Hyper strength, high sensitivity integrated wearable signal sensor based on non-covalent interaction of an ionic liquid and bacterial cellulose for human behavior monitoring.

Ion-sensing hydrogels exhibit electrical conductivity, softness, and mechanical and sensory properties akin to human tissue, rendering them an ideal material for mimicking human skin. In the realm of fabricating sensors for detecting human physiological activities, they present an ideal alternative to traditional rigid metal conductors. Nevertheless, achieving ionic hydrogels with outstanding tensile properties, toughness, ionic conductivity, and transport stability poses a significant challenge. This paper describes a simple method of forming a basic network by free radical polymerization of acrylamide, and then bacterial cellulose (BC) and 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl) were introduced into the basic network. The polyhydrogen bonds and electrostatic interactions in the system gave the hydrogel notable tensile properties (3271 ± 37%), toughness (7.39 ± 0.13 MJ m-3), and high ultimate tensile stress (385.1 ± 7.2 kPa). In addition, the combination of BC and [EMIM]Cl collaboratively enhanced the mechanical properties and electrical conductivity. Ion sensing hydrogels have a wide operating strain range (≈1000%) and high sensitivity (gage factor (GF) = 11.85), and are therefore considered promising candidates for next-generation gel-based strain sensor platforms.

Bacterial cellulose/gelatin-based pH-responsive functional film for food freshness monitoring.

Food safety is related to public health and environmental safety. Therefore, it is necessary to develop accurate and effective detection methods to assess food quality and safety. In this study, a pH-responsive functional film (BC/GA/FITC/PCA) was generated for the real-time and visual monitoring of shrimp freshness. Bacterial cellulose /Gelatin (BC/GA) was used as a film-forming matrix, and fluorescein isothiocyanate (FITC) and red cabbage (PCA) were used as the response signals. The addition of FITC and PCA increased the shading capacity (< 30 %) and antioxidant properties (22.8 %) of the films. WCA (82.73 ± 0.95°), WVP (1.48 × 10-11 g·cm/cm2·s·Pa) and OTR (2.42 × 10-15 cm3·cm/cm2·s·Pa) indicated that the film possessed water resistance and oxygen barrier properties. When exposed to daylight, the film underwent a color transition from purple to green as the ammonia concentration increased. In addition, the blue-green fluorescence of the films gradually increased and the detection limit was low (170 ppb). In particular, the change in film color caused by shrimp spoilage corresponded to the TVBN value. This study work provides a new strategy for controlling and monitoring food safety and has a wide range of applications in the fields of food-active packaging and smart packaging.

Super-stretching and high-performance ionic thermoelectric hydrogels based on carboxylated bacterial cellulose coordination for self-powered sensors.

Self-powered sensors that do not require external power sources are crucial for next-generation wearable electronics. As environment-friendly ionic thermoelectric hydrogels can continuously convert the low-grade heat of human skin into electricity, they can be used in intelligent human-computer interaction applications. However, their low thermoelectric output power, cycling stability, and sensitivity limit their practical applications. This paper reports a 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized carboxylated bacterial cellulose (TOBC) coordination double-network ionic thermoelectric hydrogel with lithium bis(trifluoromethane) sulfonimide (LiTFSI) as an ion provider for thermodiffusion, as LiTFSI exhibits excellent thermoelectric properties with a maximum power output of up to 538 nW at a temperature difference of 20 K. The interactions between the ions and the hydrogel matrix promote the selective transport of conducting ionic ions, producing a high Seebeck coefficient of 11.53 mV K-1. Hydrogen bonding within the polyacrylamide (PAAm) network and interactions within the borate ester bond within the TOBC confer excellent mechanical properties to the hydrogel such that the stress value at a tensile deformation of 3100 % is reaches 0.85 MPa. The combination of the high ionic thermovoltage and excellent mechanical properties ionic thermoelectric hydrogels provides an effective solution for the design and application of self-powered sensors based on hydrogels.

Highly robust and sensitive dual-network freeze-resistant organic hydrogel thermocells.

Thermocells (TECs) are eco-friendly and ideal power-generation devices that sustainably convert waste heat into electricity to power wearable electronics. However, their poor mechanical properties, limited operating temperature, and low sensitivity limit their practical application. Hence, K3/4Fe(CN)6 and NaCl thermoelectric materials were introduced into a bacterial cellulose-reinforced polyacrylic acid double-network structure and permeated into a glycerol (Gly)/water binary solvent to prepare an organic thermoelectric hydrogel. The resulting hydrogel had a tensile strength of approximately 0.9 MPa and a stretched length of approximately 410 %; moreover, it worked stably even in the stretched/twisted state. Owing to the introduction of Gly and NaCl, the as-prepared hydrogel exhibited excellent freezing tolerance (- 22 °C). In addition, the TEC also demonstrated excellent sensitivity (~13 s). Good environmental stability and high sensitivity make this hydrogel TEC a promising candidate for thermoelectric power-generation/temperature-monitoring systems.

