Efficient Removal of Pb2+ from Water by Bamboo-Derived Thin-Walled Hollow Ellipsoidal Carbon-Based Adsorbent.

Lead ion (Pb2+) is one of the most common water pollutants. Herein, with bamboo as the raw material, we fabricate a thin-walled hollow ellipsoidal carbon-based adsorbent (CPCs900) containing abundant O-containing groups and carbon defects and having a specific surface area as large as 730.87 m2 g-1. CPCs900 shows a capacity of 37.26 mg g-1 for adsorbing Pb2+ in water and an efficiency of 98.13% for removing Pb2+ from water. This is much better than the activated carbon commonly used for removing Pb2+ from water (12.19 mg g-1, 30.48%). The bond interaction of Pb2+ with the O-containing groups on CPCs900 and the electrostatic interaction of Pb2+ with the electron-rich carbon defects on CPCs900 could be the main forces to drive Pb2+ adsorption on CPCs900. The outstanding adsorption performance of CPCs900 could be due to the abundant O-containing groups and carbon defects as well as the large specific surface area of CPCs900. Bamboo has a large reserve and a low price. The present work successfully converts bamboo into adsorbents with outstanding performances in removing Pb2+ from water. This is of great significance for meeting the huge industrial demand on highly efficient adsorbents for removing toxic metal ions from water.

Development of cellulose/ZnO based bioplastics with enhanced gas barrier, UV-shielding effect and antibacterial activity.

Development of renewable and biodegradable plastics with good properties, such as the gas barrier, UV-shielding, solvent resistance, and antibacterial activity, remains a challenge. Herein, cellulose/ZnO based bioplastics were fabricated by dissolving cellulose carbamate in an aqueous solution of NaOH/Zn(OH)42-, followed by coagulation in aqueous Na2SO4 solution, and subsequent hot-pressing. The carbamate groups detached from cellulose, and ZnO which transformed from cosolvent to nanofiller was uniformly immobilized in the cellulose matrix during the dissolution/regeneration process. The appropriate addition of ZnO (below 10.67 wt%) not only improved the mechanical properties but also enhanced the water and oxygen barrier properties of the material. Additionally, our cellulose/ZnO based bioplastic demonstrated excellent UV-blocking capabilities, increased water contact angle, and enhanced antibacterial activity against S. aureus and E. coli, deriving from the incorporation of ZnO nanoparticles. Furthermore, the material exhibited resistance to organic solvents such as acetone, THF, and toluene. Indeed, the herein developed cellulose/ZnO based bioplastic presents a promising candidate to replace petrochemical plastics in various applications, such as plastic toys, anti-UV guardrails, window shades, and oil storage containers, offering a combination of favorable mechanical, gas barrier, UV-blocking, antibacterial, and solvent-resistant properties.

Flexible cellulose nanofibers/MXene composite films for UV-shielding packaging.

Cellulose nanofibers (CNF) based films are promising packaging materials, but the lack of special functions (especially UV-shielding property) usually restrict their further applications. In this work, MXene was incorporated into the CNF film by a direct solvent volatilization induced film forming method to study its UV-shielding property for the first time, which avoided the using of a vacuum filtration equipment. The composite films containing glycerin could be folded repeatedly without breaking, showing good flexibility. The structure and properties of MXene/CNF composite films (CMF) were characterized systematically. The results showed that MXene distributed uniformly in the CNF film matrix and there was strong hydrogen bonding interaction between CNF and MXene. The tensile strength and Young's modulus of the composite films could reach 117.5 MPa and 2.23 GPa, which was 54.1 % and 59.2 % higher than those of pure CNF film, respectively. With the increase of MXene content, both the UVA and UVB shielding percentages increased significantly from 17.2 % and 25.5 % to 100.0 %, showing excellent UV-shielding property. Moreover, CMF exhibited a low oxygen permeability (OP) value of 0.39 cc µm d-1 m-2 kPa-1, a low water vapor permeability (WVP) value of 5.13 × 10-11 g-1s-1Pa-1 and a high antibacterial rate against E. coli (94.1 % at 24 h), showing potential application in the packaging field.

Green preparation of antibacterial shape memory foam based on bamboo cellulose nanofibril and waterborne polyurethane for adaptive relief of plantar pressure.

