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Disease outbreaks are a major impediment to aquaculture production, and vaccines are integral for disease management. Vaccines can be expensive, vary in effectiveness, and come with adjuvant-induced adverse effects, causing fish welfare issues and negative economic impacts. Three-dimensional biopolymer hydrogels are an appealing new technology for vaccine delivery in aquaculture, with the potential for controlled release of multiple immunomodulators and antigens simultaneously, action as local depots, and tunable surface properties. This research examined the intraperitoneal implantation of a cross-linked TEMPO cellulose nanofiber (TOCNF) hydrogel formulated with a Vibrio anguillarum bacterin in Atlantic salmon with macroscopic and microscopic monitoring to 600-degree days post-implantation. Results demonstrated a modified passive integrated transponder tagging (PITT) device allowed for implantation of the hydrogel. However, the Atlantic salmon implanted with TOCNF hydrogels exhibited a significant foreign body response (FBR) compared to sham-injected negative controls. The FBR was characterized by gross and microscopic external and visceral proliferative lesions, granulomas, adhesions, and fibrosis surrounding the hydrogel using Speilberg scoring of the peritoneum and histopathology of the body wall and coelom. Acutely, gross monitoring displayed rapid coagulation of blood in response to the implantation wound with development of fibrinous adhesions surrounding the hydrogel by 72 h post-implantation consistent with early stage FBR. While these results were undesirable for aquaculture vaccines, this work informs on the innate immune response to an implanted biopolymer hydrogel in Atlantic salmon and directs future research using cellulose nanomaterial formulations in Atlantic salmon for a new generation of aquaculture vaccine technology.
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Celulose Oxidada , Doenças dos Peixes , Nanofibras , Salmo salar , Animais , Hidrogéis , Antígenos , Adjuvantes Imunológicos , Vacinas Bacterianas , Celulose , AquiculturaRESUMO
The transformative and versatile role of cellulose nanomaterials (CNMs) as an enabling technology in the preparation of multiscale mesostructured ceramics, with pore sizes in the meso- (2-50 nm) and macroporosity (above 50 nm) range with controlled porous architecture across the structure is explored. CNMs have revolutionized functional advanced materials concepts and technology by using natural resources to derive superb properties. Its unique chemical and physical properties have inspired its exploitation as a reinforcement agent, stimuli responsive tool, and templating agent mostly for biologic and polymeric materials, as well as for metals and ceramics. CNMs can act as a sacrificial filler templating agent, a surface modifier agent, and as an aid for shaping macrostructures into bulk samples. A deep knowledge of the synergistic interaction mechanisms between CNMs and ceramic particles to assemble them in solution and into solid structures is key to advance this technology, and to develop a predictive understanding of synthesis and processing mechanisms that relates morphology evolution, processing, and final physical properties. The potential ease of processing and versatility of CNMs for functional ceramic technology, intimately linked to the CNMs' nature and properties, will make a significant impact with respect to the current state of the art.
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Cellulose is the most abundant natural polymer on earth, providing a sustainable green resource that is renewable, degradable, biocompatible, and cost effective. Recently, nanocellulose-based mesoporous structures, flexible thin films, fibers, and networks are increasingly developed and used in photovoltaic devices, energy storage systems, mechanical energy harvesters, and catalysts components, showing tremendous materials science value and application potential in many energy-related fields. In this Review, the most recent advancements of processing, integration, and application of cellulose nanomaterials in the areas of solar energy harvesting, energy storage, and mechanical energy harvesting are reviewed. For solar energy harvesting, promising applications of cellulose-based nanostructures for both solar cells and photoelectrochemical electrodes development are reviewed, and their morphology-related merits are discussed. For energy storage, the discussion is primarily focused on the applications of cellulose-based nanomaterials in lithium-ion batteries, including electrodes (e.g., active materials, binders, and structural support), electrolytes, and separators. Applications of cellulose nanomaterials in supercapacitors are also reviewed briefly. For mechanical energy harvesting, the most recent technology evolution in cellulose-based triboelectric nanogenerators is reviewed, from fundamental property tuning to practical implementations. At last, the future research potential and opportunities of cellulose nanomaterials as a new energy material are discussed.