Bifunctional collagen fiber/carbon quantum dot fluorescent adsorbent for efficient adsorption and detection of Pb2.

In this work, fluorescent adsorbents that can efficiently detect and remove Pb2+ were developed by integrating the designed amino-modified carbon quantum dots and carboxyl-modified collagen. The adsorption properties of the fluorescent adsorbent were further optimized and analyzed using a series of response surface experiments. The maximum adsorption concentration for Pb2+ was 183 mg.g-1. The adsorption isotherms fit well with the Langmuir model, and the adsorption kinetics fit with the pseudo-second-order model. The emission intensity of the fluorescent adsorbent gradually decreased with the increase of the concentration of Pb2+, and had a good linear correlation. In addition, the mechanism of detection and removal of Pb2+ by fluorescent adsorbents was further demonstrated. The novel three-dimensional structured fluorescent aerogel can be used as a promising adsorbent with good adsorption concentration and sensing ability for Pb2+, which shows great prospects in wastewater.

Bacterial cellulose-based dual chemical reaction coupled hydrogel thermocells for efficient heat harvesting.

Reasonable and efficient utilization of low-grade thermal energy in nature is the choice for sustainable energy development. We demonstrate a bacterial cellulose (BC) hydrogel thermocell (TEC) based on BC electrolyte combined with carbon fiber paper and copper composite electrode sheets. The large specific surface area of carbon fiber paper provides a large number of active sites for thermoelectric ions, which drives the redox reaction inside the electrolyte and stimulates the chemical reaction between the electrolyte and the electrode. The combination of the two chemical reactions significantly improves the thermoelectric performance of the thermocell. The thermopower of the BC-TEC reaches 5.9 mV·K-1 at a temperature difference of 50 K. The TEC consisting of 6-units in series produces an open-circuit voltage of about 2 V and a peak power of 535 µW. The TEC shows new potential and prospects in ambient thermoelectric energy conversion by rationally designing the power generation principle.

Nanoarchitectonics for High Adsorption Capacity Carboxymethyl Cellulose Nanofibrils-Based Adsorbents for Efficient Cu2+ Removal.

In the present study, carboxymethyl cellulose nanofibrils (CMCNFs) with different carboxyl content (0.99-2.01 mmol/g) were prepared via controlling the ratio of monochloroacetic acid (MCA) and sodium hydroxide to Eucalyptus bleached pulp (EBP). CMCFs-PEI aerogels were obtained using the crosslinking reaction of polyethyleneimine (PEI) and CMCNFs with the aid of glutaraldehyde (GA). The effects of pH, contact time, temperature, and initial Cu2+ concentration on the Cu2+ removal performance of CMCNFs-PEI aerogels was highlighted. Experimental data showed that the maximum adsorption capacity of CMCNF30-PEI for Cu2+ was 380.03 ± 23 mg/g, and the adsorption results were consistent with Langmuir isotherm (R2 > 0.99). The theoretical maximum adsorption capacity was 616.48 mg/g. After being treated with 0.05 M EDTA solution, the aerogel retained an 85% removal performance after three adsorption-desorption cycles. X-ray photoelectron spectroscopy (XPS) results demonstrated that complexation was the main Cu2+ adsorption mechanism. The excellent Cu2+ adsorption capacity of CMCNFs-PEI aerogels provided another avenue for the utilization of cellulose nanofibrils in the wastewater treatment field.

Degradable collagen/sodium alginate/polyvinyl butyral high barrier coating with water/oil-resistant in a facile and effective approach.

Degradable bio-based materials have been widely considered as functional coatings, however, it is a great challenge to fabricate biodegradable coatings with high barrier, water- and oil- resistance. In this work, such coatings were fabricated by using collagen fibers (CF), sodium alginate (SA), and polyvinyl butyral (PVB). CF and SA were mixed evenly and coated on Ca2+ pretreated filter paper. It was mainly due to the electrostatic adsorption between collagen fibers and sodium alginate, and the crosslinking between the adsorption products and Ca2+. By coating PVB solution, the barrier performance was further improved. Notably, the composite exhibited excellent water vapor resistance (48 g/m2·24 h), water resistance (31 g/m2), oil resistance (kit rating: 12/12) and good mechanical properties. This degradable, environmentally friendly, and simple composite paper method has excellent barrier properties, mechanical properties and fluorine-free properties, and will have many applications in the food and packaging fields.