This study developed an aqueous solution blending and freeze-drying method to prepare an antibacterial shape memory foam (WPPU/CNF) based on waterborne PHMG-polyurethane and cellulose nanofibers derived from bamboo in response to the increasing demand for environmentally friendly, energy conserving, and multifunctional foams. The obtained WPPU/CNF composite foam has a highly porous network structure with well-dispersed CNFs forming hydrogen bonds with the WPPU matrix, which results in a stable and rigid cell skeleton with enhanced mechanical properties (80 KPa) and anti-abrasion ability. The presence of guanidine in the polyurethane chain endowed the WPPU/CNF composite foam with an instinctive and sustained antibacterial ability against Escherichia coli and Staphylococcus aureus. The WPPU/CNF composite foam exhibited a water-sensitive shape memory function in a cyclic shape memory program because of the chemomechanical adaptability of the hydrogen-bonded network of CNFs in the elastomer matrix. The shape-fixation ratio for local compression reached 95 %, and the shape-recovery rate reached 100 %. This allows the WPPU/CNF pad prototype to reversibly adjust the undulation height to adapt to plantar ulcers, which can reduce the local plantar pressure by 60 %. This study provides an environmentally friendly strategy for cellulose-based composite fabrication and enriches the design and application of intelligent foam devices.

Efficient fabrication of anisotropic regenerated cellulose films from bamboo via a facile wet extrusion strategy.

Bamboo, featuring fast growth rate and high cellulose content, is considered to be one of the most attractive feedstocks for degradable bio-materials as a substitute for plastics. However, those was limited to the fields of bamboo structural materials mainly by physical processes. Herein, we report a facile continuous wet extrusion strategy for scalable manufacturing of anisotropic regenerated cellulose films in alkali/urea aqueous solution for the first time. The bamboo cellulose solution was regenerated in H2SO4/Na2SO4/ZnSO4 aqueous solution to facilitate the construction of dense fibrils networks. Moreover, under the synergistic effect of shear orientations and stretching processes in wet extrusion molding, the cellulose networks promoted further orientated assembly into aligned fibrils. Therefore, these anisotropic cellulose hydrogels exhibited good mechanical properties, and the tensile strength was increased from 1.67 MPa of anisotropic cellulose hydrogel with 1.0 of stretching ration (ACH-1.0) to 2.13 MPa of ACH-1.4 with increasing stretching ratio from 1.0 to 1.4, which was about 1.34 times higher than that of the isotropic hydrogel fabricated by tape-casting. Moreover, ACH-1.4 exhibited commendable thermal stability and air barrier properties. This work demonstrated a simple and continuous bottom-up approach for fabrication of anisotropic bamboo-based cellulose hydrogels and films with excellent mechanical properties.

Effect of hemicellulose content on the solution properties of cellulose carbamates in NaOH/ZnO aqueous system.

Hemicellulose removal from bleached bamboo pulp is key to produce qualified dissolving pulps. In this work, alkali/urea aqueous solution was firstly applied to remove hemicellulose in bleached bamboo pulp (BP). The effect of urea usage, time and temperature on the hemicellulose content of BP was studied. The reduction of hemicellulose content from 15.9 to 5.7 % was achieved in 6 wt% NaOH/1 wt% urea aqueous solution at 40 °C for 30 min. Cellulose carbamates (CCs) were obtained from the esterification of BP with urea. The dissolution behavior of CCs in NaOH/ZnO aqueous solutions with different degree of polymerization (DP), hemicellulose and nitrogen contents were studied by using optical microscope and rheology. The highest solubility was up to 97.7 % when the hemicellulose was 5.7 % and Mη was 6.5 × 104 (g/mol). With the decrease of hemicellulose content from 15.9 % to 8.60 % and 5.70 %, the gel temperature increased from 59.0, 69.0 to 73.4 °C. The apparent gelation time increased from 5640 to 12,120 s with the hemicellulose content increased from 8.60 % to 15.9 %. CC solution with 5.70 % hemicellulose always keeps a liquid-state (G" > G') until the test time reached 17,000 s. The results showed that the removal of hemicellulose, the decrease of DP and the increase of esterification endowed CC with higher solubility and solution stability.

