these aerogels showcase remarkable mechanical robustness and flexibility, tunable electrical conductivity and magnetization intensity, and excellent electromagnetic wave absorption performance. Achieving a reflection loss of -70.8 dB and a broadened effective absorption bandwidth of 6.0 GHz at a filling fraction of merely 2.2 wt.%, leading to a specific reflection loss of -1450 dB mm-1, surpassing all carbon-based aerogel absorbers so far reported. Meanwhile, the aerogel manifests high magnetic sensing sensibility and excellent thermal insulation. This work provides an extendable in situ growth strategy for synthesizing MOF-modified cellulose nanofibril structures, thereby promoting the development of high-value-added multifunctional magnetic carbon aerogels for applications in electromagnetic compatibility and protection, thermal management, diversified sensing, Internet of Things devices, and aerospace.
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Regioselective C6 and C2,C3 carboxylated cellulose nanofibrils (CNFs) have been robustly generated from dissolving pulp, a readily available source of unmodified cellulose, via stoichiometrically optimized 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO)-mediated and sequential sodium periodate-sodium chlorite (PC) oxidation coupled with high-speed blending. Both regioselectively optimized carboxylated CNF series possess the widest ranges of comparable charges (0.72-1.48 mmol/g for T-CNFs vs. 0.72-1.10 mmol/g for PC-CNFs), but similar ranges of thickness (1.3-2.4 nm for T-CNF, 1.8-2.7 nm PC-CNF), widths (4.6-6.6 nm T-CNF, 5.5-5.9 nm PC-CNF), and lengths (254-481 nm T-CNF, 247-442 nm PC-CNF). TEMPO-mediated oxidation is milder and one-pot, thus more time and process efficient, whereas the sequential periodate-chlorite oxidation produces C2,C3 dialdehyde intermediates that are amenable to further chemical functionalization or post-reactions. These two well-characterized regioselectively carboxylated CNF series represent coherent cellulose nanomaterial models from a single woody source and have served as references for their safety study toward the development of a safer-by-design substance evaluation tool.
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Cellulose nanofibrils (CNFs) exhibit excellent mechanical properties and are used to reinforce various composites. The effects of incorporating CNFs into commercial mineral trioxide aggregate (MTA) cements (NEX MTA (NEX) and ProRoot® MTA (PR)) on the underwater setting properties, compressive strength, and flowability were estimated in this study. NEX mixed without CNFs disintegrated after water immersion. NEX mixed with CNF-suspended solutions showed good setting properties under water immersion and a similar compressive strength, which was kept in air (100% relative humidity). PR did not degrade after water immersion, regardless of the presence of CNFs, and no significant difference in the compressive strength caused by CNFs incorporation was detected. The relative flowability of the NEX mixture decreased with increasing CNFs content up to 1.0 w/v%. The application of CNF-incorporated MTA in various dental cases is promising because CNFs prevent the water-immersion-dependent collapse of some MTA cements immediately after mixing.
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Celulose , Materiais Restauradores do Canal Radicular , Óxidos , Compostos de Cálcio , Água , Silicatos , Compostos de Alumínio , Combinação de MedicamentosRESUMO
Developing high-performance microwave absorption (MA) materials becomes an urgent concern in the field of electromagnetic protection. Constructing porous framework is an efficient approach to MA owing to the abilities of adjusting impedance matching and providing more reflection and scattering paths for electromagnetic waves. Herein, a cellulose nanofibril (CNF)/honeycomb-like carbon-shell encapsulated FeCoNi@C/carbon nanotube (CNT) composite aerogel was fabricated via a facile freeze-drying method. The super-lightweight composites showed a distinctive gradient structure for reflection and scattering inside aerogel pores, micrometer small pores, and nano-fillers on the pore walls. The composite aerogel showed an ideal minimum reflection loss (RLmin) of -43.6 dB and remarkable adjustable effective absorption bandwidth (EAB) of 12.18 GHz due to good impedance matching, unique gradient porous structure, and synergies of multiple loss mechanisms. Therefore, this work will provide a viable strategy to improve the MA capability of absorbers by taking full advantage of constructing gradient reflection and scattering porous structure.
