Tailoring Hydronium ion Driven Dissociation-Chemical Cross-Linking for Superfast One-Pot Cellulose Dissolution and Derivatization to Build Robust Cellulose Films.

Concepts of sustainability must be developed to overcome the increasing environmental hazards caused by fossil resources. Cellulose derivatives with excellent properties are promising biobased alternatives for petroleum-derived materials. However, a one-pot route to achieve cellulose dissolution and derivatization is very challenging, requiring harsh conditions, high energy consumption, and complex solubilizing. Herein, we design a one-pot tailoring hydronium ion driven dissociation-chemical cross-linking strategy to achieve superfast cellulose dissolution and derivatization for orderly robust cellulose films. In this strategy, there is a powerful driving force from organic acid with a pKa below 3.75 to dissociate H+ and trigger the dissolution and derivatization of cellulose under the addition of H2SO4. Nevertheless, the driving force can only trigger a partial swelling of cellulose but without dissolution when the pKa of organic acid is above 4.26 for the dissociation of H+ is inhibited by the addition of inorganic acid. The cellulose film has high transmittance (up to ∼90%), excellent tensile strength (∼122 MPa), and is superior to commercial PE film. Moreover, the tensile strength is increased by 400% compared to cellulose film prepared by the ZnCl2 solvent. This work provides an efficient solvent, which is of great significance for emerging cellulose materials from renewable materials.

Advanced Functionalized Materials Based on Layer-by-Layer Assembled Natural Cellulose Nanofiber for Electrodes: A Review.

The depletion of fossil fuel resources and its impact on the environment provide a compelling motivation for the development of sustainable energy sources to meet the increasing demand for energy. Accordingly, research and development of energy storage devices have emerged as a critical area of focus. The electrode materials are critical in the electrochemical performance of energy storage devices, such as energy storage capacity and cycle life. Cellulose nanofiber (CNF) represents an important substrate with potentials in the applications of green electrode materials due to their environmental sustainability and excellent compatibility. By utilizing the layer-by layer (LbL) process, well-defined nanoscale multilayer structure is prepared on a variety of substrates. In recent years, increasing attention has focused on electrode materials produced from LbL process on CNFs to yield electrodes with exceptional properties, such as high specific surface area, outstanding electrical conductivity, superior electrochemical activity, and exceptional mechanical stability. This review provides a comprehensive overview on the development of functional CNF via the LbL approach as electrode materials.

Aqueous Sol-Gel Synthesis and Shaping of Covalent Organic Frameworks.

The intrinsic fragility and insoluble nature of covalent organic frameworks (COFs) have strongly impeded their processability for practical applications. Herein, an aqueous-based sol-gel synthetic strategy is reported for the synthesis and shaping of COFs with task-specific applications that satisfy the principles of green chemistry for gram-scale production of crystalline materials. Our successful approach involves three pivotal aspects: the "prodrug mimic" design of water-soluble monomers, the utilization of hydrolyzable bonds, and the manipulation of reaction kinetics. The generality of the method is demonstrated by the successful preparation of representative high-surface area two-dimensional (2D) COFs with several commonly used amines. By virtue of this strategy, a COF colloidal dispersion is achieved and can be formulated into processable fluids, structured films, and COF monoliths. Remarkably, the obtained lightweight (∼0.020 g cm-3) and robust aerogels displayed outstanding adsorption capacity (exceeding 57 times its own weight) toward a variety of organic solvents and exhibited superior thermal insulating properties compared to the widely used sponge and cotton. This work demonstrates a versatile strategy for the synthesis and shaping of processable COF materials in water that will contribute to the development of COF monoliths for advanced applications.

Surface Modification, Topographic Design and Applications of Superhydrophobic Systems.

Superhydrophobic surfaces with expanded wetting behaviors, like tunable adhesion, hybrid surface hydrophobicity and smart hydrophobic switching have attracted increasing attention due to their broad applications. Herein, the construction methods, mechanisms and advanced applications of special superhydrophobicity are reviewed, and hydro/superhydrophobic modifications are categorized and discussed based on their surface chemistry, and topographic design. The formation and maintenance of special superhydrophobicity in the metastable state are also examined and explored. In addition, particular attention is paid to the use of special wettability in various applications, such as membrane distillation, droplet-based electricity generators and anti-fogging surfaces. Finally, the challenges for practical applications and future research directions are discussed.

Topographical Design and Thermal-Induced Organization of Interfacial Water Structure to Regulate the Wetting State of Surfaces.