One-Step Treatment for Upgrading Bleached Bamboo Pulp to Dissolving Pulp High Solvency in Green Alkali/Urea Aqueous Solution.

Bleached bamboo pulp, as a kind of natural cellulose, has received significant attention in the field of biomass materials due to its advantages of environmental protection and the abundance of raw materials. Low-temperature alkali/urea aqueous system is a green dissolution technology for cellulose, which has promising application prospects in the field of regenerated cellulose materials. However, bleached bamboo pulp, with high viscosity average molecular weight (Mη) and high crystallinity, is difficult to dissolve in an alkaline urea solvent system, restraining its practical application in the textile field. Herein, based on commercial bleached bamboo pulp with high Mη, a series of dissolvable bamboo pulps with suitable Mη was prepared using a method of adjusting the ratio of sodium hydroxide and hydrogen peroxide in the pulping process. Due to the hydroxyl radicals being able to react with hydroxyls of cellulose, molecular chains are cut down. Moreover, several regenerated cellulose hydrogels and films were fabricated in an ethanol coagulation bath or a citric acid coagulation bath, and the relationship between the properties of the regenerated materials and the Mη of the bamboo cellulose was systematically studied. The results showed that hydrogel/film had good mechanical properties, as the Mη is 8.3 × 104 and the tensile strength of a regenerated film and the film have values up to 101 MPa and 3.19 MPa, respectively. In this contribution, a simple method of a one-step oxidation of hydroxyl radicals to prepare bamboo cellulose with diversified Mη is presented, providing an avenue for a preparation of dissolving pulp with different Mη in an alkali/urea dissolution system and expanding the practical applications of bamboo pulp in biomass-based materials, textiles, and biomedical materials.

Surface Charges Control the Structure and Properties of Layered Nanocomposite of Cellulose Nanofibrils and Clay Platelets.

The interfacial bonding and structure at the nanoscale in the polymer-clay nanocomposites are essential for obtaining desirable material and structure properties. Layered nanocomposite films of cellulose nanofibrils (CNFs)/montmorillonite (MTM) were prepared from the water suspensions of either CNFs bearing quaternary ammonium cations (Q-CNF) or CNFs bearing carboxylate groups (TO-CNF) with MTM nanoplatelets carrying net surface negative charges by using vacuum filtration followed by compressive drying. The effect of the ionic interaction between cationic or anionic charged CNFs and MTM nanoplatelets on the structure, mechanical properties, and flame retardant performance of the TO-CNF/MTM and Q-CNF/MTM nanocomposite films were studied and compared. The MTM nanoplatelets were well dispersed in the network of TO-CNFs in the form of nanoscale tactoids with the MTM content in the range of 5-70 wt %, while an intercalated structure was observed in the Q-CNF/MTM nanocomposites. The resulting TO-CNF/MTM nanocomposite films had a better flame retardant performance as compared to the Q-CNF/MTM films with the same MTM content. In addition, the effective modulus of MTM for the TO-CNF/MTM nanocomposites was as high as 129.9 GPa, 3.5 times higher than that for Q-CNF/MTM (37.1 GPa). On the other hand, the Q-CNF/MTM nanocomposites showed a synergistic enhancement in the modulus and tensile strength together with strain-to-failure and demonstrated a much better toughness as compared to the TO-CNF/MTM nanocomposites.

2D ultrathin carbon nanosheets with rich N/O content constructed by stripping bulk chitin for high-performance sodium ion batteries.

Two-dimensional (2D) nanomaterials hold considerable potential in reforming the energy storage performance, and the efficient production of high-performance 2D energy storage materials through facile and sustainable approaches is highly desirable. Herein, for the first time, large-area and ultrathin carbon nanosheets doped with N/O were constructed by stripping bulk chitin via a "top-down" method. On the basis of the specific layered structure composed of nanofibers, chitin samples after removing the protein and CaCO3 could be efficiently exfoliated into nanosheets (CNs) via the hydrothermal method, which were then carbonized into N/O co-doped porous carbon nanosheets (CCNs). The CCNs with a thickness of about 3.8 nm retained the original nanosheet structure consisting of nanofibers, leading to a 2D structure with hierarchical porosities. When used as anode materials for sodium-ion batteries, the 2D porous nanostructures and abundant N/O doping of CCNs-600 (carbonized at 600 °C) enable a high reversible capacity of 360 mA h g-1 at 50 mA g-1, a good rate capability of 102 mA h g-1 at 10 A g-1, and an excellent cycling stability of 140 mA h g-1 after 10 000 cycles at a high density of 5 A g-1. Full cells consisting of a CCN anode and a Na3V2(PO4)3/C cathode exhibited favorable rate performance and cycling stability, showing potential application prospects in highly efficient energy storage systems.