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Celulose/química , Nanoestruturas/química , Eletrodos , Energia Solar , Propriedades de Superfície , TermodinâmicaRESUMO
A recent publication in "Particle and Fibre Toxicology" reported on the gender differences in pulmonary toxicity from oro-pharyngeal aspiration of a high dose of cellulose nanocrystals. The study is timely given the growing interest in diverse commercial applications of cellulose nanomaterials, and the need for studies addressing pulmonary toxicity. The results from this study are interesting and can be strengthened with a discussion of how differences in the weights of female and male C57BL/6 mice was accounted for. Without such a discussion, the observed differences could be partially explained by the lower body weights of females, resulting in higher doses than males when standardized to body weight or lung volume. Further, few conclusions can be drawn about the pulmonary toxicity of cellulose nanocrystals given the study design: examination of a single high dose of cellulose nanocrystals, administered as a bolus, without positive or negative controls or low dose comparisons, and at an unphysiological and high dose rate. Simulating the bolus type delivery by inhalation would require a highly unrealistic exposure concentration in the g/m3 range of extremely short duration. A discussion of these limitations is missing in the paper; further speculative comparisons of cellulose nanocrystals toxicity to asbestos and carbon nanotubes in the abstract are both unwarranted and can be misleading, these materials were neither mentioned in the manuscript, nor evaluated in the study.
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Celulose , Nanotubos de Carbono , Animais , Pulmão , Camundongos , Camundongos Endogâmicos C57BL , NanopartículasRESUMO
Barrier materials are crucial in preserving product quality, safety and longevity across numerous applications, thereby contributing to sustainability, reducing waste and advancing technology. Among these materials, cellulose nanomaterials (CNs) have emerged as promising alternatives for traditional petroleum-based polymers. However, the wide range of sources and the different methods used to isolate and process CN-based materials can result in significant variations in moisture and oxygen barrier performance. In this review, we provide an in-depth discussion on the latest advancements in CN-based green barrier materials. We begin by offering a critical assessment of the barrier performance of CNs, both in their isolated form and when combined as hybrid materials. This includes their applications as standalone films, fillers and coatings in nanocomposites. This review also covers the influence of the isolation process and the stages of film formation on barrier efficacy. We further discuss the implications of the recycling process on barrier properties of CN-based materials, drawing a connection between barrier characteristics and the product's end-of-life. We conclude by highlighting the significant developments over the past five years, the present challenges, and the prospective future of CN-based materials in barrier applications.
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Hemicellulose plays a key role in both the production of cellulose nanofibrils (CNF) and their properties as suspensions and films. While the use of enzymatic and chemical pre-treatments for tailoring hemicellulose levels is well-established, post-treatment methods using enzymes remain relatively underexplored and hold significant promise for modifying CNF film properties. This study aimed to investigate the effects of enzymatic xylan removal on the properties of CNF film for packaging applications. The enzymatic post-treatment was carried out using an enzymatic cocktail enriched with endoxylanase (EX). The EX post-treated-CNFs were characterized by LALLS, XRD, and FEG-SEM, while their films were characterized in terms of physical, morphological, optical, thermal, mechanical, and barrier properties. Employing varying levels of EX facilitated the hydrolysis of 8 to 35 % of xylan, yielding CNFs with different xylan contents. Xylan was found to be vital for the stability of CNF suspensions, as its removal led to the agglomeration of nanofibrils. Nanostructures with preserved crystalline structures and different morphologies, including nanofibers, nanorods, and their hybrids were observed. The EX post-treatment contributed to a smoother film surface, improved thermostability, and better moisture barrier properties. However, as the xylan content decreased, the films became lighter (lower grammage), less strong, and more brittle. Thus, the enzymatic removal of xylan enabled the customization of CNF films' performance without affecting the inherent crystalline structure, resulting in materials with diverse functionalities that could be explored for use in packaging films.