Smart surfaces with superhydrophobic/superhydrophilic characteristics can be controlled by external stimuli, such as temperature. These transitions are attributed to the molecular-level conformation of the grafted polymer chains due to the varied interactions at the interface. Here, tunable surfaces were prepared by grafting two well-known thermo-responsive polymers, poly(N-isopropylacrylamide) (PNIPAM) and poly(oligoethylene glycol)methyl ether acrylate (POEGMA188) onto micro-pollen particles of uniform morphology and roughness. Direct Raman spectra and thermodynamic analyses revealed that above the lower critical solution temperature, the bonded and free water at the interface partially transformed to intermediate water that disrupted the "water cage" surrounding the hydrophobic groups. The increased amounts of intermediate water produced hydrogen bonding networks that were less ordered around the polymer grafted microparticles, inducing a weaker binding interaction at the interface and a lower tendency to wet the surface. Combining the roughness factor, the bulk surface assembled by distinct polymer-grafted-pollen microparticles (PNIPAM or POEGMA188) could undergo a different wettability transition for liquid under air, water, and oil. This work identifies new perspectives on the interfacial water structure variation at a multiple length scale, which contributed to the temperature-dependent surface wettability transition. It offers inspiration for the application of thermo-responsive surface to liquid-gated multiphase separation, water purification and harvesting, biomedical devices, and printing.

Application of Pickering emulsions in probiotic encapsulation- A review.

Probiotics are live microorganisms that confer health benefits to host organisms when consumed in adequate amounts and are often incorporated into foods for human consumption. However, this has negative implications on their viability as large numbers of these beneficial bacteria are deactivated when subjected to harsh conditions during processing, storage, and passage through the gastrointestinal tract. To address these issues, numerous studies on encapsulation techniques to protect probiotics have been conducted. This review focuses on emulsion technology for probiotic encapsulation, with a special focus on Pickering emulsions. Pickering emulsions are stabilized by solid particles, which adsorb strongly onto the liquid-liquid interfaces to prevent aggregation. Pickering emulsions have demonstrated enhanced stability, high encapsulation efficiency, and cost-effectiveness compared to other encapsulation techniques. Additionally, Pickering emulsions are regarded as safe and biocompatible and utilize natural materials, such as cellulose and chitosan derived from plants, shellfish, and fungi, which may also be viewed as more acceptable in food systems than common synthetic and natural molecular surfactants. This article reviews the current status of Pickering emulsion use for probiotic delivery and explores the potential of this technique for application in other fields, such as livestock farming, pet food, and aquaculture.

Cellulose-based aerogel beads for efficient adsorption- reduction- sequestration of Cr(VI).

The reduction and sequestration of toxic Cr(VI) via a one-step process in an aqueous solution is critical to eliminate its environmental risk. In this study, amine functionalized cellulose-based aerogel beads (CGP) was developed for simultaneous and efficient adsorption- reduction- sequestration of Cr(VI). CGP showed a maximum Cr(VI) adsorption capacity of 386.40 mg/g at 25 °C due to its strong electrostatic attraction towards Cr(VI). The simultaneous Cr(VI) adsorption- reduction- sequestration performance of CGP over a wide Cr(VI) concentration range was examined. The mechanism was investigated in-depth via the analysis of adsorption kinetics, XPS spectra, and FTIR spectra. Moreover, the Cr immobilization stability of CGP after adsorption was evaluated in simulated neutral, acidic, and alkaline conditions. The effect of pH, temperature, ionic strength and the presence of interfering ions on CGP adsorption performance were investigated by batch adsorption experiments. Fixed-bed column adsorption study was performed to explore the application potential of CGP beads in a wastewater treatment process.

Synthesis of silver nanoclusters in colloidal scaffold for biolabeling and antimicrobial applications.

A robust method to prepare silver nanoclusters (AgNCs) inside a methacrylic acid-ethyl acrylate (MAA-EA) nanogel is proposed, where AgNCs were produced within the nanogel scaffold via UV-photoreduction. The impact of UV irradiation time on the formation of AgNCs and their application in biolabeling and antimicrobial properties were examined. The AgNCs formation is described by two stages; (1) Agn (n = 2-8) nanoclusters formation between 0 and 25 min, and (2) larger silver nanoparticles (AgNPs) formed via aggregation inside the nanogel. The antimicrobial performance depended on the size and concentration of silver ions (Ag+). A maximum inhibitory concentration (MIC) of 1.1 ppm was observed for antimicrobial test with yeast, and a MIC of 11 and 22 ppm was recorded for Escherichia. coli and Staphylococcus aureus respectively. Combining with the green illumination property of AgNCs (emitted at 525 nm) with dead yeast, it could be used for biolabeling. By tuning the size through photoirradiation, the nanogel templated AgNCs is a promising candidate for antimicrobial and biolabeling applications.