Distinctive Construction of Chitin-Derived Hierarchically Porous Carbon Microspheres/Polyaniline for High-Rate Supercapacitors.

Recently, nanostructured porous carbons are attracting significant interest in various important applications. However, a green and innovative method to fabricate hierarchically porous-structured carbon is still a challenge. In the present work, hierarchically porous carbon microspheres (HCMs) were prepared by pyrolyzing the chitin microspheres fabricated from a chitin/chitosan blend solution, in which chitosan was used as a forming agent of nanopores/nanochannels to construct the microspheres. The HCM displayed hierarchical porous structure and improved specific surface area of 1450 m2/g. For the application of HCM in hybrid electrode materials as supercapacitors, polyaniline (PANI) nanoclusters were further deposited on the surface of HCM. A symmetric supercapacitor based on HCM-PANI exhibited high rate capability with retaining over 64% of the capacitance as the scan rate increased from 2 to 500 mV/s. This work introduced a distinctive and green method to fabricate hierarchically porous carbon materials, having considerable application prospect for energy storage.

Targeting expression of antimicrobial peptide CAMA-Syn by adenovirus vector in macrophages inhibits the growth of intracellular bacteria.

Although purified and synthesized Cecropin A-magainin 2 (CAMA-syn) shows potent antibacterial activity in vitro, its ability to inhibit bacteria within mammal cells mediated by virus vector has not yet been investigated. To enhance its antimicrobial potential and reduce systemic side effects, it would be desirable to deliver CAMA-syn in macrophages by adenovirus vector. In this study,recombinant adenovirus Ad-MSP-CAMA/GFP were used to infect macrophages RAW264.7 cells in vitro and macrophages cells of lungs in vivo and the expression of CAMA-syn was detected by RT-PCR and observation of co-expression of GFP. Antimicrobial activity in cells was evaluated by colony enumeration. The results showed that expression of CAMA-syn in macrophages conferred antimicrobial activity against a series of bacteria, including E. coli and BCG(Bacillus Calmette-Guérin). To establish BCG infection animal model, 40 Kunming mice were randomly divided into the following four groups: adenoviral delivery of Ad-MSP-CAMA/GFP, Ad-CMV-CAMA/GFP, empty-virus Ad-GFP, and control PBS, respectively. The expression of CAMA-syn in mouse was confirmed by real-time PCR and GFP co-expression. In brief, 3 days after injection of adenoviral vector, mice were scarified, different tissues were sectioned and homogenized and colony-forming efficiency by these treated tissues was determined. The colony-forming efficiency of Ad-MSP-CAMA/GFP (78.31%) and Ad-CMV-CAMA/GFP (61.68%) showed significant reduction compared to control groups. No inhibition of bacterial colony was observed from tissues treated by the PBS or empty-virus control. In conclusion, our results demonstrated that macrophages-specific expression of antimicrobial peptide CAMA-syn in macrophages inhibited the growth of intracellular bacteria, providing a promise approach for the control of refractory intracellular infection.

Polyaniline promotes peripheral nerve regeneration by enhancement of the brain­derived neurotrophic factor and ciliary neurotrophic factor expression and activation of the ERK1/2/MAPK signaling pathway.