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Celulose , Nanofibras , Xilanos , Xilanos/química , Nanofibras/química , Celulose/química , Hidrólise , Endo-1,4-beta-Xilanases/química , Endo-1,4-beta-Xilanases/metabolismoRESUMO
Cellulose nanopaper has shown great potential in diverse fields including optoelectronic devices, food packaging, biomedical application, and so forth, owing to their various advantages such as good flexibility, tunable light transmittance, high thermal stability, low thermal expansion coefficient, and superior mechanical properties. Herein, recent progress on the fabrication and applications of cellulose nanopaper is summarized and discussed based on the analyses of the latest studies. We begin with a brief introduction of the three types of nanocellulose: cellulose nanocrystals, cellulose nanofibrils and bacterial cellulose, recapitulating their differences in preparation and properties. Then, the main preparation methods of cellulose nanopaper including filtration method and casting method as well as the newly developed technology are systematically elaborated and compared. Furthermore, the advanced applications of cellulose nanopaper including energy storage, electronic devices, water treatment, and high-performance packaging materials were highlighted. Finally, the prospects and ongoing challenges of cellulose nanopaper were summarized.
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Cellulose nanomaterials (CNMs) have emerged recently as an important group of sustainable bio-based nanomaterials (NMs) with potential applications in multiple sectors, including the food, food packaging, and biomedical fields. The widening of these applications leads to increased human oral exposure to these NMs and, potentially, to adverse health outcomes. Presently, the potential hazards regarding oral exposure to CNMs are insufficiently characterised. There is a need to understand and manage the potential adverse effects that might result from the ingestion of CNMs before products using CNMs reach commercialisation. This work reviews the potential applications of CNMs in the food and biomedical sectors along with the existing toxicological in vitro and in vivo studies, while also identifying current knowledge gaps. Relevant considerations when performing toxicological studies following oral exposure to CNMs are highlighted. An increasing number of studies have been published in the last years, overall showing that ingested CNMs are not toxic to the gastrointestinal tract (GIT), suggestive of the biocompatibility of the majority of the tested CNMs. However, in vitro and in vivo genotoxicity studies, as well as long-term carcinogenic or reproductive toxicity studies, are not yet available. These studies are needed to support a wider use of CNMs in applications that can lead to human oral ingestion, thereby promoting a safe and sustainable-by-design approach.
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To improve the mechanical and barrier properties of cellulose and chitosan (CS) and to allow the application of volatile antibacterial benzyl isothiocyanate (BITC) in active packaging, a double-layer nanocomposite film was prepared. Cellulose nanofibers (CNF) were crosslinked with CS via genipin to build the substrate. Quaternized cellulose nanocrystals (QCNC) were synthesized for carrying BITC as the coating material. By the layer-by-layer self-assembly approach, CS-CNF/QCNC-BITC film was fabricated. This film possessed the tensile strength of 33.75 MPa, low permeabilities of oxygen (6.9 × 10-17 m3/s·m·Pa) and moisture (1.2 × 10-11 g/s·m·Pa), and good antibacterial activity with the inhibition zone diameters of 4.9, 4.2 and 2.7 cm against Escherichia coli, Salmonella typhimurium and Staphylococcus aureus. The total viable count, total volatile basic nitrogen and thiobarbituric acid-reactive substances of the chicken wrapped CS-CNF/QCNC-BITC were only 4.4 log CFU/g, 17.7 mg/100 g and 0.44 mg/kg at 14 days, indicating a potential application of CS-CNF/QCNC-BITC for food packaging.
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Quitosana , Nanocompostos , Nanofibras , Antibacterianos/química , Antibacterianos/farmacologia , Celulose/química , Quitosana/química , Embalagem de Alimentos , Isotiocianatos , Nanocompostos/química , Nanofibras/químicaRESUMO
The potential applications of cellulose nanomaterials (CNMs) as food additives or in food packaging, present a possible source of human ingestion. While micron- and macro-scale cellulose products are classified as Generally Regarded As Safe, the safety of ingested nano-scale cellulose is largely unknown. Using fully differentiated Caco-2 cells, the perturbation of intestinal barrier function and cytotoxicity was investigated for four nanocellulose crystals (CNCs) and four nanocellulose fibrils (CNFs) following 24 h of exposure at 50 µg/mL. Scanning electron microscope showed some aggregation of both CNCs and CNFs. X-ray photoelectron spectroscopy analyses showed that carbon and oxygen were the main elements. The zeta-potential for CNMs formulated in cell culture medium showed a negative surface charge. Two CNMs increased cell membrane permeability and three CNMs decreased the cell metabolic activity. While three CNMs lead to cytotoxic responses, no changes in apparent permeability coefficient (Papp) for dextran or tight junction integrity were found. Our results show that three CNMs induce cytotoxicity in differentiated Caco-2 cells, demonstrating the need to understand the role of size and shape. The interaction between CNMs and the intestinal epithelium needs to be evaluated to understand potential intestinal barrier dysfunction and resulting health implications following CNM ingestion.