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In this work, carboxylated and amination modified cellulose nanofibrils (CNFs) were fabricated via the TEMPO catalytic oxidation system and diethylenetriamine, and collagen composite aerogels were fabricated through a simple self-assembly pretreatment and directional freeze-drying technology. Morphology analysis showed that the collagen composite aerogels had distinct layered-oriented double network structures after the self-assembly pretreatment. The intermolecular interactions between the collagen fibrils and functionalized CNFs (fCNFs) on the structures and properties of the composite aerogels were also examined through various characterization techniques. Water contact angle tests demonstrated the pH-responsive characteristics of the collagen/fCNF composite aerogels. Using 5-fluorouracil as the model drug, the pH-response mechanism was revealed. These results indicated that the collagen/fCNF composite aerogels exhibited excellent pH-responsive drug release capacities. Therefore, these pH-responsive collagen composite aerogels might have potential applications in industrial production in the biomedical, drug delivery, and tissue engineering fields.
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Nanofibras , Géis/química , Nanofibras/química , Celulose/química , Sistemas de Liberação de Medicamentos , Colágeno , Concentração de Íons de HidrogênioRESUMO
The current requirements of food safety regulations and the environmental impact stemming from plastic packaging can only be addressed by developing suitable bio-nanocomposite films. Therefore, this study is dedicated to the fabrication of multifunctional film composed of gelatin, bacterial cellulose nanofibrils (BCNF), and black pepper essential oil nanoemulsion (BPEONE) and application for duck meat preservation. BCNF was prepared through ultrasonication of cellulose derived from Komagataeibacter xylinus. BPEONE observed spherical morphology with a diameter ranging from 83.7 to 118 nm. A film matrix containing a higher gelatin proportion than BCNF was more effective in trapping BPEONE. However, increasing the BPEONE fraction showed more surface abrasion and voids in the film morphology. A flexible film with good interaction, crystallinity, and greater thermal stability (421 °C) was developed. Nevertheless, film hydrophobicity (118.89°) declined, resulting in a notable effect on water solubility, swelling, and water vapor permeability. Moreover, the film had improved antibacterial and antioxidant activities, coupled with controlled release characteristics. Consequently, the developed film effectively retarded the lipid oxidation, inhibited microbial growth, and extended the shelf life of duck meat at refrigeration (4 °C) by 3 days, and made the film a promising alternative in the realm of bio-active packaging technology.
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Celulose , Gelatina , Embalagem de Alimentos/métodos , Antibacterianos/farmacologia , Antioxidantes/farmacologiaRESUMO
Cellulosic aerogels are sustainable, biodegradable, and ultra-light porous materials with three-dimensional networks having high specific surface area. Depending on the source of precursor materials, they are categorized into plant-based aerogel, bacterial cellulosic aerogel. Different types of aerogels are also produced from microcrystalline cellulose (MCC), nanocrystalline cellulose (NCC), cellulose microfibril (CMF) and cellulose nanofibril (CNF). Furthermore, inorganic and organic substances are embedded to produce hybrid aerogel or composite aerogel for the enhancement of its performance in various fields. Mixing, gelation, solvent exchange, and drying (e.g., super critical carbon dioxide or freeze drying) are the basic steps involved in cellulosic aerogel synthesis. Based on the composition of precursors during aerogel synthesis, cellulosic aerogels have broad applications in various fields such as adsorbents, electrodes, sensors, captive deionization materials, catalysts, drug delivery, thermal and sound insulating materials. This review provided consolidated information on: (i) classification of cellulosic aerogels based on the sources of raw materials, (ii) processes involved to produce the cellulosic aerogel, (iii) cellulosic aerogel synthesized from MCC, NCC, CMF and CNF, (iv) nano particle doped cellulosic aerogel, and (v) its application in various field with future perspectives.
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Dióxido de Carbono , Celulose , Parede Celular , Dessecação , Sistemas de Liberação de MedicamentosRESUMO
A novel cellulose nanofibril/titanate nanofiber modified with CdS quantum dots hydrogel (CTH) was synthesized as an effective, stable, and recyclable photocatalytic adsorbent using cellulose nanofibril (CN), titanate nanofiber (TN), and CdS quantum dots. Within the CTH structure, CN formed an essential framework, creating a three-dimensional (3D) porous structure that enhanced the specific surface area and provided abundant adsorption sites for Cr(VI). Simultaneously, TN modified with CdS quantum dots (TN-CdS) served as a nanoscale Z-type photocatalyst, facilitating the efficient separation of photoinduced electrons and holes, further increasing the photocatalytic efficiency. The morphological, chemical, and optical properties of CTH were thoroughly characterized. The CTH demonstrated the maximum theoretical adsorption capacity of 373.3 ± 14.2 mg/g, which was 3.4 times higher than that of CN hydrogel. Furthermore, the photocatalytic reduction rate constant of the CTH was 0.0586 ± 0.0038 min-1, which was 6.4 times higher than that of TN-CdS. Notably, CTH displayed outstanding stability, maintaining 84.9 % of its initial removal efficiency even after undergoing five consecutive adsorption-desorption cycles. The remarkable performance of CTH in Cr(VI) removal was attributed to its 3D porous structure, comprising CN and TN-CdS. These findings provide novel insights into developing a stable photocatalytic adsorbent for Cr(VI) removal.
