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Carbohydrate-binding modules (CBM) have emerged as useful tools for a wide range of tasks, including the use as purification tags or for cellulose fiber modification. For this purpose, the CBM needs to be attached to a target protein leading to large constructs. We investigated if short peptides from the carbohydrate binding site of CBMs can bind in a similar way as native, full-length CBMs to nanocrystalline cellulose (NCC) or cotton linter paper. We designed our cellulose-binding peptides to be less hydrophobic and shorter than those previously reported. Starting from the binding site of Cel7A-CBM1, we incorporated the essential amino acids involved in cellulose binding into our peptides. These peptides, as well as control peptides with scrambled sequences or a lack of essential amino acids, bound to cellulose with similar affinity as CBM regardless of their secondary structure, sequence, or hydrophobicity. This unspecific mode of cellulose binding displayed by the presented peptides may be exploited to functionalize cellulose-based biomaterials by means of peptide-conjugates.

It has been widely accepted that sustainable polymers derived from renewable resources are able to replace the short-turnover petroleum-based materials and reduce environmental impact in the future. However, their hydrophilic chemical structures rich with oxygen groups could lead to easy growth of bacteria, which greatly limit their applications in packaging materials. Here, we present an intelligent food-packaging material with sustained-release antibacterial and real-time monitoring ability based on totally biobased contents. In detail, sodium alginate with Artemisia argyi emission oil (encapsulated in gelatin-Arabic gum microcapsules) and citric acid-sourced pH-responsive carbon quantum dots (CQDs) are coated on bamboo cellulose papers. The obtained biobased composite material (almost 100% biocarbon content) with antibacterial ability is able to extend the shelf life of fresh shrimps and can be biodegraded. Moreover, owing to the introduction of CQDs, the composite can rapidly (within 1 s) detect slight pH variations (response pH ∼5, 10 -9 mol/L of OH - ) through an obvious color change (hue value from 305 to 355°). The developed strategy may open up new opportunities in the design of multifunctional biobased composites for intelligent applications.

Photocatalytic degrading pollutants driven by visible-light irradiation has attracted tremendous attention. One strategy of preparing carbonized cellulose nanofibrils/Ti 3 C 2 T x MXene/g-C 3 N 4 (CMCN) as a photocatalyst was developed. The as-prepared CMCN was comprehensively characterized in terms of the chemical composition, chemical and crystal structure, morphology, and photoelectrochemical properties. The CMCN was explored as a photocatalyst and exhibited good photocatalytic performance in degrading MB (96.5%), RhB (95.4%), and TC (86.5%) under visible-light conditions. In addition, the CMCN as a photocatalyst exhibited good reusability and stability. It is found that the incorporation of cellulose nanofibrils provided a high carbon content, a high porosity, and a large specific surface area, enhanced the electron transfer, improved the photocatalytic performance, and ensured a semiconductor with a high stability. It is believed that this study would provide an effective approach to preparing a photocatalyst and broaden the potential application of cellulose nanofibrils in photocatalysis.

The fabrication of commercial cellulose nanofibrils (CNFs) into arrays with long-range ordering is of great significance for their extended applications, which, however, is severely hindered by their high disorder, aggregation, and hornified features. Herein, sub-nanoscale anionic metal oxide clusters (phosphotungstic acid, H 3 PW 12 O 40 , PTA) are applied to complex with commercial CNFs (dried powder DCNF and aqueous suspension WCNF) in aqueous media, and a long-range ordered layer structure can be facilely fabricated via typical unidirectional freezing. The surface complexation of the commercial CNFs and PTA can be confirmed through the small-angle scattering studies of the complex hydrogels. The hydrogels present similar correlation lengths in small-angle X-ray and neutron scattering measurements, suggesting the homogeneous distribution of PTA along the commercial CNFs. This gives rise to the negatively charged surface feature and further leads to strong repulsion among the commercial CNFs. Due to the disparity in sizes, the influence of PTA on the density of hydrogel networks is suppressed, and the network density is mainly dependent on the mass content of CNFs. The studies provide guidance to fabricate hydrogels with catalytic and photosensitive properties and also to design and stabilize long-range ordered structured aerogels during the removal of the nonfreezing bound water absorbed by the commercial CNFs after unidirectional freezing. This facile strategy shows great potential to broaden the application of commercial CNFs in thermal insulators, super-adsorbent materials, and supercapacitors in electrical devices.

Thermal insulating fibers can effectively regulate the human body temperature and decrease indoor energy consumption. However, designing super thermal insulating fibers integrating a sponge and aerogel structure based on biomass resources is still a challenge. Herein, a flow-assisted dynamic dual-cross-linking strategy is developed to realize the steady fabrication of regenerated all-cellulose graded sponge-aerogel fibers (CGFs) in a microfluidic chip. The chemically cross-linked cellulose solution is used as the core flow, which is passed through two sheath flow channels, containing either a diffusion solvent or a physical cross-linking solvent, resulting in CGFs with a porous sponge outer layer and a dense aerogel inner layer. By regulating and simulating the flow process in the microfluidic chip, CGFs with adjustable sponge thicknesses, excellent toughness (26.20 MJ m -3 ), and ultralow thermal conductivity (0.023 W m -1 K -1 ) are fabricated. This work provides a new method for fabricating graded biomass fibers and inspires attractive applications for thermal insulation in textiles.

In this study, a new cellulose nanofibril (CNF) composite aerogel was fabricated using a green and facile mussel-inspired coating strategy. First, the CNF hydrogel was crosslinked by calcium ion followed by immersion in dopamine solution. Second, the surface of CNF was modified using polydopamine (PDA) to obtain PDA@CNF (PCNF) composite aerogel. The PCNF composite aerogels had large surface areas (368.15 m 2 /g) and low bulk density (27.2 mg/cm 3 ). The composite aerogel exhibited improved mechanical properties, which were almost three times compared with those of CNF aerogel. Moreover, PCNF composite aerogel had good resilience under a wet state. The PDA functional layer remarkably enhanced the adsorption capacities of the composite aerogel for methylene blue (MB). The maximum adsorption of MB was 208 mg/g at an initial dye concentration of 50 mg/L. The adsorption isotherm and kinetic behaviors of the composite aerogel were consistent with Langmuir and pseudo-second-order models. In addition, the PCNF composite aerogels had a high adsorption capacity over a wide pH range. The reuse experiment showed that the removal efficiency of the composite aerogel remained higher than 85% after five cycles. Therefore, PCNF composite aerogels may have potential application in wastewater treatment due to its environmental sustainability and low energy consumption.