Flexible, anti-damage, and non-contact sensing electronic skin implanted with MWCNT to block public pathogens contact infection.

If a person comes into contact with pathogens on public facilities, there is a threat of contact (skin/wound) infections. More urgently, there are also reports about COVID-19 coronavirus contact infection, which once again reminds that contact infection is a very easily overlooked disease exposure route. Herein, we propose an innovative implantation strategy to fabricate a multi-walled carbon nanotube/polyvinyl alcohol (MWCNT/PVA, MCP) interpenetrating interface to achieve flexibility, anti-damage, and non-contact sensing electronic skin (E-skin). Interestingly, the MCP E-skin had a fascinating non-contact sensing function, which can respond to the finger approaching 0-20 mm through the spatial weak field. This non-contact sensing can be applied urgently to human-machine interactions in public facilities to block pathogen. The scratches of the fruit knife did not damage the MCP E-skin, and can resist chemical corrosion after hydrophobic treatment. In addition, the MCP E-skin was developed to real-time monitor the respiratory and cough for exercise detection and disease diagnosis. Notably, the MCP E-skin has great potential for emergency applications in times of infectious disease pandemics. Electronic Supplementary Material: Supplementary material (fabrication of MCP E-skin, laser confocal tomography, parameter optimization, mechanical property characterization, finite element simulation, sensing mechanism, signal processing) is available in the online version of this article at 10.1007/s12274-021-3831-z.

Sustainable Superhydrophobic Surface with Tunable Nanoscale Hydrophilicity for Water Harvesting Applications.

Superwettable surfaces show great potential in water harvesting applications, however, a scalable water harvesting surface remains elusive due to the trade-off between water deposition and transport. Herein, we report a unique superhydrophobic surface with tunable nanoscale hydrophilicity constructed by structured Pickering emulsions. Preferential exposure of the cellulose nanocrystal's outer surface and wax microspheres accelerates droplet deposition allowing for the manipulation of droplet mobility. Appropriate tuning of the wetting characteristics of the surfaces, optimizing the hydrophobicity and density of the water affinity nanodomains enhance the water deposition rate without the sacrifice of water transport rate, achieving an optimal water harvesting flux of 3.402 L m-2 h-1 for a plate and 5.02 L m-2 h-1 for a mesh. This hydrophilic/superhydrophobic surface allows the controllable manipulation of droplet nucleation and removal to enhance the water harvesting efficiency.

Highly sensitive self-healable strain biosensors based on robust transparent conductive nanocellulose nanocomposites: Relationship between percolated network and sensing mechanism.

The conventional skin sensor detection of human physiological signals can be an effective method for disease diagnosis and health monitoring, but the poor biocompatibility, low sensitivity and complex design largely limit their applications. Developing natural nanofiller-reinforced composites as strain biosensors is an appealing solution to reduce environmental impacts and overcome technical bottleneck. Herein, a versatile nature skin-inspired composite film as flexible strain biosensor was developed based on cellulose nanocrystals-polyaniline (CNC-PANI) composites by utilizing their percolated conductive network in polyvinyl alcohol (PVA) matrix. The composite electronic skin showed robust mechanical strength (50.62 MPa) and high sensitivity (Gauge Factor = 11.467) with easy water-induced self-healing abilities. Moreover, we investigated the functioning mechanism of percolated network and the sensory behavior determined by CNC nanocomposite alignment. The percolation threshold of CNC-polyaniline (PANI) was determined at 4.278% and 5% CNC-PANI composite film shows the best overall sensing property. It was also discovered that the sensitivity of this type of conductive-filler electronic skin can be divided into two separate regions at different strain range due to its percolated network. With films prepared by dry casting and dip coating, the alignment of CNC-PANI also contributes to this unique change in electrical property. Generally, our results demonstrated the mechanism and tunability of conductive nanofiller-based composite strain biosensors as a potential alternative to commercial synthetic sensors.

Versatile nanocellulose-based nanohybrids: A promising-new class for active packaging applications.