A previous study has demonstrated a progression in the nerve regeneration by polyaniline/cellulose (PANI/RC), although the underlying mechanism was not elucidated. In the present study, regenerated nerves were investigated, using histological techniques, functional assays and western blot analysis. The triceps surae muscle weight ratio percentages of the sham, regenerated cellulose (RC) and the PANI/RC groups were 38.88±4.76 and 76.32±7.11%, respectively. The thickness of the myelin sheath for the aforementioned groups were as follows: 1.2±0.27; 0.49±0.21 and 0.93±0.28 µl. Western blot analysis demonstrated that the ciliary neurotrophic factor (CNTF) and brain­derived neurotrophic factor (BDNF) were highly expressed in the regenerated nerve in the presence of polyaniline. Phosphorylated extracellular kinase (p­ERK)1/2 expression in the PANI/RC group was significantly elevated compared with the RC group (1.83­fold) and the sham group (4.92­fold). The expression of the axon sprout­associated proteins, such as Tau, α­tubulin and growth associated protein­43, were increased (1.64, 1.59 and 1.24­fold, respectively) compared with the RC group. The results demonstrated that PANI enhances the expression and secretion of BDNF and CNTF, activates the ERK1/2 signaling pathway and increases the expression levels of the GAP­43, Tau and α­tubulin, suggesting an insight into nerve regeneration and possible clinical interventions in nerve injury.

Natural Materials Assembled, Biodegradable, and Transparent Paper-Based Electret Nanogenerator.

Developing eco-friendly and low-cost electronics is an effective strategy to address the electronic waste issue. In this study, transparent cellulose nanopaper (T-paper) and polylactic acid (PLA) electret were used to construct a biodegradable and transparent paper-based electret nanogenerator. The nanogenerator could be assembled with paper products to form a self-powered smart packaging system without impairing the appearance, due to the high transparency and desirable output performance. Furthermore, the self-degradation property in the natural soil of the nanogenerator is demonstrated, indicating that the nanogenerator is recycled and will not pollute the environment. We anticipate that this study will provide new insights to develop eco-friendly power source and paper-based electronics.

Micro-Nanostructured Polyaniline Assembled in Cellulose Matrix via Interfacial Polymerization for Applications in Nerve Regeneration.

Conducting polymers have emerged as frontrunners to be alternatives for nerve regeneration, showing a possibility of the application of polyaniline (PANI) as the nerve guidance conduit. In the present work, the cellulose hydrogel was used as template to in situ synthesize PANI via the limited interfacial polymerization method, leading to one conductive side in the polymer. PANI sub-micrometer dendritic particles with mean diameter of ∼300 nm consisting of the PANI nanofibers and nanoparticles were uniformly assembled into the cellulose matrix. The hydrophobic PANI nanoparticles were immobilized in the hydrophilic cellulose via the phytic acid as "bridge" at presence of water through hydrogen bonding interaction. The PANI/cellulose composite hydrogels exhibited good mechanical properties and biocompatibility as well as excellent guiding capacity for the sciatic nerve regeneration of adult Sprague-Dawley rats without any extra treatment. On the basis of the fact that the pure cellulose hydrogel was an inert material for the neural repair, PANI played an indispensable role on the peripheral nerve regeneration. The hierarchical micro-nanostructure and electrical conductivity of PANI could remarkably induce the adhesion and guiding extension of neurons, showing its great potential in biomedical materials.

A BCI-based environmental controller for the motion-disabled.

With the development of brain-computer interface (BCI) technology, researchers are now attempting to put current BCI techniques into practical application. This paper presents an environmental controller using a BCI technique based on steady-state visual evoked potential. The system is composed of a stimulator, a digital signal processor, and a trainable infrared remote-controller. The attractive features of this system include noninvasive signal recording, little training requirement, and a high information transfer rate. Our test results have shown that this system can distinguish at least 48 targets and provide a transfer rate up to 68 b/min. The system has been applied to the control of an electric apparatus successfully.

Design and implementation of a brain-computer interface with high transfer rates.

This paper presents a brain-computer interface (BCI) that can help users to input phone numbers. The system is based on the steady-state visual evoked potential (SSVEP). Twelve buttons illuminated at different rates were displayed on a computer monitor. The buttons constituted a virtual telephone keypad, representing the ten digits 0-9, BACKSPACE, and ENTER. Users could input phone number by gazing at these buttons. The frequency-coded SSVEP was used to judge which button the user desired. Eight of the thirteen subjects succeeded in ringing the mobile phone using the system. The average transfer rate over all subjects was 27.15 bits/min. The attractive features of the system are noninvasive signal recording, little training required for use, and high information transfer rate. Approaches to improve the performance of the system are discussed.