Wood-inspired high strength and lightweight aerogel based on carbon nanotube and nanocellulose fiber for heat collection.

Wood is one of the most abundant materials in nature, with excellent mechanical properties and anisotropy. Its main component, cellulose has excellent dispersion properties and biocompatibility after nano-treatment, which has aroused the interest of researchers. Therefore, this study prepared a thermoelectric aerogel based on carboxylated nanocellulose fiber and carbon nanotube, and made it have a wood-like anisotropic structure through directional freezing technology. The aerogel exhibited excellent mechanical properties and had the stress of up to 152 kPa when compressed at 90%. It also exhibited low thermal conductivity (0.03-0.08 W/mK) and density (7.5 mg/cm3). When the device was at a temperature difference of 30 K, the single output power was 0.23 nW. This work confirmed the dispersion effect of carboxylated nanocellulose fiber on carbon nanotube, and the enhancement of the wood-like structure on thermoelectric generators. It provided new ideas and solutions for the construction of thermoelectric devices.

In vitro gastrointestinal digestibility of corn oil-in-water Pickering emulsions stabilized by three types of nanocellulose.

The effect of three nanocellulose (various in crystalline allomorph and morphology) on lipid in vitro gastrointestinal digestibility was investigated. Corn oil-in-water emulsions were prepared by CNCs-I, CNCs-II and CNFs respectively. The variations of droplets diameter D[4,3], zeta potential, and microstructure were measured during gastrointestinal digestion (mouth, stomach and small intestine), and the free fatty acid (FFA) released in the small intestine phase were examined. The FFA-released test results indicated that both crystalline allomorph and morphology of nanocellulose affected the degree of lipid digestion, especially the morphology. FFA released amount was ranked in the order of CNCs-I (56.60%), CNCs-II (48.67%) and CNFs (28.21%). This is mainly due to the difference in the self-assembly behavior of nanocellulose at the interface. Our findings provide an innovative solution that using nanocellulose as food-grade particle stabilizer to modulate the digestion of Pickering emulsified lipids, which would benefit the development of given functional foods.

Co3O4 Nanoneedle Array Grown on Carbon Fiber Paper for Air Cathodes towards Flexible and Rechargeable Zn-Air Batteries.

An economical and efficient method is developed for preparing flexible cathodes. In this work, a dense mesoporous Co3O4 layer was first hydrothermally grown in situ on the surface of chopped carbon fibers (CFs), and then carbon fiber paper (Co3O4/CP) was prepared by a wet papermaking process as a flexible zinc-air battery (ZAB). The high-performance air cathode utilizes the high specific surface area of a single chopped carbon fiber, which is conducive to the deposition and adhesion of the Co3O4 layer. Through the wet papermaking process, Co3O4/CP has ultra-thin, high mechanical stability and excellent electrical conductivity. In addition, the assembled ZAB exhibits relatively excellent electrochemical performance, with a continuous cycle of more than 180 times at a current density of 2 mA·cm-2. The zinc-air battery can maintain a close fit and work stably and efficiently even under high bending conditions. This process of combining single carbon fibers to prepare ultra-thin, high-density, high-conductivity carbon fiber paper through a papermaking process has huge application potential in the field of flexible wearables.

Excellent coating of collagen fiber/chitosan-based materials that is water- and oil-resistant and fluorine-free.

Collagen fiber has attracted much attention due to its good biocompatibility and biodegradability. In the present research, we prepared a type of non-fluorine hydrophobic and oil-resistant material using collagen fiber, chitosan, and polydimethylsiloxane (PDMS) as raw materials. To improve oil/grease resistance, the first layer filled the porous matrix and was made from the cross-linking product of collagen fiber/chitosan and glutaraldehyde. This was followed by a simple coating of PDMS, to increase hydrophobicity and water resistance. Notably, 10 g/m2 of cross-linking product and 6 g/m2 of PDMS had a low pore size as well as a smooth and uniform surface, which made the composites exhibit excellent hydrophobic and oil-resistant properties (water contact angles of 141°), water and oil resistance (kit rating value of 12/12) and mechanical properties. Fluorine-free environment-friendly materials with high water and oil resistance play an important role in promoting the development of high-performance materials for food packaging.

Pickering emulsions stabilized by spherical cellulose nanocrystals.

