Cellulose Nanocrystals/ZnO as a Bifunctional Reinforcing Nanocomposite for Poly(vinyl alcohol)/Chitosan Blend Films: Fabrication,Characterization and Properties

In this study, cellulose nanocrystals/zinc oxide (CNCs/ZnO) nanocomposites were dispersed as bifunctional nano-sized fillers into poly(vinyl alcohol) (PVA) and chitosan (Cs) blend by a solvent casting method to prepare PVA/Cs/CNCs/ZnO bio-nanocomposites films. The morphology, thermal, mechanical and UV-vis absorption properties, as well antimicrobial effects of the bio-nanocomposite films were investigated. It demonstrated that CNCs/ZnO were compatible with PVA/Cs and dispersed homogeneously in the polymer blend matrix. CNCs/ZnO improved tensile strength and modulus of PVA/Cs significantly. Tensile strength and modulus of bio-nanocomposite films increased from 55.0 to 153.2 MPa and from 395 to 932 MPa, respectively with increasing nano-sized filler amount from 0 to 5.0 wt %. The thermal stability of PVA/Cs was also enhanced at 1.0 wt % CNCs/ZnO loading. UV light can be efficiently absorbed by incorporating ZnO nanoparticles into a PVA/Cs matrix, signifying that these bio-nanocomposite films show good UV-shielding effects. Moreover, the biocomposites films showed antibacterial activity toward the bacterial species Salmonella choleraesuis and Staphylococcus aureus. The improved physical properties obtained by incorporating CNCs/ZnO can be useful in variety uses.     

再生纤维素/壳聚糖/银纳米线抗菌复合膜制备及性能

以1-丁基-3甲基咪唑氯盐（[Bmim]Cl）为溶剂体系，通过微晶纤维素（MCC）溶解再生制备基膜，壳聚糖（CS）、银纳米线（AgNW）共混液包覆方法制备抗菌复合膜，通过FTIR、XRD、SEM和热重分析对复合膜的形貌和结构进行表征及对力学、光学、阻隔、抑菌等性能测试分析。结果表明，壳聚糖和银纳米线成功复合于纤维素基膜，与再生纤维素膜相比，当AgNW质量分数为0.5%时，复合膜的拉伸强度提升了12.2%，透光率保持在89.82%，氧气透过率下降了86.7%，且对大肠杆菌具有良好的抑制作用，制备出一种力学性能、光学性能、阻隔性能、抗菌性能优异的可降解纤维素/壳聚糖/银纳米线抗菌复合膜。     

Manufacture and performance of ethylamine hydroxyethyl chitosan/cellulose fiber in N-methylmorpholine-N-oxide system

Ethylamine hydroxyethyl chitosan (EHC), a novel chitosan derivative which is soluble in aqueous N-methylmorpholine-N-oxide (NMMO) and antibacterial to Escherichia coli (E. coli) was synthesized. The structure, solubility and antibacterial capability of EHC were investigated. Results demonstrated the potential application for EHC in manufacture of antibacterial EHC/cellulose Lyocell fiber. Through environment-friendly Lyocell process in aqueous NMMO, the EHC/cellulose fiber was successfully fabricated and the various properties of EHC/cellulose fiber were studied. Results showed the EHC/cellulose fiber exhibited favorable consistency, antibacterial activity, mechanical properties and water retention compared with the fiber without EHC.     

Alternating Current Electrophoretic Deposition of Antibacterial Bioactive Glass-Chitosan Composite Coatings

Alternating current (AC) electrophoretic deposition (EPD) was used to produce multifunctional composite coatings combining bioactive glass (BG) particles and chitosan. BG particles of two different sizes were used, i.e., 2 μm and 20–80 nm in average diameter. The parameter optimization and characterization of the coatings was conducted by visual inspection and by adhesion strength tests. The optimized coatings were investigated in terms of their hydroxyapatite (HA) forming ability in simulated body fluid (SBF) for up to 21 days. Fourier transform infrared (FTIR) spectroscopy results showed the successful HA formation on the coatings after 21 days. The first investigations were conducted on planar stainless steel sheets. In addition, scaffolds made from a TiAl4V6 alloy were considered to show the feasibility of coating of three dimensional structures by EPD. Because both BG and chitosan are antibacterial materials, the antibacterial properties of the as-produced coatings were investigated using E. coli bacteria cells. It was shown that the BG particle size has a strong influence on the antibacterial properties of the coatings.     