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The present study attempts to elucidate the network structure-property relationships of bacterial cellulose (BC) hydrogels comprising cellulose nanofibrils with favorable mechanical properties. To achieve this, it is necessary to establish a method based on quantitative evaluation of nanofibril network structure, rather than a simple application of classical polymer network theory. BC hydrogels with various network structures related to their mechanical properties were prepared from seven bacterial strains. The crosslink densities of the gels were determined quantitatively by a combination of fluorescence microscopy and image analysis. The tensile tests showed that the stress-strain curves of BC hydrogels exhibited strain hardening according to the power law for strain, and the power exponent had a linear relationship with the crosslink density. This result provides insight into the structure-property relationships of BC hydrogels, which could be used to inform quality control, process optimization, and high-throughput property prediction during manufacture.
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Celulose , Hidrogéis , Polímeros , Bactérias , Processamento de Imagem Assistida por ComputadorRESUMO
BNNS (boron nitride nanosheets)-CNF (cellulose nanofibrils) nanocomposite films have attracted increasing attention for advanced thermal management applications. However, the nanocomposite films reported so far generally suffer from unsatisfactory overall performance, especially for thermal conductivity and tensile strength. In this work, a nanocomposite film with excellent overall performance was prepared by using CCNF1.2 (carboxymethylated CNF with 1.2 mmol·g-1 carboxyl content) simultaneously as effective dispersant and reinforcement matrix for BNNS. The high aspect ratio of CCNF1.2 is primarily responsible for its excellent dispersion capability for BNNS, which provides strong steric hindrance repulsion force. Meanwhile, CCNF1.2 manifests the strongest hydrophobic-hydrophobic interactions with BNNS, and its carboxyl groups completely interact with the -OH of BNNS by hydrogen bonding. As a result, the BNNS-CCNF1.2 film (50 wt% BNNS) exhibits compacted aligned structure and superior comprehensive performance (125.0 MPa tensile strength, 17.3 W·m-1·K-1 in-plane thermal conductivity, and improved water resistance). This work demonstrates the effectiveness of CCNF in improving the overall performance of BNNS-CNF films and paves the way for their practical application in the advanced thermal management of next-generation electronic devices.
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The phenol-sulfuric acid (PSA) method is a widely used colorimetric method for determining the total saccharides. Microplate-based PSA methods have been developed to handle a large number of samples and reduce the use of hazardous chemicals. However, the optimal procedures and measurement conditions for this method have not yet been fully established. To address this gap, we investigated the optimal procedure for microplate-based PSA. In addition to glucose (Glc), two types of cellulose nanofibers (CNFs) were also evaluated as they are a new type of nanomaterial, and a technique to quantify the concentration of CNFs is required in their safety assessment. The results showed that the thermal reaction with sulfuric acid before the addition of phenol resulted in a higher coloration than was shown after the addition of phenol. Furthermore, the longer the resting time after shaking with phenol, the greater the coloration and smaller the variation, with a resting time of 60 min or longer being optimal. This research provides valuable insights into improving the reliability and efficiency of the PSA method, which can facilitate the analysis of saccharides and other substances in a range of applications.
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Nanofibras , Fenol , Celulose/química , Reprodutibilidade dos Testes , Fenóis , Carboidratos/análiseRESUMO
The fundamental understanding concerning cellulose-cellulose interactions under wet and dry conditions remains unclear. This is especially true regarding the drying-induced association of cellulose, commonly described as an irreversible phenomenon called hornification. A fundamental understanding of the mechanisms behind hornification would contribute to new drying techniques for cellulose-based materials in the pulp and paper industry while at the same time enhancing material properties and facilitating the recyclability of cellulose-rich materials. In the present work, the irreversible joining of cellulose-rich surfaces has been studied by subjecting cellulose nanofibril (CNF) films to different heat treatments to establish a link between reswelling properties, structural characteristics as well as chemical and mechanical analyses. A heating time/temperature dependence was observed for the reswelling of the CNF films, which is related to the extent of hornification and is different for different chemical compositions of the fibrils. Further, the results indicate that hornification is related to a diffusion process and that the reswellability increases very slowly over long time, indicating that equilibrium is not reached. Hence, hornification is suggested to be a kinetically limited phenomenon governed by non-covalent reversible interactions and a time/temperature dependence on their forming and breaking.