Cellulose nanocrystals (CNC) are green, safe, and renewable nanomaterials with a variety of excellent performances but their morphologies are notoriously difficult to control as this is unfavorable to the diversification of the end products. Allomorphic conversion plays an important role in diversifying the morphology of CNC. However, this further complicates the prediction, design, and control of the geometric dimensions of CNC. Herein, allomorphically modified cellulose (mercerized cellulose, ethylenediamine (EDA)-treated cellulose, and ball-milled cellulose) is designed and used as the starting material for CNC isolation. Subsequently, the morphological evolution of cellulose particles during acid hydrolysis is traced by scanning electron microscopy observations. A mechanism that facilitates further understanding of CNC shaping during sulfuric acid hydrolysis is proposed. According to the CNC shaping mechanism, precise prediction, design, and efficient control of the morphology of CNC (needle-like, ribbon-like, ellipsoid, and spherical) can be realized. CNC with various morphologies are favorable for their applications, such as templating synthesis of porous materials and Pickering emulsion dispersion.

Cellulose-water interactions are crucial to understand biological processes as well as to develop tailor made cellulose-based products. However, the main challenge to study these interactions is the diversity of natural cellulose fibers and alterations in their supramolecular structure. Here, we study the humidity response of different, well-defined, ultrathin cellulose films as a function of industrially relevant treatments using different techniques. As treatments, drying at elevated temperature, swelling, and swelling followed by drying at elevated temperatures were chosen. The cellulose films were prepared by spin coating a soluble cellulose derivative, trimethylsilyl cellulose, onto solid substrates followed by conversion to cellulose by HCl vapor. For the highest investigated humidity levels (97%), the layer thickness increased by ca. 40% corresponding to the incorporation of 3.6 molecules of water per anhydroglucose unit (AGU), independent of the cellulose source used. The aforementioned treatments affected this ratio significantly with drying being the most notable procedure (2.0 and 2.6 molecules per AGU). The alterations were investigated in real time with X-ray reflectivity and quartz crystal microbalance with dissipation, equipped with a humidity module to obtain information about changes in the thickness, roughness, and electron density of the films and qualitatively confirmed using grazing incidence small angle X-ray scattering measurements using synchrotron irradiation.

Excessive bleeding in traumatic hemorrhage is the primary concern for natural wound healing and the main reason for trauma deaths. The three-dimensional (3D) bioprinting of bioinks offers the desired structural complexity vital for hemostasis activity and targeted cell proliferation in rapid and controlled wound healing. However, it is challenging to develop suitable bioinks to fabricate specific 3D scaffolds desirable in wound healing. In this work, a 3D composite scaffold is designed using bioprinting technology and synergistic hemostasis mechanisms of cellulose nanofibrils (TCNFs), chitosan, and casein to control blood loss in traumatic hemorrhage. Bioinks that consist of casein bioconjugated TCNF (with a casein content of 104.5 ± 34.1 mg/g) using the carbodiimide cross-linker chemistry were subjected to bioprinting for customizable 3D scaffold fabrication. Further, the 3D composite scaffolds were in situ cross-linked using a green ionic complexation approach. The covalent conjugation among TCNF, casein, and chitosan was confirmed by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), and X-ray diffraction (XRD) studies. The in vitro hemostasis activity of the 3D composite scaffold was analyzed by a human thrombin-antithrombin (TAT) assay and adsorption of red blood cells (RBCs) and platelets. The 3D composite scaffold had a better swelling behavior and a faster whole blood clotting rate at each time point than the 3D TCNF scaffold and commercial cellulose-based dressings. The TAT assay demonstrated that the 3D composite scaffold could form a higher content of thrombin (663.29 pg/mL) and stable blood clot compared to a cellulosic pad (580.35 pg/mL), 3D TCNF (457.78 pg/mL), and cellulosic gauze (328.92 pg/mL), which are essential for faster blood coagulation. In addition, the 3D composite scaffold had a lower blood clotting index (23.34%) than the 3D TCNF scaffold (41.93%), suggesting higher efficiencies for RBC entrapping to induce blood clotting. The in vivo cytocompatibility was evaluated by a 3D cell culture study, and results showed that the 3D composite scaffold could promote growth and proliferation of NIH 3T3 fibroblast cells, which is vital for wound healing. Cellulase-based in vitro deconstruction of the 3D composite scaffold showed significant weight loss (80 ± 5%) compared to the lysozyme hydrolysis (22 ± 5%) after 28 days of incubation, suggesting the biodegradation potential of the composite scaffold. In conclusion, this study proposes efficient prospects to develop a 3D composite scaffold from bioprinting of TCNF-based bioinks that can accelerate blood clotting and wound healing, suggesting its potential application in reducing blood loss during traumatic hemorrhage.

Bioactive substances, displaying excellent biocompatibility, chemical stability, and processability, could be extensively applied in biomedicine and tissue engineering. In recent years, plant-based bioactive substances such as flavonoids, vitamins, terpenes, and lignin have received considerable attention due to their human health benefits and pharmaceutical/medical applications. Among them is lignin, an amorphous biomacromolecule mainly derived from the combinatorial radical coupling of three phenylpropane units ( p -hydroxypenyl, guaiacyl, and syringyl) during lignification. Lignin possesses intrinsic bioactivities (antioxidative, antibacterial, anti-UV activities, etc.) against phytopathogens. Lignin also enhances the plant resistance (adaptability) against environmental stresses. The abundant structural features of lignin offer other significant bioactivities including antitumor and antivirus bioactivities, regulation of plant growth, and enzymatic hydrolysis of cellulose. This Review reports the latest research results on the bioactive potential of lignin and lignin-based substances in biomedicine, agriculture, and biomass conversion. Moreover, the interfacial reactions and bonding mechanisms of lignin with biotissue/cells and other constituents were also discussed, aiming at promoting the conversion or evolution of lignin from industrial wastes to value-added bioactive materials.

The fabrication of biomimetic photonic materials with environmental stimuli-responsive functions from entirely biobased materials is becoming increasingly challenging with the growing demand for biodegradable materials. Herein, the effect of glucan with different molecular weights on the mechanical performance and tunable structural color of iridescent CNC composite films was investigated. The existence of glucan did not influence the self-assembly performance of CNCs, but rather led to an improvement in the mechanical performance, enabling cholesteric CNC composite films with an adjustable structural color. Simultaneously, the iridescent films showed a conspicuous redshift and enlarged initial pitch without obstruction of the chiral structure. In response to environmental humidity, the structural colors of the iridescent composite films can be changed by regulating their chiral nematic structure. In particular, the films demonstrate a reversible structural color change between blue and red at RH between 50 and 98%. The resulting biobased iridescent composite films have potential applications in decorative coating, optical and humidity sensing, and anticounterfeiting.