Fabrication of Chitosan/Silk Fibroin Composite Nanofibers for Wound-dressing Applications

Chitosan, a naturally occurring polysaccharide with abundant resources, has been extensively exploited for various biomedical applications, typically as wound dressings owing to its unique biocompatibility, good biodegradability and excellent antibacterial properties. In this work, composite nanofibrous membranes of chitosan (CS) and silk fibroin (SF) were successfully fabricated by electrospinning. The morphology of electrospun blend nanofibers was observed by scanning electron microscopy (SEM) and the fiber diameters decreased with the increasing percentage of chitosan. Further, the mechanical test illustrated that the addition of silk fibroin enhanced the mechanical properties of CS/SF nanofibers. The antibacterial activities against Escherichia coli (Gram negative) and Staphylococcus aureus (Gram positive) were evaluated by the turbidity measurement method; and results suggest that the antibacterial effect of composite nanofibers varied on the type of bacteria. Furthermore, the biocompatibility of murine fibroblast on as-prepared nanofibrous membranes was investigated by hematoxylin and eosin (H&E) staining and MTT assays in vitro, and the membranes were found to promote the cell attachment and proliferation. These results suggest that as-prepared chitosan/silk fibroin (CS/SF) composite nanofibrous membranes could be a promising candidate for wound healing applications.     

Fabrication of ZnO@Plant Polyphenols/Cellulose as Active Food Packaging and Its Enhanced Antibacterial Activity

To investigate the efficient use of bioresources and bioproducts, plant polyphenol (PPL) was extracted from larch bark and further applied to prepare ZnO@PPL/Cel with cellulose to examine its potential as an active package material. The structure and morphology were fully characterized by XRD, SEM, FTIR, XPS and Raman spectra. It was found that PPL is able to cover ZnO and form a coating layer. In addition, PPL cross-links with cellulose and makes ZnO distribute evenly on the cellulose fibers. Coating with PPL creates a pinecone-like morphology in ZnO, which is constructed by subunits of 50 nm ZnO slices. The interactions among ZnO, PPL and cellulose have been attributed to hydrogen bonding, which plays an important role in guiding the formation of composites. The antibacterial properties against Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) were tested by the inhibition zone method. Our composite ZnO@PPL/Cel has superior antibacterial activity compared to ZnO/Cel. The antibacterial mechanism has also been elaborated on. The low cost, simple preparation method and good performance of ZnO@PPL/Cel suggest the potential for it to be applied as active food packaging.     

Dielectric,magnetic, and mechanical properties of composites consisting of biopolymer chitosan matrix and hybrid spinel/cellulose filler

The composites consisting of a biopolymer chitosan matrix and hybrid spinel/cellulose filler were prepared by solvent casting method whereas the spinel CoFe₂O₄ was obtained by mechanical synthesis followed by thermal annealing. Incorporation of cellulose to the spinel – chitosan composite significantly modified dielectric, magnetic and mechanical properties of a composite consisting of the biopolymer with hybrid filler. In dielectric response the presence of the filler in the chitosan matrix hindered the molecular motion. The lowering of the activation energy and the cooperativity of the motion was observed. According to the magnetic properties, addition of cellulose to the filler enhanced coercivity field H_c in comparison to the pure spinel powder from value 0.1453 to 0.2033?T. In mechanical properties incorporation of the filler resulted in improvement of Young's modulus and tensile strength in comparison to unfilled chitosan. For composites with nanocellulose filler tensile strength was over two times higher than for chitosan.     