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Celulose , Nanoestruturas , Células CACO-2 , Celulose/química , Celulose/toxicidade , Humanos , Nanoestruturas/química , Nanoestruturas/toxicidade , Permeabilidade , Junções ÍntimasRESUMO
An optimal methodology for locating and tracking cellulose nanofibers (CNFs) in vitro and in vivo is crucial to evaluate the environmental health and safety properties of these nanomaterials. Here, we report the use of a new boron-dipyrromethene (BODIPY) reactive fluorescent probe, meso-DichlorotriazineEthyl BODIPY (mDTEB), tailor-made for labeling CNFs used in simulated or in vivo ingestion exposure studies. Time-correlated single photon counting (TCSPC) fluorescence lifetime imaging microscopy (FLIM) was used to confirm covalent attachment and purity of mDTEB-labeled CNFs. The photoluminescence properties of mDTEB-labeled CNFs, characterized using fluorescence spectroscopy, include excellent stability over a wide pH range (pH2 to pH10) and high quantum yield, which provides detection at low (µM) concentrations. FLIM analysis also showed that lignin-like impurities present on the CNF reduce the fluorescence of the mDTEB-labeled CNF, via quenching. Therefore, the chemical composition and the methods of CNF production affect subsequent studies. An in vitro triculture, small intestinal, epithelial model was used to assess the toxicity of ingested mDTEB-labeled CNFs. Zebrafish (Danio rerio) were used to assess in vivo environmental toxicity studies. No cytotoxicity was observed for CNFs, or mDTEB-labeled CNFs, either in the triculture cells or in the zebrafish embryos.
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Researches of cellulose nanomaterials have seen nearly exponential growth over the past several decades for versatile applications. The characterization of nanostructural arrangement and local chemical distribution is critical to understand their role when developing cellulose materials. However, with the development of current characterization methods, the simultaneous morphological and chemical characterization of cellulose materials at nanoscale resolution is still challenging. Two fundamentally different nanoscale infrared spectroscopic techniques, namely atomic force microscope based infrared spectroscopy (AFM-IR) and infrared scattering scanning near field optical microscopy (IR s-SNOM), have been established by the integration of AFM with IR spectroscopy to realize nanoscale spatially resolved imaging for both morphological and chemical information. This review aims to summarize and highlight the recent developments in the applications of current state-of-the-art nanoscale IR spectroscopy and imaging to cellulose materials. It briefly outlines the basic principles of AFM-IR and IR s-SNOM, as well as their advantages and limitations to characterize cellulose materials. The uses of AFM-IR and IR s-SNOM for the understanding and development of cellulose materials, including cellulose nanomaterials, cellulose nanocomposites, and plant cell walls, are extensively summarized and discussed. The prospects of future developments in cellulose materials characterization are provided in the final part.
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Nanoscale-interfaced cellulose nanomaterials are extracted from polysaccharides, which are widely available in nature, biocompatible and biodegradable. Moreover, the latter have a potential to be recycled, upcycled, and formulate therefore a great theoretical predisposition to be used in a number of applications. Nanocrystals, nano-fibrils and nanofibers possess reactive functional groups that enable hydrophobic surface modifications. Analysed literature data, concerning mechanisms, pathways and kinetics, was screened, compared and assessed with regard to the demand of a catalyst, different measurement conditions and added molecule reactions. There is presently only a scarce technique description for carbonOH bond functionalization, considering the elementary chemical steps, sequences and intermediates of these (non)catalytic transformations. The overview of the prevailing basic research together with in silico modelling approach methodology gives us a deeper physical understanding of processes. Finally, to further highlight the applicability of such raw materials, the review of the development in several multidisciplinary fields was presented.