The food packaging industry is rapidly growing as a consequence of the development of nanotechnology and changing consumers' preferences for food quality and safety. In today's globalization of markets, active packaging has achieved many advantages with the capability to absorb or release substances for prolonging the food shelf life over the traditional one. Therefore, it is critical to developing multifunctional active packaging materials from biodegradable polymers with active agents to decrease environmental challenges. This review article addresses the recent advances in nanocelluloses (NCs)- baseds nanohybrids with new function features in packaging, focusing on the various synthesis methods of NCs-based nanohybrids, and their reinforcing effects as active agents on food packaging properties. The applications of NCs-based nanohybrids as antioxidants, antimicrobial agents, and UV blocker absorbers for prolonging food shelf-life are also reviewed. Overall, these advantages make the CNs-based nanohybrids with versatile properties promising in food and packaging industries, which will impact more readership with concern for future research.

Co(III)-Salen immobilized cellulose nanocrystals for efficient catalytic CO2 fixation into cyclic carbonates under mild conditions.

Searching for green, recyclable and highly efficient catalyst for the synthesis of cyclic carbonates from CO2 is of great importance because it is profitable for reducing the greenhouse effects and meets the principles of green chemistry. Herein, a series of cellulose nanocrystals, either the pristine or modified ones (TEMPO oxidized and Co(III)salen immobilized), were explored as catalysts for cycloaddition of epoxides and carbon dioxide. The impact of surface properties on the performance of the as-made catalysts was investigated. Co(III)-salen grafted cellulose nanocrystals was proven to be the most effective catalyst in this study, which could afford excellent yield up to 99 % after 24 h even under low CO2 pressures of 0.1 MPa. They can be easily recovered and reused for at least 4 times, demonstrating their excellent stability. We found that the surface functional groups such as enriched sulfate or carboxylic groups could also account for the enhanced catalytic activity. This work highlights the applications of green and sustainable nanoparticles in a cycloaddition reaction and offers a sustainable solution in industrial catalysis related to CO2 conversions.

Carbodiimide coupling versus click chemistry for nanoparticle surface functionalization: A comparative study for the encapsulation of sodium cholate by cellulose nanocrystals modified with ß-cyclodextrin.

Grafting beta-cyclodextrin (ß-CD) onto cellulose nanocrystals (CNC) with the formation of well-dispersed nanoparticles (CNC-CD) and understanding their physicochemical properties are appealing but still challenging in controlled-release applications. Two immobilization methods were proposed and examined in this study; (i) copper (I) catalyzed click chemistry (CuACC) and (ii) carbodiimide coupling. Fourier-transform infrared spectroscopy (FTIR), UV-vis, elementary analysis, contact angle measurements, and thermogravimetric analysis (TGA) were conducted to elucidate the surface modifications. Phenolphthalein (PHTH) titration was used to quantify the grafting efficiency of ß-CD on the CNC surface. The carbodiimide coupling in dimethyl sulfoxide was effective to introduce the highest amounts of ß-CD (0.17 mmol/g sample) to the CNC in this study. The encapsulation process of bile surfactant, sodium cholate (NaC) was investigated by isothermal titration calorimeter (ITC), and the thermodynamic parameters were determined. The "molecular docking" brought by ß-CD offers possible new applications of this sustainable nanohybrid system in the environmental, biomedical and pharmaceutical sectors.

Carboxylated cellulose cryogel beads via a one-step ester crosslinking of maleic anhydride for copper ions removal.

In this study, we developed a one step protocol to prepare highly carboxylated and chemically crosslinked cellulose nanofibril (CNF) cryogel beads using maleic anhydride (MA). Fourier transform infrared spectroscopy (FTIR) and conductometric-potentiometric titration results confirmed the presence of carboxyl groups and ester linkages produced simultaneously during the ring open reaction of MA, yielding a carboxylic content of up to 2.78 mmol/g. The effect of CNF concentration on the morphology and wet mechanical strength of the crosslinked cryogel beads were also investigated, and results suggested that higher CNF concentration yielded a compact network that displayed a maximum compressive stress of 2800 Pa at 60 % strain. In addition, the heavy metal ions (i.e., Cu (II)) removal capacity, kinetics, mechanism as well as the recyclability of the resulted CNF-MA cryogel beads were examined.

Double stimuli-responsive cellulose nanocrystals reinforced electrospun PHBV composites membrane for intelligent drug release.