Facile Synthesis and Characterization of Palm CNF-ZnO Nanocomposites with Antibacterial and Reinforcing Properties

Cellulose nanofibers (CNF) isolated from plant biomass have attracted considerable interests in polymer engineering. The limitations associated with CNF-based nanocomposites are often linked to the time-consuming preparation methods and lack of desired surface functionalities. Herein, we demonstrate the feasibility of preparing a multifunctional CNF-zinc oxide (CNF-ZnO) nanocomposite with dual antibacterial and reinforcing properties via a facile and efficient ultrasound route. We characterized and examined the antibacterial and mechanical reinforcement performances of our ultrasonically induced nanocomposite. Based on our electron microscopy analyses, the ZnO deposited onto the nanofibrous network had a flake-like morphology with particle sizes ranging between 21 to 34 nm. pH levels between 8–10 led to the formation of ultrafine ZnO particles with a uniform size distribution. The resultant CNF-ZnO composite showed improved thermal stability compared to pure CNF. The composite showed potent inhibitory activities against Gram-positive (methicillin-resistant Staphylococcus aureus (MRSA)) and Gram-negative Salmonella typhi (S. typhi) bacteria. A CNF-ZnO-reinforced natural rubber (NR/CNF-ZnO) composite film, which was produced via latex mixing and casting methods, exhibited up to 42% improvement in tensile strength compared with the neat NR. The findings of this study suggest that ultrasonically-synthesized palm CNF-ZnO nanocomposites could find potential applications in the biomedical field and in the development of high strength rubber composites.     

Preparation and antibacterial properties of titanium-doped ZnO from different zinc salts

To research the relationship of micro-structures and antibacterial properties of the titanium-doped ZnO powders and probe their antibacterial mechanism, titanium-doped ZnO powders with different shapes and sizes were prepared from different zinc salts by alcohothermal method. The ZnO powders were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED), and the antibacterial activities of titanium-doped ZnO powders on Escherichia coli and Staphylococcus aureus were evaluated. Furthermore, the tested strains were characterized by SEM, and the electrical conductance variation trend of the bacterial suspension was characterized. The results indicate that the morphologies of the powders are different due to preparation from different zinc salts. The XRD results manifest that the samples synthesized from zinc acetate, zinc nitrate, and zinc chloride are zincite ZnO, and the sample synthesized from zinc sulfate is the mixture of ZnO, ZnTiO₃, and ZnSO₄ · 3Zn (OH)₂ crystal. UV-vis spectra show that the absorption edges of the titanium-doped ZnO powders are red shifted to more than 400 nm which are prepared from zinc acetate, zinc nitrate, and zinc chloride. The antibacterial activity of titanium-doped ZnO powders synthesized from zinc chloride is optimal, and its minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) are lower than 0.25 g L⁻¹. Likewise, when the bacteria are treated by ZnO powders synthesized from zinc chloride, the bacterial cells are damaged most seriously, and the electrical conductance increment of bacterial suspension is slightly high. It can be inferred that the antibacterial properties of the titanium-doped ZnO powders are relevant to the microstructure, particle size, and the crystal. The powders can damage the cell walls; thus, the electrolyte is leaked from cells.     

Preparation of nylon-6/chitosan composites by nanospider technology and their use as candidate for antibacterial agents

Electrospun nylon-6/chitosan (nylon-6/Ch) nanofibers were prepared by nanospider technology. Quaternary ammonium salts as antibacterial agent were immobilized onto electrospun nylon-6/Ch nanofibers via surface modification by soaking the mat in aqueous solution of glycidyltrimethylammonium chloride (GTMAC) at room temperature overnight to give nylon-6/N-[(2-hydroxy-3-trimethylammonium)propyl] chitosan chloride (nylon-6/HTCC). The morphological, structural and thermal properties of the nylon-6/ch nanofibers were studied by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). Biological screening has demonstrated the antibacterial activity of the electrospun nanofibers against Gram negative bacteria, Escherichia coli 35218, and Pseudomonas aeruginosa and Gram positive bacteria, Staphylococcus aureus 24213 among the tested microbes. Thus, the study ascertains the value of the use of electrospun nanofibers, which could be of considerable interest to the development of new antibacterial materials for biomedical applications.     