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Ecofriendly multifunctional films with only biomass-based components have gathered significant interest from researchers as next-generation materials. Following this trend, a TEMPO-oxidized cellulose nanofibril (TOCNF) film containing hydrophilic lignin (CL) was fabricated. To produce the lignin, peracetic acid oxidation was carried out, leading to the introduction of carboxyl groups into the lignin structure. By adding hydrophilic lignin, various characteristics (e.g., surface smoothness, UV protection, antimicrobial activity, and barrier properties) of the TOCNF film were enhanced. In particular, the shrinkage of CNF was successfully prevented by the addition of CL, which is attributed to the lower surface roughness (Ra) from 18.93 nm to 4.99 nm. As a result, the smooth surface of the TOCNF/CL film was shown compared to neat TOCNF film and TOCNF/Kraft lignin composite film. In addition, the TOCNF/CL film showed a superior UV blocking ability of 99.9 % with high transparency of 78.4 %, which is higher than that of CNF-lignin composite films in other research. Also, water vapor transmission rate was reduced after adding CL to TOCNF film. Consequently, the developed TOCNF/CL film can be potentially utilized in various applications, such as food packaging.
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Celulose Oxidada , Nanofibras , Celulose/química , Lignina/química , Nanofibras/química , VaporRESUMO
The composite lightweight porous material (TOCNF-G-LPM) based on TEMPO-oxidized cellulose nanofibril (TOCNF) and gelatin were facilely prepared by ambient pressure drying using glutaraldehyde as crosslinking agent. The influence of gelatin addition on the physicochemical properties of TOCNF-G-LPM was investigated. The long-size entangled structure of TOCNF maintained the skeleton network of TOCNF-G-LPM while gelatin can adjust the characteristics of highly porous network (porosity of 98.53%-97.40%) and light weight (density of 0.0236-0.0372 g/cm3) with increasing gelatin concentration (0.2-1.0 wt%). The results of scanning electron microscopy (SEM) and confocal laser scanning microscope (CLSM) indicated that the internal structure of TOCNF-G-LPM became more ordered, uniform and denser as gelatin concentration increased. Introducing gelatin decreased water and oil absorption properties, but improved the thermal, mechanical properties and shape recovery ability of TOCNF-G-LPM at appropriate addition. Furthermore, TOCNF-G-LPM showed no significant effect on the growth and reproduction of Caenorhabditis elegans (C. elegans), confirming a good biocompatibility.
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Materiais Biocompatíveis , Gelatina , Animais , Materiais Biocompatíveis/química , Porosidade , Gelatina/química , Caenorhabditis elegans , Glutaral/químicaRESUMO
This study aimed to evaluate the influence of the addition of the cationic surfactant cetyltrimethylammonium bromide (CTAB) in microfibrillated cellulose (MFC/CNFs) suspensions submitted to different pretreatments to produce redispersible spray-dried (SD) MFC/CNFs. Suspensions pretreated with 5 % and 10 % sodium silicate and oxidized with 2,2,6,6,-tetramethylpiperidinyl-1-oxyl (TEMPO) were modified with CTAB surfactant and subsequently dried by SD. The SD-MFC/CNFs aggregates were redispersed by ultrasound to produce cellulosic films by the casting method. In summary, the results demonstrated that the addition of CTAB surfactant to the TEMPO-oxidized suspension was critical to achieving the most effective redispersion. The experimental results obtained using micrographs, optical (UV-Vis), mechanical, water vapor barrier properties, and the quality index confirmed that the addition of CTAB to the TEMPO-oxidized suspension favored the redispersion of spray-dried aggregates, development of cellulosic films with attractive properties, offering possibilities for the elaboration of new products, for example, in the production of bionanocomposites with higher mechanical performance. This research brings interesting insights into the redispersion and application of SD-MFC/CNFs aggregates, strengthening the commercialization of MFC/CNFs for industrial use.