Lignin/tannin/ZnONP composite coatings were designed for paper-based green packaging. Multiple functions, such as high strength, moisture resistance, low air permeance, heat endurance, UV aging resistance, and antibacterial/mold properties, were successfully integrated into one biobased coating. Prepolymerization improved the physical properties of coatings at high lignin contents. The best ingredient ratio was: 40% lignin, 15% tannin, and 10% ZnONPs (based on tannin weight), and the as-prepared biocoating was labeled LTZn-10. After coated with LTZn-10, the tensile strength and bursting strength of the packaging were efficiently enhanced by more than 3 times and were dramatically increased by 51.6 and 5.6 times at the wet state, respectively, which reveals that the packaging has favorable moisture resistance and it can be used in high humidity environments. Scanning electron microscopy (SEM) proved that most of the pores on the paper were blocked by the coatings, which helped to decrease the air permeance by 10.3 times. Meanwhile, ZnONPs were evenly spread on the coatings, which endowed the packaging with excellent antibacterial/mold performance. No colony or mycelium was found in the test against Gram-negative/positive bacteria and eight common molds. Besides, antibacterial activity is only available while the bacteria come in contact with the coating and no active substances were released into the culture medium, which is a good property that can keep the cargo from contamination of antibacterial agents. In addition, the coated paper presented an improved T and thermal degradation temperature, indicating that the coated package has favorable thermostability and can maintain its outstanding physical properties in a wider temperature range. Lignin and tannin promoted the UV stability and service life of the coated paper, as a rare physical decrease was observed after UV aging for 72 h. The function-integrated biobased coating with favorable sustainability is a good candidate to be widely used in paper-based green packaging fields.g and thermal degradation temperature, indicating that the coated package has favorable thermostability and can maintain its outstanding physical properties in a wider temperature range. Lignin and tannin promoted the UV stability and service life of the coated paper, as a rare physical decrease was observed after UV aging for 72 h. The function-integrated biobased coating with favorable sustainability is a good candidate to be widely used in paper-based green packaging fields.

Cellulose nanopaper (CNP) has been considered as a promising material with great application potential in diverse fields. However, the hydrophilic nature of CNP significantly limits its practical application. In order to improve its water resistance, we demonstrate a facile approach to functionalize CNP by impregnating it with chitosan (CS), followed by in situ polymerization of polypyrrole (PPy). The results indicate that the obtained CNP/CS/PPy shows excellent water resistance with the wet tensile strength of up to 80 MPa, which is more than 10 times higher than that of the pure CNP. Intriguingly, new features ( e.g. , electrical conductivity, antibacterial activity, and so forth) are achieved at the same time. The functionalized CNP/CS/PPy shows a high conductivity of 6.5 S cm -1 , which can be used for electromagnetic interference shielding applications with a high shielding performance of around 18 dB. In addition, the CNP/CS/PPy exhibits good antibacterial activity toward Staphylococcus aureus and Escherichia coli , with the bacterial reductions of 99.28 and 95.59%, respectively. Thus, this work provides a simple and versatile approach to functionalize CNP for achieving multifunctional properties.

Cellulose nanofibrils, which attract extensive attention as a bio-based, sustainable, high-performance nanofibril, are believed to be predominantly hydrophilic. This study aimed to prove the presence of an amphiphilic "Janus-type fiber surface" in water with hydrophobic and hydrophilic faces in a cellulose nanofibril (ACC-CNF) that was prepared by the aqueous counter collision method. We clarified the surface characteristics of the ACC-CNF by confocal laser scanning microscopy with a carbohydrate-binding module and congo red probes for the hydrophobic planes on the cellulose fiber surfaces and calcofluor white as hydrophilic plane probes. The results indicated the presence of both characteristic planes on a single ACC-CNF surface, which verifies an amphiphilic Janus-type structure. Both hydrophobic probes adsorbed onto ACC-CNFs for the quantitative evaluation of the degree of ACC-CNF surface hydrophobicity by Langmuir's adsorption theory based on the optimal maximum adsorption amounts for various starting raw material types.

This work is strategically premeditated to study the potential of a herbal medicinal product as a natural bioactive ingredient to generate nanocellulose-based antibacterial architectures. In situ fibrillation of purified cellulose was done in cinnamon extract ( ci E) to obtain microfibrillated cellulose (MFC). To this MFC suspension, carboxylated cellulose nanocrystals (cCNCs) were homogeneously mixed and the viscous gel thus obtained was freeze-dried to obtain lightweight and flexible composite aerogel architectures impregnated with ci E, namely, ci MFC/cCNCs. At an optimal concentration of 0.3 wt % cCNCs (i.e., for ci MFC/cCNCs_0.3), an improvement of around 106% in compressive strength and 175% increment in modulus were achieved as compared to pristine MFC architecture. The efficient loading and interaction of ci E components, specifically cinnamaldehyde, with MFC and cCNCs resulted in developing competent antibacterial surfaces with dense and uniform microstructures. Excellent and long-term antimicrobial activity of the optimized architectures ( ci MFC/cCNCs_0.3) was confirmed through various antibacterial assays like the zone inhibition method, bacterial growth observation at OD 600 , minimum inhibitory concentration (MIC, here 1 mg/mL), minimum bactericidal concentration (MBC, here 3-5 mg/mL), and Live/Dead BacLight viability tests. The changes in the bacterial morphology with a disrupted membrane were further confirmed through various imaging techniques like confocal laser scanning microscopy, FESEM, AFM, and 3D digital microscopy. The dry composite architecture showed the persuasive capability of suppressing the growth of airborne bacteria, which in combination with antibacterial efficiency in the wet state is considered as an imperative aspect for a material to act as the novel biomaterial. Furthermore, these architectures demonstrated excellent antibacterial performance under real "in use" contamination prone conditions. Hence, this work provides avenues for the application of crude natural extracts in developing novel forms of advanced functional biomaterials that can be used for assorted biological/healthcare applications such as wound care and antimicrobial filtering units.

The development of intelligent and multifunctional hydrogels having photothermal properties, good mechanical properties, sustained drug release abilities with low burst release, antibacterial properties, and biocompatibility is highly desirable in the biomaterial field. Herein, mesoporous polydopamine (MPDA) nanoparticles wrapped with graphene oxide (GO) were physically cross-linked in cellulose nanofibril (CNF) hydrogel to obtain a novel MPDA@GO/CNF composite hydrogel for controllable drug release. MPDA nanoparticles exhibited a high drug loading ratio (up to 35 wt %) for tetracycline hydrochloride (TH). GO was used to encapsulate MPDA nanoparticles for extending the drug release time and reinforcing the physical strength of the obtained hydrogel. The mechanical strength of the as-fabricated MPDA@GO/CNF composite hydrogel was five times greater compared to that of the pure CNF hydrogel. Drug release experiments demonstrated that burst release behavior was significantly reduced by adding MPDA@GO. The drug release time of the MPDA@GO/CNF composite hydrogel was 3 times and 7.2 times longer than that of the polydopamine/CNF hydrogel and pure CNF hydrogel, respectively. The sustained and controlled drug release behaviors of the composite hydrogel were highly dependent on the proportion of MPDA and GO. Moreover, the rate of drug release could be accelerated by near-infrared (NIR) light irradiation and pH value change. The drug release kinetics of the as-prepared composite hydrogel was well described by the Korsmeyer-Peppas model, and the drug release mechanism of TH from the composite hydrogel was anomalous transport. Importantly, this carefully designed MPDA@GO/CNF composite hydrogel showed good biocompatibility through an in vitro cytotoxicity test. In particular, the toxicity of GO was well shielded by the CNF hydrogel. Therefore, this novel MPDA@GO/CNF composite hydrogel with an encapsulation structure for controllable drug release and toxicity shielding of GO could be used as a very promising controlled drug delivery carrier, which may have potential applications for chemical and physical therapies.