Double stimuli-responsive functionalized cellulose nanocrystal-poly[2-(dimethylamino)ethyl methacrylate] (CNC-g-PDMAEMA) reinforced poly(3-hydroxybutyrate-co-3-hydroxy valerate) (PHBV) electrospun composite membranes were explored as drug delivery vehicles using tetracycline hydrochloride (TH) as a model drug. It was found that rigid CNC-g-PDMAEMA nanoparticles enhanced thermal, crystallization and hydrophilic properties of PHBV. Moreover, great improvements in fiber diameter uniformity, crystallization ability and maximum decomposition temperature (Tmax) could be achieved at 6 wt% CNC-g-PDMAEMA. Furthermore, by introducing stimuli-responsive CNC-g-PDMAEMA nanofillers, intelligent and long-term sustained release behavior of composite membranes could be achieved. The releasing mechanism of composite membranes based on zero order, first order, Higuchi and Korsmeyere-Peppas mathematical models was clearly demonstrated, giving effective technical guidance for practical drug delivery systems.

Novel design of Fe-Cu alloy coated cellulose nanocrystals with strong antibacterial ability and efficient Pb2+ removal.

We report a facile method to prepare a novel composite based on Fe-Cu alloy decorated cellulose nanocrystals (Fe-Cu@CNC) via simple oxidation-reduction reaction. Spherical zero-valent iron nanoparticles (NZVI) and sheet-like copper nanoparticles were serially anchored on the CNC surface, and the generated composite exhibited excellent antibacterial activities and highly efficient Pb2+ removal. The composites had high antibacterial ratios of 95.9 %-99.9 %, because superoxide radicals can cause irreversible damage to the bacteria, eventually leading to apoptosis and bacterial death. Meanwhile, the Fe-Cu@CNC composite showed quick Pb2+ ion removal, reaching a 70.76 % removal within 5 min, a total removal of 93.98 % after 1 h, and excellent reusability (retaining removal efficiency of 80.41 % after six cycles). The adsorption kinetics demonstrated that the adsorption behavior can be described by pseudo-second-order kinetic model (R2>0.99). This study offers a new strategy to prepare a promising composite with advanced antibacterial and heavy metal removal properties for wastewater treatment.

Self-healing stimuli-responsive cellulose nanocrystal hydrogels.

A facile and universal approach to prepare cellulose nanocrystal reinforced functional hydrogels is proposed. An organic solvent-free and eco-friendly method was adopted, where both the modification and polymerization were conducted in an aqueous solution. Cellulose nanocrystal (CNC) and sodium alginate (SA) were first oxidized under mild conditions to introduce aldehyde groups. Subsequently, amine-containing vinyl functionalized monomers were introduced to the surface of CNC or backbone of oxidized SA via a dynamic Schiff-base reaction. The bio-based hydrogels were then prepared via a one-pot in-situ polymerization, where the functional CNC and SA served as novel macro-cross-linkers that contributed to the structural integrity and mechanical stability of the hydrogels. The hydrogels displayed uniform chemical and macroscopic structures and could self-heal within several hours at room temperature. The design of specific monomers will allow the introduction of stimuli-responsive properties to the functional hydrogels and a chemically robust thermally-triggered actuator was demonstrated. Due to its flexible design and practical approach, the hydrogels could find potential uses in agricultural and pharmaceutical products.

Designing Highly Luminescent Cellulose Nanocrystals with Modulated Morphology for Multifunctional Bioimaging Materials.

Spherical cellulose nanocrystals (SCNs) and rod-shaped cellulose nanocrystals (RCNs) were extracted from different cellulose materials. The two shape forms of cellulose nanocrystals (CNs) were designed with a combination of isothiocyanate (FITC), and both the obtained FITC-SCNs and FITC-RCNs exhibited high fluorescence brightness. The surfaces of SCNs and RCNs were subjected to a secondary imino group by a Schiff reaction and then covalently bonded to the isothiocyanate group of FITC through a secondary imino group to obtain fluorescent cellulose nanocrystals (FITC-CNs). The absolute ζ-potential and dispersion stability of FITC-CNs (FITC-SCNs and FITC-RCNs) were improved, which also promoted the increase in the fluorescence quantum yield. FITC-RCNs had a fluorescence quantum yield of 30.7%, and FITC-SCNs had a morphological advantage (better dispersion, etc.), resulting in a higher fluorescence quantum yield of 35.9%. Cell cytotoxicity experiments demonstrated that the process of FITC-CNs entering mouse osteoblasts (MC3T3) did not destroy the cell membrane, showing good biocompatibility. On the other hand, FITC-CNs with good dispersibility can significantly enhance poly(vinyl alcohol) (PVA) and poly(lactic acid) (PLA); their mechanical properties were improved (the highest sample reached to 243%) and their fluorescent properties were imparted. This study provides a simple surface functionalization method to produce high-luminance fluorescent materials for bioimaging, multifunctional nanoenhancement/dispersion marking, and anticounterfeiting materials.