Effects of gamma irradiation on the thermal and mechanical properties of chitosan/PVA nanofibrous mats

Chitosan/poly(vinyl alcohol) (PVA) nanofibrous mats were prepared by the electrospinning method. The morphology and structure of electrospun nanofibers were investigated by scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. SEM images showed that the uniform and bead-free fibers were obtained at concentrations greater than 8 wt%. Chitosan/PVA mats were irradiated with different doses (50–200 kGy) of ⁶⁰Co gamma rays. The effect of irradiation dose on the mechanical and thermal properties of these films was also investigated. Increasing the irradiation dose led to a decrease in tensile strength. FT-IR and DSC demonstrated that there were strong intermolecular hydrogen bonds between the chitosan and PVA molecules.     

ZnO nanocrystallites/cellulose hybrid nanofibers fabricated by electrospinning and solvothermal techniques and their photocatalytic activity

ZnO nanocrystallites have been in situ embedded in cellulose nanofibers by a novel method that combines electrospinning and solvothermal techniques. Zn(OAc)₂/cellulose acetate (CA) precursor hybrid nanofibers with diameter in the range of 160–330 nm were first fabricated via the electrospinning technique using zinc acetate as precursor, CA as the carrier, and dimethylformamide (DMF)/acetone(2 : 1) mixture as cosolvent. The precursor nanofibers were transformed into ZnO/cellulose hybrid fibers by hydrolysis in 0.1 mol/L NaOH aqueous solution. Subsequently, these hybrid fibers were further solvothermally treated in 180°C glycerol oil bath to improve the crystallite structure of the ZnO nanoparticles containing in the nanofibers. The structure and morphology of nanofibers were characterized by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. It was found that hexagonal structured ZnO nanocrystallites with the size of ～ 30 nm were dispersed on the nanofiber surfaces and within the nanofibers with diameter of about 80 nm. The photocatalytic property of the ZnO/cellulose hybrid nanofibers toward Rhodamine (RhB) was tested under the irradiation of visible light. As a catalyst, it inherits not only the photocatalytic ability of nano‐ZnO, but also the thermal stability, good mechanical property, and solvent‐resistibility of cellulose nanofibers. The key advantages of this hybrid nanofiber over neat ZnO nanoparticles are its elasticity, dimensional stability, durability, and easy recyclability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A study of wet and dry strength properties of unaged and hygrothermally aged paper sheets reinforced with biopolymer composites

Biopolymers and their composites were added during the formation of unbleached Kraft bagasse pulp paper sheets to improve the mechanical strength properties of the produced hand sheets. The biopolymers (cellulose, chitosan, and chitosan‐cellulose composite) were either crosslinked or noncrosslinked and they were added in series of concentrations from 0.1% to 1.5%. The characterization of the samples using the Fourier transform infrared (IR) technique identified differences in the intensities of the characteristic IR absorption bands for chitosan, cellulose, and their composites, these differences are due to the various degrees of hydrogen bonding. The surface morphology of the biopolymers composites and the treated paper sheets were studied using SEM technique. Both the equilibrium moisture sorption and the diffusion coefficient of the paper sheets containing 1% additives were evaluated at regular time intervals. The long‐term stability of the treated paper with biopolymers was verified by exposing the treated and the untreated sheets to hygrothermal ageing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40761.     

Surface properties,thermal, and mechanical characteristics of poly(vinyl alcohol)–starch‐bacterial cellulose composite films

Nanocomposite films for food packaging applications were developed using bacterial cellulose (BC) nanofibers in different amount in a poly(vinyl alcohol)/starch (PVA/St) matrix. In search of a better method to reduce the harmful ingredients in food packaging, the cellulose nanofibers were obtained by the mechanical defibrillation of BC pellicles thus avoiding the addition of chemicals in the final packaging material. Improved mechanical performances were obtained starting from just 1% BC nanofibers in PVA/St. Atomic force microscopy images showed a uniform dispersion of BC nanofibers on the surface of nanocomposites. A twofold increase of both tensile strength and modulus was obtained for 2 wt % BC in the composite. BC nanofibers have greatly improved the barrier properties of PVA/St matrix, a twofold increase of water vapor permeability being obtained for only 2 wt % BC nanofibers in the composite film. PVA/St/2BC was proposed as a high potential material for food packaging applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45800.     