Multilayered and stacked cellulose paper has emerged as a promising platform for construction of three-dimensional (3D) cell culture because of its low cost, good biocompatibility, and high porosity. However, its poor light transmission makes it challenging to directly and clearly monitor cell behaviors (e.g., growth and proliferation) on the paper-based platform using an optical microscope. In this work, we developed a transparent microcrystalline cellulose/polyvinyl alcohol (MCC/PVA) paper with irregular pores through dissolution and regeneration of microcrystalline nanocellulose, addition of a porogen reagent (NaCl), and subsequently dipping in PVA solutions. The transparent MCC paper displays high porosity (up to 90%), adjustable pore size (between 23 and 46 μm), large thickness (from 315 to 436 μm), and high light transmission under water (>95%). Through further modification of the transparent MCC paper with PVA, the obtained transparent MCC/PVA paper shows enhanced mechanical properties (dry and wet strengths), good hydrophilicity (with a contact angle of 70.8°), and improved biocompatibility (cell viability up to 90%). By stacking and destacking multiple layers of the transparent MCC/PVA paper, it has been used for both two-dimensional and three-dimensional cell culture platforms. The transparent MCC/PVA paper under water enables both direct observation of cell morphology by an optical microscope via naked eyes and fluorescence microscope after staining. We envision that the developed transparent MCC/PVA paper holds great potential for future applications in various bioanalytical and biomedical fields, such as drug screening, tissue engineering, and organ-on-chips.

In this study, a carboxyl-modified cellulosic hydrogel was developed as the base material for wound dressings. ε-poly-l-lysine, a natural polyamide, was then covalently linked to the hydrogel through a bioconjugation reaction, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). The antibacterial efficacy of the hydrogel was tested against two model bacteria, Staphylococcus aureus and Pseudomonas aeruginosa , two of the most commonly found bacteria in wound infections. Bacterial viability and biofilm formation after exposure of bacteria to the hydrogels were used as efficacy indicators. Live/Dead assay was used to measure the number of compromised bacteria using a confocal laser scanning microscope. The results show that the antibacterial hydrogel was able to kill approximately 99% of the exposed bacteria after 3 h of exposure. In addition, NIH/3T3 fibroblasts were used to study the biocompatibility of the developed hydrogels. Water-soluble tetrazolium salt (WST)-1 assay was used to measure the metabolic activity of the cells and Live/Dead assay was used to measure the viability of the cells after 24, 48, and 72 h. The developed antibacterial hydrogels are light weight, have a high water-uptake capacity, and show high biocompatibility with the model mammalian cells, which make them a promising candidate to be used for wound dressing applications.

Ionic conductors are normally prepared from water-based materials in the solid form and feature a combination of intrinsic transparency and stretchability. The sensitivity toward humidity inevitably leads to dehydration or deliquescence issues, which will limit the long-term use of ionic conductors. Here, a novel ionic conductor based on natural bacterial cellulose (BC) and polymerizable deep eutectic solvents (PDESs) is developed for addressing the abovementioned drawbacks. The superstrong three-dimensional nanofiber network and strong interfacial interaction endow the BC-PDES ionic conductor with significantly enhanced mechanical properties (tensile strength of 8 × 10 5 Pa and compressive strength of 6.68 × 10 6 Pa). Furthermore, compared to deliquescent PDESs, BC-PDES composites showed obvious mechanical stability, which maintain good mechanical properties even when exposed to high humidity for 120 days. These materials were demonstrated to possess multiple sensitivity to external stimulus, such as strain, pressure, bend, and temperature. Thus, they can easily serve as supersensitive sensors to recognize physical activity of humans such as limb movements, throat vibrations, and handwriting. Moreover, the BC-PDES ionic conductors can be used in flexible, patterned electroluminescent devices. This work provides an efficient strategy for making cellulose-based sustainable and functional ionic conductors which have broad application in artificial flexible electronics and other products.

Cellulose nanocrystals (CNCs), having a high specific surface area and versatile surface chemistry, provide considerable potential to interact by various mechanisms with enzymes for nano-immobilization purposes. However, engineering chemically safe CNCs, suitable for edible administrations, presents a significant challenge. A reliable carboxylate form of H-CNCs was formed using H 2 O 2 oxidation of softwood pulp under mild thermal conditions. Negatively charged carboxyl groups (∼0.9 mmol g -1 ) played a key role in lysozyme immobilization via electrostatic interactions and covalent linkages, as evidenced by Fourier transform infrared and 13 C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopies. Adsorption isotherms showed a high loading capacity of H-CNCs (∼240 mg g -1 ), and fitting the data to the Langmuir model confirmed monolayer coverage of lysozyme on their surface. Using a non-toxic coupling agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, lysozyme-conjugated H-CNCs were developed with an immobilization yield of ∼65% and relative catalytic activity of ∼60%, similar to lysozyme adsorption on H-CNCs. These H-CNC-lysozyme nanohybrids, rationally processed via safe and green strategies, are specifically exploitable as catalytically active emulsifiers in food and pharmaceutical sectors.

Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 Å. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.

Stretchable and compressible hydrogels based on natural polymers have received immense considerations for electronics. The feasibility of using pure natural polymer-based hydrogels could be improved if their mechanical behaviors satisfy the requirements of practical applications. Herein, we report highly stretchable (tensile strain ∼126%) and compressible (compression strain ∼80%) cellulose ionic hydrogels (CIHs) among pure natural polymer-based hydrogels including cellulose, chitin, and chitosan via chemical cross-linking based on free radical polymerization of allyl cellulose in NaOH/urea aqueous solution. In addition, the hydrogels have good transparency (transmittance of ∼89% at 550 nm) and ionic conductivity (∼0.16 mS cm -1 ) and can be worked at -20 °C without freezing and visual loss of transparency. Moreover, the CIHs can serve as reliable and stable strain sensors and have been successfully used to monitor human activities. Significantly, the various properties of hydrogel can be controlled through rationally adjusting the chemically cross-linked density. Our methodology will prove useful in developing the satisfied mechanical and transparent CIHs for a myriad of applications in flexible electronics.