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Cellulose nanomaterials (CNMs), mainly including nanofibrillated cellulose (NFC) and cellulose nanocrystals (CNCs), have attained enormous interest due to their sustainability, biodegradability, biocompatibility, nanoscale dimensions, large surface area, facile modification of surface chemistry, as well as unique optical, mechanical, and rheological performance. One of the most fascinating properties of CNMs is their aqueous suspension rheology, i.e., CNMs helping create viscous suspensions with the formation of percolation networks and chemical interactions (e.g., van der Waals forces, hydrogen bonding, electrostatic attraction/repulsion, and hydrophobic attraction). Under continuous shearing, CNMs in an aqueous suspension can align along the flow direction, producing shear-thinning behavior. At rest, CNM suspensions regain some of their initial structure immediately, allowing rapid recovery of rheological properties. These unique flow features enable CNMs to serve as rheological modifiers in a wide range of fluid-based applications. Herein, the dependence of the rheology of CNM suspensions on test protocols, CNM inherent properties, suspension environments, and postprocessing is systematically described. A critical overview of the recent progress on fluid applications of CNMs as rheology modifiers in some emerging industrial sectors is presented as well. Future perspectives in the field are outlined to guide further research and development in using CNMs as the next generation rheological modifiers.
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Cellulose nanomaterials (CNs) are an emerging class of materials with numerous potential applications, including as additives or reinforcements for thermoplastics. Unfortunately, the preparation of CNs typically results in dilute, aqueous suspensions, and the lack of efficient water removal methods has hindered commercialization. However, water may also present opportunities for improving overall efficiencies if its potential is better understood and if it is better managed through the various stages of CN and composite production. Wet compounding represents one such possible opportunity by leveraging water's ability to aid in CN dispersion, act as a transport medium for metering and feeding of CNs, plasticize some polymers, or potentially facilitate the preparation of CNs during compounding. However, there are also considerable challenges and much investigation remains. Here, we review various wet compounding approaches used in the preparation of cellulose nanocomposites as well as the related concepts of wet feeding and wet extrusion fibrillation of cellulose. We also discuss potential opportunities, remaining challenges, and research and development needs with the ultimate goal of developing a more integrated approach to cellulose nanocomposite preparation and a more sophisticated understanding of water's role in the compounding process.
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Cellulose nanomaterials (CNMs) are a class of materials that have recently garnered attention in fields as varied as structural materials, biomaterials, rheology modifiers, construction, paper enhancement, and others. As the principal structural reinforcement of biomass giving wood its mechanical properties, CNM is strong and stiff, but also nontoxic, biodegradable, and sustainable with a very large (Gton yr-1 ) source. Unfortunately, due to the relatively young nature of the field and inherent incompatibility of CNM with most man-made materials in use today, research has tended to be more basic-science oriented rather than commercially applicable, so there are few CNM-enabled products on the market today. Herein, efforts are presented for preparing and forming cellulose nanomaterial nanocomposites. The focus is on recent efforts attempting to mitigate common impediments to practical commercialization but is also placed in context with traditional efforts. The work is presented in terms of the progress made, and still to be made, on solving the most pressing challenges-getting properties that are competitive with currently used materials, removing organic solvent, solving the inherent incompatibility between CNM and polymers of interest, and incorporation into commonly used industrial processing techniques.
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With the increasing demand for greener alternatives to fossil-derived products, research on cellulose nanomaterials (CNMs) has rapidly expanded. The combination of nanoscale properties and sustainable attributes makes CNMs an asset in the quest for a sustainable society. However, challenges such as the hydrophilic nature of CNMs, their low compatibility with non-polar matrices and modest thermal stability, slow the development of end-uses. Combination of CNMs with amphiphilic lignin can improve the thermal stability, enhance the compatibility with non-polar matrices and, additionally, endow CNMs with new functionalities e.g., UV shielding or antioxidative properties. This article comprehensively reviews the different design strategies and their influence on properties and applications of CNMs containing lignin in various forms; either as residual lignin, added technical lignin, or nanoscale particles. The review focuses especially on the synergy created between CNMs and lignin, paving the way for new production routes and use of CNM/lignin materials in high-performance applications.