Development of g-C3N4/ZnO nanocomposite as a novel,highly effective and durable photocatalytic antibacterial coating for cotton fabric

Photocatalytic antibacterial coats are considered among the best solutions to bacterial contamination of fabrics, with the drawback of reduced efficacy after continued use and washing. In the present study, the g-C₃N₄/ZnO (CNZ) nanocomposite has been introduced as a novel cotton fabric coating, with high durability, and CNZ nanopowders were synthesized using a two-step thermal synthesis process and directly coated onto cotton fabric using the sonication technique. The synthesized nanoparticles (NPs) were examined using X-ray diffraction (XRD), UV–visible spectroscopy, photoluminescence (PL), Brunauer-Emmett-Teller (BET), and Fourier transform infrared (FTIR) analyzes. Besides, the SEM analysis confirmed the successful deposition of NPs on cotton fabric. The photodegradation of methylene blue (MB) stain was assessed as a functional test for the photocatalytic effectiveness of the coated fabric, then its antibacterial properties were evaluated under visible light, by direct contact with bacterial suspensions and culturing. The results revealed that the CNZ-coated cotton fabric containing 30% ZnO (CNZ-30) has significant photocatalytic antibacterial activity against both Escherichia coli (gram-negative), and Staphylococcus aureus (gram-positive) bacteria. The bacterial reduction rate of CNZ-30 coated fabric for both E. coli and S. aureus was above 98%, even after 18 washing cycles. This excellent performance is attributed to the effective coupling of ZnO with g-C₃N₄, improved light absorption, and reduced e⁻/h⁺ pair recombination rates. This study novel coating method can offer an environmentally friendly, cost-effective, and simple process to manufacture hybrid CNZ antibacterial cotton in the textile industry.     

Bimetallic Zn/Ag doped polyurethane spider net composite nanofibers: A novel multipurpose electrospun mat

The objective of this study was to develop a new class of bimetallic ZnO/Ag embedded polyurethane multi-functional nanocomposite by a straightforward approach. Bimetallic nanomaterials, composed of two unlike metal elements, are of greater interest than the monometallic materials because of their improved characteristics. In the present study the bimetallic composite was prepared using sol–gel via the facile electrospinning technique. The utilized sol–gel was composed of zinc oxide, silver and poly(urethane). The physicochemical properties of as-spun composite mats were determined by X-ray diffraction pattern, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy and transmission electron microscopy. The antibacterial activity was tested using Escherichia coli as model organism. The antibacterial test showed that ZnO:Ag/polyurethane composite possesses superior antimicrobial activity than pristine PU and ZnO/PU hybrids. Furthermore, our results illustrate that the synergistic effect of ZnO and Ag resulted in the advanced antimicrobial action of bimetallic ZnO/Ag composite mat. The viability and proliferation properties of NIH 3T3 mouse fibroblast cells on the ZnO:Ag/polyurethane composite nanofibers were analyzed by in vitro cell compatibility test. Our results indicated the non-cytotoxic behavior of bimetallic ZnO:Ag/polyurethane nanofibers towards the fibroblast cell culture. In summary, novel ZnO:Ag/polyurethane composite nanofibers which possess large surface to volume ratio with excellent antimicrobial activity were fabricated. The unique combination of ZnO and Ag nanoparticles displayed potent bactericidal effect due to a synergism. Hence the electrospun bimetallic composite indicates the huge potential in water filtration, clinical and biomedical applications.     