Nanotechnology has been identified as having great potential for improving the efficiency of water prevention and purification while reducing costs. In this field, two applications of nanocellulose have generated attention and have proven to be a sound strategy as an adsorbent and as a membrane for the removal of contaminants. This potential is attributed to its high aspect ratio, high specific surface area, high capacity retention, and environmental inertness. In addition to the aforementioned advantages, the presence of active sites allows the incorporation of chemical moieties that may enhance the binding efficiency of pollutants to the surface. This review paper intends to understand how nanocellulose affects the adsorption behavior of water pollutants, e.g., heavy metal ions, microbes, dyes, and organic molecules, and is divided in two parts. First, a general overview of the different strategies for the preparation of nanocellulose is described, and its specific properties are reported. The second section reports some of its application as adsorbent nanomaterial or separation membrane. It appears that the use of nanocellulose for these applications is very promising for wastewater treatment industries.

A green and facile method was designed to isolate a type of cellulose nanocrystal (CNC) with carboxylated surfaces from native cellulose materials. Because isolation and modification processes of cellulosic particles are generally performed separately using harmful chemicals and multiple steps, the one-pot approach employed in this work is interesting from both an economical and ecological point of view. The reaction is carried out by adding hydrogen peroxide as an oxidant and copper(II) sulfate as a catalyst in acidic medium under mild thermal conditions. The charge content of the carboxylated CNC is about 1.0 mmol g -1 , measured by a conductometric titration. Fourier transform infrared spectroscopy also proved the presence of carboxyl groups on the CNC particles. Atomic force microscopy along with optical polarized microscopy readily showed a rod shape morphology for the cellulosic particles. An average length of 263 nm and width of 23 nm were estimated by transmission electron microscopy. Dynamic laser scattering on carboxylated CNC suspensions by adding salt confirmed that nanoparticles are electrostatically stable. Carboxylated CNCs were furthermore characterized by solid carbon-13 nuclear magnetic resonance and X-ray spectroscopy.

Cellulosic nanomaterials (CNMs) are organic, green nanomaterials that are obtained from renewable sources and possess exceptional mechanical strength and biocompatibility. The associated unique physical and chemical properties have made these nanomaterials an intriguing prospect for various applications including the food and nutraceutical industry. From the immobilization of various bioactive agents and enzymes, emulsion stabilization, direct food additives, to the development of intelligent packaging systems or pathogen or pH detectors, the potential food related applications for CNMs are endless. Over the past decade, there have been several reviews published covering different aspects of cellulosic nanomaterials, such as processing-structure-property relationship, physical and chemical properties, rheology, extraction, nanocomposites, etc. In this critical review, we have discussed and provided a summary of the recent developments in the utilization of cellulosic nanomaterials in applications related to food and nutraceuticals.

Knowledge gaps in the biosafety data of the nanocellulose (NC) for biomedical use through various routes of administration call for closer look at health and exposure evaluation. This work evaluated the potentially immunogenic contaminants levels, for example, endotoxin and (1,3)-β-d-glucan, in four representative NCs, that is, wood-based NCs and bacterial cellulose (BC). The hot-water extracts were analyzed with ELISA assays, HPSEC-MALLS, GC, and NMR analysis. Varying levels of endotoxin and (1,3)-β-d-glucan contaminats were found in these widely used NCs. Although the β-(1,3)-d-glucan was not detected from the NMR spectra due to the small extract samples amount (2-7 mg), the anomerics and highly diastereotopic 6-CH 2 signals may suggest the presence of β-(1,4)-linkages with β-(1,6) branching in the polysaccharides of NCs' hot-water extracts, which were otherwise not detectable in the enzymatic assay. In all, the article highlights the importance of monitoring various water-soluble potentially immunogenic contaminants in NC for biomedical use.

We present an approach to construct biocompatible and photoluminescent hybrid materials comprised of carbon quantum dots (CQDs) and TEMPO-oxidized cellulose nanocrystals (TO-CNCs). First, the amino-functionalized carbon quantum dots (NH 2 -CQDs) were synthesized using a simple microwave method, and the TO-CNCs were prepared by hydrochloric acid (HCl) hydrolysis followed by TEMPO-mediated oxidation. The conjugation of NH 2 -CQDs and TO-CNCs was conducted via carbodiimide-assisted coupling chemistry. The synthesized TO-CNC@CQD hybrid nanomaterials were characterized using X-ray photoelectron spectroscopy, cryo-transmittance electron microscopy, confocal microscopy, and fluorescence spectroscopy. Finally, the interactions of TO-CNC@CQD hybrids with HeLa and RAW 264.7 macrophage cells were investigated in vitro. Cell viability tests suggest the surface conjugation with NH 2 -CQDs not only improved the cytocompatibility of TO-CNCs, but also enhanced their cellular association and internalization on both HeLa and RAW 264.7 cells after 4 and 24 h incubation.

The state of dispersion and the interactions between a polymer and a filler in a nanocomposite crucially define its properties and performance. The affinity of polylactide (PLA) with vegetable and animal proteins (casein, gelatin, soy protein isolate, and hydrolysate) is investigated and their role as eco-friendly dispersants and compatibilizers of cellulose nanofibrils (CNF) is elucidated. The affinity of the proteins with PLA is determined by using sensograms acquired by electroacoustic (quartz crystal microgravimetry) and optical (surface plasmon resonance) techniques. The surface energy of PLA increases upon protein adsorption while the opposite effect is observed for CNF, under identical experimental conditions. A significant improvement in the thermodynamic work of adhesion for PLA/CNF systems is predicted by application of the denatured proteins at low concentrations (∼20% and ∼15% enhancement with soy protein and casein at pH 3 and pH 8, respectively). We offer a robust method to screen denatured proteins and to tailor the wettability and material compatibility in the synthesis of bionanocomposites based on CNF and PLA.

The current study aims to demonstrate the influence of the surface chemistry of wood-derived cellulose nanofibril (CNF) hydrogels on fibroblasts for tissue engineering applications. TEMPO-mediated oxidation or carboxymethylation pretreatments were employed to produce hydrogels with different surface chemistry. This study demonstrates the following: first, the gelation of CNF with cell culture medium and formation of stable hydrogels with improved rheological properties; second, the response of mouse fibroblasts cultured on the surface of the hydrogels or sandwiched within the materials with respect to cytotoxicity, cell attachment, proliferation, morphology, and migration. Indirect cytotoxicity tests showed no toxic effect of either hydrogel. The direct contact with the carboxymethylated hydrogel adversely influenced the morphology of the cells and limited their spreading, while typical morphology and spreading of cells were observed with the TEMPO-oxidized hydrogel. The porous fibrous structure may be a key to cell proliferation and migration in the hydrogels.