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Celulose/química , Química Verde , Lignina/química , Nanoestruturas/química , Nanotecnologia/métodos , Anti-Infecciosos/química , Antioxidantes/química , Biomassa , Coloides , HumanosRESUMO
The objective of this study is to convert bamboo into a transparent material with great optical transmittance and good strength. Bamboo has a much faster regeneration rate than wood, but its high density and high extractive content make it challenging to produce transparent products. This study presents a simple and effective approach that could address this challenge. Pretreatment of bamboo with low concentration sodium hydroxide greatly improved the preparation efficiency of transparent bamboo. The transparent bamboo with a thickness of 1 mm and cellulose volume fraction of 22% made from the pretreated bamboo exhibited an improved total optical transmissivity up to 80%, which was 60% higher than that of untreated bamboo. Compared to transparent wood (TW), although the transmissivity of transparent bamboo was slightly lower, its mechanical strength was almost doubled. Besides, the developed transparent bamboo exhibited a low heat conductivity of 0.203 W m-1 K-1, being about 10% lower than that of TW (0.225 W m-1 K-1) and approximately 80% lower than that of common glass material (0.974 W m-1 K-1). The transparent bamboo would significantly enhance energy-saving performance, being a promising alternative to traditional glass.
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Cellulose nanomaterial aerogels are macroscopic porous solids with relatively high surface areas and are thus an interesting basis for renewable catalyst materials. Cross-linked acid-base bifunctional catalyst aerogels are produced here from TEMPO-oxidized cellulose nanofibrils (TOCNF) and demonstrated in both batch and flow catalysis. Recently established acid-base modification for catalysis is expanded upon for chemical or physical cross-linking with small molecules and polymers. Low density and relatively high surface area (up to 74â¯m2â¯g-1) aerogel catalysts are produced with a variety of processing approaches and then freeze-dried from water or tert-butyl alcohol/water mixtures. Finer pore structure and increased surface area are achieved with tert-butyl alcohol as co-solvent. Chemical cross-linking improved aerogel stability to solvents. Homogeneous and aerogel TOCNF catalysts are shown to be effective acid-base cooperative catalysts for aldol condensation reactions in batch reactions. Continuous flow reactions are performed with glass column reactors packed with aerogel catalysts that showed improved rates relative to batch experiments, while also demonstrating physical stability. Catalyst deactivation in flow reactions is observed and observations of deactivation support previously reported mechanisms of site poisoning by competitive chemisorption of reactants in analogous acid-base catalysts. This report is a key demonstration of cellulose nanofibril aerogels for catalysis in continuous liquid flow reactions.
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Developing advanced building materials with both excellent thermal insulating and optical properties to replace common glass (thermal conductivity of â¼1 W m-1 K-1) is highly desirable for energy-efficient applications. The recent development of transparent wood suggests a promising building material with many advantages, including high optical transmittance, tunable optical haze, and excellent thermal insulation. However, previous transparent wood materials generally have a high haze (typically greater than 40%), which is a major obstacle for their practical application in the replacement of glass. In this work, we fabricate a clear wood material with an optical transmittance as high as 90% and record-low haze of 10% using a delignification and polymer infiltration method. The significant removal of wood components results in a highly porous microstructure, much thinner wood cell walls, and large voids among the cellulose fibrils, which a polymer can easily enter, leading to the dense structure of the clear wood. The separated cellulose fibrils that result from the removal of the wood components dramatically weaken light scattering in the clear wood, which combined with the highly dense structure produces both high transmittance and extremely low haze. In addition, the clear wood exhibits an excellent thermal insulation property with a low thermal conductivity of 0.35 W m-1 K-1 (one-third of ordinary glass); thus, the application of clear wood can greatly improve the energy efficiency of buildings. The developed clear wood, combining excellent thermal insulating and optical properties, represents an attractive alternative to common glass toward energy-efficient buildings.