Construction of Er-doped ZnO/SiO2 composites with enhanced antimicrobial properties and analysis of antibacterial mechanism

Herein, silica carrier was used as underlying structure to prepare composite material loaded with rare earth element Er and Zn. Rare earth elements can improve antimicrobial effects of ZnO due to their specific electronic structure. Er–ZnO/SiO₂ hybrid antibacterial material was prepared through sol-gel method and its structure and morphology were characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma emission spectroscopy and Brunauer-Emmett-Teller measurements. E. coli and S. aureus were selected as model bacteria to assess antibacterial activity of prepared hybrid material by plate coating method. Er–ZnO/SiO₂ exhibited good antibacterial activity towards E. coli and S. aureus. Increase in Er³⁺ concentration from 0.12% to 1.10% led to increase in antibacterial performance followed by subsequent decrease. Improving effect of Er relied on the molar ratio of Er doped in ZnO/SiO₂ hybrid material. The optimal sample was found to be 0.60%Er–ZnO/SiO₂, with antibacterial rates of 93.71% and 70.46% against E. coli and S. aureus, respectively. Antibacterial mechanism was assessed by fluorescence detection of reactive oxygen species. In addition, flame atomic absorption spectrometry was used to measure the amount of released Zn²⁺. Results also showed that 0.60%Er–ZnO/SiO₂ hybrid material generated more reactive oxygen species, released more Zn²⁺ ions, and had the largest surface area, which improved its antibacterial rate. Thus, Er enhanced antibacterial properties of ZnO/SiO₂, providing these composite materials with great potential as antibacterial products.     

Enhanced simulated solar sono-photocatalytic performance and antibacterial activities of ZnO/NiO heterojunction nanofibrous membranes

ZnO/NiO heterojunction nanofibrous membranes with different Zn/Ni molar ratios were successfully prepared via electrospinning. The microstructures of the nanofibers were characterized by using scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The ZnO/NiO heterojunction nanofibrous membranes showed superior photocatalytic performance on Congo red, particularly under ultrasonic action and simulated solar irradiation. The degradation of Congo red could reach 100% after 40 min with a high degradation constant of 0.064 min^?1. Additionally, the catalyst maintained high photocatalytic activity over five cycles. Furthermore, the heterojunction nanofibrous membranes had good antibacterial effects on Escherichia coli and Staphylococcus aureus with an inhibition zone width of above 8 mm. The generation of superoxide free radical and hydroxyl free radicals played important roles for the heterojunction nanofibrous membranes. This work is significant for studying the potential applications of nanofibers in waste water remediation.     

Facile preparation and characterization of poly(vinyl alcohol)/chitosan/graphene oxide biocomposite nanofibers

Poly(vinyl alcohol) (PVA)/chitosan (CS)/graphene oxide (GO) biocomposite nanofibers have been successfully prepared using aqueous solution by electrospinning. CS colloidal gel in 1% acetic acid can be changed to homogeneous solution by using electron beam irradiation (EBI). The uniform distributions of GO sheets in the nanofibers were investigated by field emission scanning electron microscopy (FESEM) and Raman spectroscopy. FESEM images illustrated that the spread single GO sheet embedding into nanofibers was formed via self-assembly of GO sheet and PVA/CS chains. And the average diameters of the biocomposite nanofibers decreased (200, 173, 160 and 123 nm) with increasing the contents of GO (0.05, 0.2, 0.4 and 0.6 wt%). Raman spectra verified the presence of GO in the biocomposite nanofibrous mats. The mechanical properties of as-prepared materials related with GO contents. It revealed that the highest tensile strength was 2.78 MPa, which was 25% higher than that of neat PVA/CS nanofibers. Antibacterial test demonstrated that the addition of GO to PVA/CS nanofiber had great ability to increase inhibition zone till 8.6 mm. Overall, these features of PVA/CS/GO nanofibers which were prepared by eco-friendly solvent can be a promising candidate material in tissue engineering, wound healing and drug delivery system.     

改性纤维素和壳聚糖共混膜的制备及性能研究

将水溶性的纤维素衍生物——羟乙基纤维素与壳聚糖乙酸水溶液用溶液浇铸法制得羟乙基纤维素/壳聚糖(HEC/CS)共混膜。确定了该共混膜的最佳制备条件,并测试了其力学性能和生物降解性能。结果表明:HEC/CS共混膜具有好的抗菌性。