We present an efficient approach to develop cellulose nanocrystal (CNC) hybrids with magnetically responsive Fe 3 O 4 nanoparticles that were synthesized using the (Fe 3+ /Fe 2+ ) coprecipitation. After 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-catalyzed oxidation of CNC, carbodiimide (EDC/NHS) was used for coupling amine-containing iron oxide nanoparticles that were achieved by dopamine ligand exchange (NH 2 -Fe 3 O 4 NPs). The as-prepared hybrids (Fe 3 O 4 @CNC) were further complexed with Cu(II) ions to produce specific protein binding sites. The performance of magnetically responsive Cu-Fe 3 O 4 @CNC hybrids was assessed by selectively separating lysozyme from aqueous media. The hybrid system displayed a remarkable binding capacity with lysozyme of 860.6 ± 14.6 mg/g while near full protein recovery (∼98%) was achieved by simple elution. Moreover, the regeneration of Fe 3 O 4 @CNC hybrids and efficient reutilization for protein separation was demonstrated. Finally, lysozyme separation from matrices containing egg white was achieved, thus revealing the specificity and potential of the presented method.

The temperature-dependence of xyloglucan (XG) adsorption onto smooth cellulose model films regenerated from N-methylmorpholine N-oxide (NMMO) was investigated using surface plasmon resonance spectroscopy, and it was found that the adsorbed amount increased with increasing temperature. This implies that the adsorption of XG to NMMO-regenerated cellulose is endothermic and supports the hypothesis that the adsorption of XG onto cellulose is an entropy-driven process. We suggest that XG adsorption is mainly driven by the release of water molecules from the highly hydrated cellulose surfaces and from the XG molecules, rather than through hydrogen bonding and van der Waals forces as previously suggested. To test this hypothesis, the adsorption of XG onto cellulose was studied using cellulose films with different morphologies prepared from cellulose nanocrystals (CNC), semicrystalline NMMO-regenerated cellulose, and amorphous cellulose regenerated from lithium chloride/dimethylacetamide. The total amount of high molecular weight xyloglucan (XGHMW) adsorbed was studied by quartz crystal microbalance and reflectometry measurements, and it was found that the adsorption was greatest on the amorphous cellulose followed by the CNC and NMMO-regenerated cellulose films. There was a significant correlation between the cellulose dry film thickness and the adsorbed XG amount, indicating that XG penetrated into the films. There was also a correlation between the swelling of the films and the adsorbed amounts and conformation of XG, which further strengthened the conclusion that the water content and the subsequent release of the water upon adsorption are important components of the adsorption process.

Cellulose nanofibrils (CNFs) are produced and commonly used in the form of aqueous suspensions or gels. A number of studies have focused lately on rheological properties of CNF suspensions, which gives insight into properties of such materials and can reflect their behavior during handling. This Review summarizes the recent progress in rheological studies on CNF aqueous suspensions using rotational rheometry. Here, we discuss linear viscoelastic properties, i.e., frequency-dependent storage and loss moduli; shear flow behavior, i.e., apparent viscosity and shear stress as a function of shear rate; local flow characteristics, etc. In this Review, we point out that the rheological behavior of at least two types of CNF suspensions should be distinguished: (i) ones produced using mechanical fibrillation with or without enzymatic pretreatment (no surface chemical modification), which possess highly flocculated structure, and (ii) ones produced involving chemical modification pretreatments, e.g., carboxylation, carboxymethylation, quaternization, or sulfonation, which possess better colloidal stability and do not evidently flocculate.

In this work, we take advantage of the rod-like structure of electrosterically stabilized nanocrystalline cellulose (ENCC, with a width of about 7 nm and a length of about 130 nm), which has dicarboxylated cellulose (DCC) chains protruding from both ends, providing electrosterical stability for ENCC particles, to chemically end-to-end assemble these particles into nanocellulose fibers. ENCC with shorter DCC chains can be obtained by a mild hydrolysis of ENCC with HCl, and subsequently the hydrolyzed ENCC (HENCC, with a width of about 6 nm and a length of about 120 nm) is suitable to be assembled into high aspect ratio nanofibers by chemically cross-linking HENCC from one end to another. Two sets of HENCC were prepared by carbodiimide-mediated formation of an alkyne and an azide derivative, respectively. Cross-linking these two sets of HENCC was performed by a click reaction. HENCCs were also end-to-end cross-linked by a bioconjugation reaction, with a diamine. From atomic force microscopy (AFM) images, about ten HENCC nanoparticles were cross-linked and formed high aspect ratio nanofibers with a width of about 6 nm and a length of more than 1 μm.

Contact active surfaces are an innovative tool for developing antibacterial products. Here, the microfibrillated cellulose (MFC) surface was modified with the β-lactam antibiotic benzyl penicillin in aqueous medium to prepare antimicrobial films. Penicillin was grafted on the MFC surface using a suspension of these nanofilaments or directly on films. Films prepared from the penicillin-modified MFC were characterized by Fourier transform infrared spectroscopy, contact angle measurements, elemental analysis, and X-ray photoelectron spectroscopy and tested for antibacterial activity against the Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. Penicillin-grafted MFC films exhibited successful killing effect on Gram-positive bacteria with 3.5-log reduction whereas bacteriostatic efficiency was found in penicillin-grafted MFC suspension. The zone of inhibition test and leaching dynamic assay demonstrated that penicillin was not diffused into the surrounding media, thus proving that the films were indeed contact active. Thus, penicillin can be chemically bound to the modified substrate surface to produce promising nonleaching antimicrobial systems.

Toward our goal of scalable, antimicrobial materials based on photodynamic inactivation, paper sheets comprised of photosensitizer-conjugated cellulose fibers were prepared using porphyrin and BODIPY photosensitizers, and characterized by spectroscopic (infrared, UV-vis diffuse reflectance, inductively coupled plasma optical emission) and physical (gel permeation chromatography, elemental, and thermal gravimetric analyses) methods. Antibacterial efficacy was evaluated against Staphylococcus aureus (ATCC-2913), vancomycin-resistant Enterococcus faecium (ATCC-2320), Acinetobacter baumannii (ATCC-19606), Pseudomonas aeruginosa (ATCC-9027), and Klebsiella pneumoniae (ATCC-2146). Our best results were achieved with a cationic porphyrin-paper conjugate, Por((+))-paper, with inactivation upon illumination (30 min, 65 ± 5 mW/cm(2), 400-700 nm) of all bacterial strains studied by 99.99+% (4 log units), regardless of taxonomic classification. Por((+))-paper also inactivated dengue-1 virus (>99.995%), influenza A (∼ 99.5%), and human adenovirus-5 (∼ 99%). These results demonstrate the potential of cellulose materials to serve as scalable scaffolds for anti-infective or self-sterilizing materials against both bacteria and viruses when employing a photodynamic inactivation mode of action.

The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-methacrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper.