Nano cellulose has attracted more attentions as promising stabilizer candidate for Pickering emulsions due to its renewable and biocompatible properties. In this work, spherical cellulose nanocrystals (S-CNCs) (diameter 30-60 nm) were prepared by mixed acid hydrolysis of mercerized microcrystalline cellulose under the treatment of ultrasonic. We characterized the Pickering emulsions stabilized by various S-CNCs concentration in the aqueous phase and visualized their distribution in emulsions system. The diameter of emulsion droplets has no increase after 7 days storage. The emulsions present ultra-low viscosity even at a high S-CNCs concentration in the aqueous phase (5 g/L). Furthermore, noting that Pickering emulsions droplets stabilized by S-CNCs exhibited high stability even pH, ionic strengths, and temperatures changed in wide range. Thus, the S-CNCs acted as a new stabilizer for Pickering emulsion open opportunities for the development of biomedicine, cosmetics, and food applications.

New insights into the autofluorescence properties of cellulose/nanocellulose.

This work explored the fluorescence properties of nano/cellulose isolated from bleached softwood kraft pulp by TEMPO oxidation. Fluorescence spectra showed that all samples exhibited a typical emission peak at 574 nm due to the probabilistic formation of unsaturated bonds by glycosidic bonds independent of lignin. Increasing the excitation wavelengths (510-530 nm) caused red shift of fluorescence emission peaks (570-585 nm) with unchanged fluorescence intensity. Conversely, changing acid/alkaline conditions led to an increase of fluorescence intensity with no shifting of fluorescence emission peak. This can be attributed to an increase in the polarity of the solution environment but does not cause interaction of functional groups within the system identified by generalized two-dimensional correlation fluorescence spectroscopy. This study provides new insight in applying nano/cellulose with special luminous characteristics in biomedicine area such as multi-color biological imaging and chemical sensing.

Effect of nanocellulose fiber hornification on water fraction characteristics and hydroxyl accessibility during dehydration.

Hornification are usually occurred in cellulosic fibers and even in nanocellulose fibrils during dehydration process but their mesoscopic structural changes is not fully understood. Here we investigated the structural features of cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNF) with different solid content. In order to avoid the effect of drying, liquid AFM mode was carried out in this work. The different water contents of nanocellulose were quantified by Differential Scanning Calorimetry (DSC). We showed evidence of extreme growth in radial direction in the redispersed nanocelluloses, analyzed by statistics of contours from microscopy images. The amount of free water, freezing bound water, and non-freezing bound water decreased gradually during water evaporation and were completely removed in sequence. In addition, the hydroxyl accessibility of both redispersed CNCs and CNF were reduced by 83.33% and 81.96% via evaluating the uptake of fluorescent dyes.

Effect of retention rate of fluorescent cellulose nanofibrils on paper properties and structure.

In this work, we report a new characterization method using fluorescent cellulose nanofibrils to analyze retention and loss rates in the papermaking process. Cellulose nanofibrils (CNF) were isolated from chemical pulp by enzymatic pretreatment and used as a strengthening additive in sheet forming. The aim of this paper was to investigate its effects on flocculation, retention and loss rate and the physical and mechanical properties. CNF was subjected to fluorescent labeling with RBITC (Rhodamine B isothiocyanate), and the retention of fluorescent cellulose nanofibrils (FCNF) was analyzed by elemental analysis and fluorescence intensity. The retention and loss rate of the FCNF decreased with increasing the addition of FCNF. Laser Confocal Scanning Microscopy (LCSM) and Scanning Electron Microscope (SEM) images confirmed that FCNF can be evenly distributed in the paper. A thorough investigation of the relation between the retention rate and papersheet performance was conducted.

Influence of binding mechanism on labeling efficiency and luminous properties of fluorescent cellulose nanocrystals.

Cellulose nanocrystals (CNCs) have excellent properties, such as reproducibility, low biodegradability and a large amount of reactive hydroxyl groups on the surface. This study focused on the labeling efficiency and fluorescent properties of the fluorescent labeling of CNCs by means of electrostatic adsorption and covalent bonding. The CNCs in the sample were approximately 94.76% successfully labeled with dyes, and the number of dye molecules adsorbed by per CNC was approximately 208 by electrostatic adsorption. For the sample covalently linked, the efficiency of the fluorescent labeling was 95.51%, and the number of dye molecules attached to per CNC was 1038. The quenching mode of the fluorescent CNCs was dynamic quenching. The fluorescence lifetime and quantum yield of the fluorescent CNCs increased by 1-2 times compared to the free dye. A thorough investigation of the relation between the binding mechanism and the fluorescent properties in fluorescent CNCs was conducted.