Acetic acid ethanol-based organosolv pretreatment of sugar cane bagasse was performed to enhance enzymatic hydrolysis. The effect of different parameters (including temperature, reaction time, solvent concentration, and acid catalyst dose) on pretreatment prehydrolyzate and subsequent enzymatic digestibility was determined. During the pretreatment process, 11.83 g of xylose based on 100 g of raw material could be obtained. After the ethanol-based pretreatment, the enzymatic hydrolysis was enhanced and the highest glucose yield of 40.99 g based on 100 g of raw material could be obtained, representing 93.8% of glucose in sugar cane bagasse. The maximum total sugar yields occurred at 190 °C, 45 min, 60:40 ethanol/water, and 5% dosage of acetic acid, reaching 58.36 g (including 17.69 g of xylose and 40.67 g of glucose) based on 100 g of raw material, representing 85.4% of total sugars in raw material. Furthermore, characterization of the pretreated sugar cane bagasse using X-ray diffraction and scanning electron microscopy analyses were also developed. The results suggested that ethanol-based organosolv pretreatment could enhance enzymatic digestibilities because of the delignification and removal of xylan.

In this work, flexible and free-standing composite films of nanofibrillated cellulose/polypyrrole (NFC/PPy) and NFC/PPy-silver nanoparticles (NFC/PPy-Ag) have been synthesized for the first time via in situ one-step chemical polymerization and applied in potential biomedical applications. Incorporation of NFC into PPy significantly improved its film formation ability resulting in composite materials with good mechanical and electrical properties. It is shown that the NFC/PPy-Ag composite films have strong inhibition effect against the growth of Gram-positive bacteria, e.g., Staphylococcus aureus. The electrical conductivity and strong antimicrobial activity makes it possible to use the silver composites in various applications aimed at biomedical treatments and diagnostics. Additionally, we report here the structural and morphological characterization of the composite materials with Fourier-transform infrared spectroscopy, atomic force microscopy, and scanning and transmission electron microscopy techniques.

Cellulose acetylation was investigated in dimethyl sulfoxide (DMSO) with isopropenyl acetate (IPA) as acetylating reagent and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) as catalyst at 70-130 °C for 3-12 h. The degree of substitution (DS) of acetylated cellulose was comparatively determined by titration and ¹H NMR and confirmed by FT-IR analysis. The results indicated that per-O-acetylation was achieved at >90 °C for a relatively long duration. The three well-resolved peaks of carbonyl carbons in ¹³C NMR spectra also provided evidence of per-O-acetylation. The solubility of cellulose acetates in common organic solvents was examined, and the result showed that chloroform can be an alternative choice as a solvent for fully acetylated cellulose formed in this study besides DMSO. The intrinsic viscosity of acetylated cellulose solution implied almost no degradation of cellulose during acetylation in DMSO except at higher temperature (130 °C) for a long time.

This article focuses on the formation of the surface tension torque (STT) phenomenon close to the dry-line boundary layer during evaporation of the liquid phase of a solution casted shape-anisotropic nanoparticle suspension (here, cellulose nanowhisker (CNW)) or dissolved polymer (here, polyvinyl alcohol (PVA)) and its effects on self-assembly of the cellulose nanocrystals and polymer chains. The results confirm that the STT tends to align both the CNWs and the PVA chains tangential to the dry-line boundary layer. By careful control of the advancement of the dry-line, achieving special linear and curved patterns of both the CNWs and the PVA chains proportional to the mold position and geometry is possible. The STT phenomenon is explained and simplified in terms of a physical model. Understanding of the STT phenomenon and its effects on the alignment and self-assembly of the CNWs and PVA chains is necessary especially when achieving alignment using a modulated external magnetic or electric field is desired. The STT is safe, inexpensive, easy, and efficient, and can be a good alternative to the magnetic and electric field orientation methods.

Traditionally, a long reaction time was required in the synthesis of cellulose esters (CEs). In this work, dimethyl sulfoxide (DMSO)/aqueous NaOH or KOH was introduced as an efficient reaction system for rapidly synthesizing CEs by transesterification. Surprisingly, cellulose could react with vinyl acetate, vinyl propionate, and vinyl butyrate and synthesized cellulose acetate, cellulose propionate, and cellulose butyrate with a high degree of substitution (2.14-2.34) in 5 min, which was in sharp contrast to hours of existing methods. The effects of solvents, catalysts, and esterifying agents on the synthesis of CEs were comparatively investigated to better understand this method. The structure and thermal properties of obtained CEs were characterized by Fourier transform infrared (FTIR) and (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopies and differential scanning calorimetry. Results from these spectra confirmed the successful synthesis of these CEs. Furthermore, these CEs showed similar thermal properties compared to products obtained from other methods.

When grafted β-cyclodextrin is used as targeting sites, Pluronic polymers have been introduced on the surface of cellulose nanocrystals by means of inclusion interaction between β-cyclodextrin and hydrophobic segment of the polymer. Because of the steric stabilization effect, surface poly(ethylene glycol) chains facilitate the dispersion and compatibility of nanocrystals, which also enhance the loading levels of nanocrystals in the hydrogel system. Meanwhile, uncovered poly(ethylene glycol) segments render the participating inclusion of α-cyclodextrin for the architecture of in situ hydrogels. Surface grafting and inclusion reactions were proved by solid (13)C NMR and FTIR. Grafting efficiency of β-cyclodextrin and inclusion efficiency of Pluronic on the surface of nanocrystals were confirmed by UV spectroscopy and elemental analysis. A significant enhancement of the structural and thermal stability of in situ hydrogels with high loading levels of modified nanocrystals (>5.77 wt %) was observed by rheological analysis. Further study reveals the performance and behavior of hydrogels under a different pH environment. Finally, in situ hydrogels were used as drug carrier for in vitro release of doxorubicin and exhibit the behavior of prolonged drug release with special release kinetics.

The present study reports for the first time a method to obtain water redispersible dried NFC using freeze-drying. No chemical surface modification was required to get this kind of product. Salt addition (sodium chloride: NaCl) strategy has been selected to block and then to regenerate hydrogen bonds during the drying and the redispersion steps, respectively. Several samples were produced at different pH (i.e., 4, 6, 8, and 10). All the redispersed NFC were characterized by different techniques (e.g., FE-SEM, XRD, EPMA-EDX) to check the effect of salt on NFC aggregation. The interactions between NFC and NaCl at different pH conditions have been discussed and the rheology of the redispersed NFC suspension has been performed. All the results prove a perfect water redispersion at pH 8 and exactly similar suspension is obtained after water dispersion of dried NFC following our procedure. These results are very promising for increasing application of NFC.

Adsorption of oligonucleotides onto model cellulose surfaces was investigated by comparing the Boese and Breaker's cellulose binding oligonucleotide (CBO) with a nonspecific oligonucleotide control (NSO). Measurements using the quartz crystal microbalance with dissipation technique confirmed that CBO adsorbed onto cellulose more than NSO, particularly at high ionic strengths (100 mM CaCl(2)). CBO showed a higher maximum adsorption on nanofibrillated and nanocrystalline cellulose than on regenerated cellulose, indicating a preference for the native cellulose I crystal structure under conditions that favored specific adsorption over calcium-mediated electrostatically driven adsorption. In addition, an anionic polyacrylamide (A-PAM) with grafted CBO also adsorbed onto the surface of cellulose in CaCl(2), whereas the unmodified A-PAM did not. This work shows that CBO performs as a "sticker", facilitating the adsorption of polyacrylamide onto cellulose, even under high ionic strength conditions where the adsorption of conventional polyelectrolytes is inhibited.

Crosslinked polysaccharide sponges have been prepared by freeze-drying of amorphous alginate-oxidized nanocellulose in the presence of a Ca(2+) ionic crosslinking agent. The new carboxyl groups on the surface of nanocellulose induced by the chemical oxidization provided the possibility of participating in the construction of an alginate-based sponge's structure and played a fundamental role in the structural and mechanical stability of ensuing sponges. Furthermore, enhanced mechanical strength induced by oxidized cellulose nanocrystals and the formation of a semi-interpenetrating polymer network from oxidized microfibrillated cellulose were reported. Together with the facile and ionic crosslinking process, the ultrahigh porosity, promising water absorption and retention, as well as the improved compression strength of the crosslinked sponges should significantly extend the use of this soft material in diverse practical applications.

Electrosterically stabilized nanocrystalline cellulose (ENCC) was modified in three ways: (1) the hydroxyl groups on C2 and C3 of glucose repeat units of ENCC were converted to aldehyde groups by periodate oxidation to various extents; (2) the carboxyl groups in the sodium form on ENCC were converted to the acid form by treating them with an acid-type ion-exchange resin; and (3) ENCC was cross-linked in two different ways by employing adipic dihydrazide as a cross-linker and water-soluble 1-ethyl-3-[3-(dimethylaminopropyl)] carbodiimide as a carboxyl-activating agent. Films were prepared from these modified ENCC suspensions by vacuum filtration. The effects of these three modifications on the properties of films were investigated by a variety of techniques, including UV-visible spectroscopy, a tensile test, thermogravimetric analysis (TGA), the water vapor transmission rate (WVTR), and contact angle (CA) studies. On the basis of the results from UV spectra, the transmittance of these films was as high as 87%, which shows them to be highly transparent. The tensile strength of these films was increased with increasing aldehyde content. From TGA and WVTR experiments, cross-linked films showed much higher thermal stability and lower water permeability. Furthermore, although the original cellulose is hydrophilic, these films also exhibited a certain hydrophobic behavior. Films treated by trichloromethylsilane become superhydrophobic. The unique characteristics of these transparent films are very promising for potential applications in flexible packaging and other high-technology products.

A series of amiphiphilic cellulose-based graft copolymers (MCC-g-PLA) with various molecular factors were synthesized in ionic liquid BmimCl and characterized by FT-IR, (1)H NMR, (13)C NMR, XRD, and TGA. Their solubility in a variety of solvents was compared. The prepared MCC-g-PLA copolymers can self-assemble into spherical nanomicelles (10-50 nm) in aqueous solution. The self-assembly behaviors of the MCC-g-PLA copolymers were systematically investigated by fluorescence probe. Furthermore, the hydrophobic antitumor drug paclitaxel (PTX) was successfully encapsulated into the MCC-g-PLA micelles. The drug encapsulation efficiency and loading content were found to be as high as 89.30% (w/w) and 4.97%, respectively. Results in this study not only suggest a promising cellulose-based antitumor drug carrier but also provide information for property-directed synthesis of the cellulose graft PLA copolymers.

The interaction between cellulose fibers in the presence of cationic polyacrylamide (CPAM) was analyzed by rheology as a function of polyelectrolyte concentration, charge density, and molecular weight. CPAM was found to strongly influence the yield stress of cellulose suspensions; low doses of CPAM increased the yield stress, but at higher concentrations the yield stress declined. The charge density of the CPAM was the most significant factor in how yield stress responded to CPAM concentration; this effect was able to be normalized to a master curve by considering only the charged fraction of the polymer. The molecular weight of CPAM samples had some effect at high concentrations, but for lower CPAM doses the yield stress was independent of molecular weight over the range studied. The data suggest that CPAM modifies the interaction between cellulose surfaces via several mechanisms, with electrostatic interactions in the form of charge neutralization and charged patch formation dominating; polymer bridging and steric repulsion also influence the overall balance of forces between interacting cellulose fibers.

The diffusion of charged polymers into the pores of cellulose fibers has not yet been fully understood due to the complexity of the interaction between polymers and fibers. In this paper, the diffusion of cationic-modified poly(vinyl alcohol) (CPVA) with tailored charge densities and a relatively high molecular weight into the pores of bleached aspen high-yield pulp (via a chemi-thermomechanical pulping process) was quantitatively investigated via an adsorption analysis, charge density analysis, and solute exclusion technique (SET). The results showed that the adsorption of the low-charged CPVA was substantially higher than that of the high-charged CPVA on fibers. The surface charge density analysis confirmed that approximately 17 mg/g of the high-charged CPVA adsorbed on the outer surface and on the macropores of fibers and the remaining (23 mg/g) diffused into the pores. The SET analysis confirmed that the pore size of fibers was more significantly reduced by applying the low-charged CPVA than the high-charged one. The influencing factors for the diffusion of CPVA into the large and small pores were related to the repulsion force developed between the adsorbed polymers and approaching polymers, entropy increase, and the polymer flexibility. The Brunauer-Emmett-Teller surface area analysis showed an increase in the surface area of fibers upon CPVA adsorption. It was proposed that the diffused CPVA prevented complete fiber pore collapse during drying, which eventually increased the surface area of fibers.

All-cellulose nanocomposite was directly fabricated using nanowelding of cellulose microfibers as a starting material, in 1-butyl-3-methylimidazolium chloride (BMIMCl) as a solvent, for the first time. The average diameter of the reinforcing component (undissolved nanofibrils) in the nanocomposite made directly from cellulose microfibers (NC-microfiber) was 53 ± 16 nm. Owing to its high mechanical properties (tensile strength of 208 MPa and Young's modulus of 20 GPa), high transparency (76% at a wavelength of 800 nm), and complete barrier to air and biodegradability, the NC-microfiber is regarded as a high multiperformance material. The NC-microfiber made directly from cellulose microfibers showed similar macro-, micro-, and nanostructures and the same properties as those made from solvent-based welding of ground cellulose nanofibers (NC-nanofiber). Omitting the step of cellulose nanofiber production makes the direct production of all-cellulose nanocomposite from cellulose microfibers easier, shorter, and cheaper than using cellulose nanofibers as starting material. The direct nanowelding of macro/micrometer-sized materials is theorized to be a fundamental approach for making nanocomposites.