壳聚糖衍生物抗菌塑料制备与性能评价

采用水相悬浮聚合法合成壳聚糖接枝苯乙烯（CTS-g-St）抗菌剂，机械共混法制备了以LDPE为基体的抗菌塑料，采用红外光谱分析抗菌剂，扫描电镜观察材料断面，定量抗菌实验对抗菌塑料抗菌活性进行了测定，并测试了材料的力学性能。结果表明：苯乙烯单体成功接枝到壳聚糖分子上；改性壳聚糖与树脂间具有很好的相容性；抗菌剂添加量为2份时，抗菌塑料对大肠杆菌、枯草杆菌在24h、48h抗菌率均超过90％；抗菌剂的加入对材料力学性能无不良影响。     

Preparation and characterization of antimicrobial PVA hybrid films with N‐halamine modified chitosan nanospheres

Chitosan is a promising candidate as an antimicrobial agent in food packaging materials and biomaterials due to its biocompatibility, biodegradability, non‐toxicity and biocidal activity. In this study, chitosan derivatives, α‐(5,5‐dimethyl hydantoin amino)‐chitosan (CS‐HDH), were synthesized. The CS‐HDH nanospheres were prepared by ionic gelation method and characterized by SEM, FT‐IR, XRD, and TGA‐DTG. The prepared novel chitosan nanospheres in the range of 200–300 nm had good dispersibility. The CS‐HDH nanospheres were used to prepare antibacterial PVA hybrid films by solvent evaporation technique. The surface morphology and thermal property of hybrid films were measured by SEM, AFM, and TGA‐DTG. The results of antibacterial test showed that the hybrid film with 1.24 × 10¹⁸ atoms/cm² of active chlorine exhibited excellent antibacterial properties against Staphylococcus aureus and Escherichia coli O157:H7, and all of bacteria could be inactivated within 5 min. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44204.     

Preparation of chitosan‐graft‐(methyl methacrylate)/Ag nanocomposite with antimicrobial activity

It has been found that composites of chitosan (CS) and Ag nanoparticles can exhibit excellent antibacterial activities. However, the weak mechanical performances of these composite materials limit their wide application. Grafting of vinyl monomers onto CS is one of the most effective methods to improve the performances of CS without sacrificing its properties. A nanocomposite of chitosan‐graft‐(methyl methacrylate) (CS‐g‐MMA) containing Ag nanoparticles was prepared by in situ chemical reduction of Ag ions in an aqueous acetic acid solution of CS and graft copolymerization of MMA onto CS. Transmission electron micrographs, X‐ray diffraction patterns and UV‐visible spectra of the nanocomposite confirmed the formation of Ag nanocrystals. X‐ray photoelectron spectroscopy proved that Ag? O bonds exist in the composite. Thermogravimetric analysis/differential scanning calorimetry showed that the decomposition temperature of CS was 319.8 °C while that of the CS‐g‐MMA/Ag composite shifted to a higher temperature of 422.1 °C. Antimicrobial experiments showed that the antimicrobial rates of the CS‐g‐MMA/Ag composite to E. coli, B. subtilis, S. aureus and P. aeruginosa were 93–98%. CS molecules can act as stabilizing agents to prevent the aggregation of Ag nanoparticles in the process of synthesizing CS‐g‐MMA/Ag nanocomposites. The antimicrobial activity of the as‐prepared nanocomposites is higher than that of CS alone. Copyright © 2009 Society of Chemical Industry     

Antibacterial activities of novel nanocomposite biofilms of chitosan/phosphoramide/Ag NPs

Novel nanocomposite films of chitosan/phosphoramide/Ag NPs were prepared containing 1–5% of silver nanoparticles. The Ag NPs were synthesized according to the citrate reduction method. The XRD and SEM analysis of Ag NPs, chitosan (CS), phosphoramide (Ph), CS/Ph, CS/Ag NPs films and the nanocomposite films 1–5 containing CS/Ph/1–5% Ag NPs were investigated. The in vitro antibacterial activities were evaluated against four bacteria including two Gram‐positive Staphylococcus aureus (S. aureus), Bacillus cereus (B. cereus) and two Gram‐negative Escherchia coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa) bacteria. Results revealed greater antibacterial effects of the films against Gram‐positive bacteria. Also, nanocomposite films containing higher percent of Ag NPs showed more antibacterial activities. POLYM. COMPOS. 36:454–466, 2015. © 2014 Society of Plastics Engineers     

Blends of LDPE/chitosan using epoxy‐functionalized LDPE as compatibilizer

LDPE and chitosan blends were prepared using an epoxy‐functionalized polyethylene as compatibilizing agent for improving interfacial adhesion. Compatibilization improved both tensile and flexural properties (with values approaching close to that of neat LDPE) when compared with that of uncompatibilized blends. However, the elongation at break reduced due to the addition of rigid chitosan. Thermogravimetric analysis showed a two‐stage degradation, while differential scanning calorimetry exhibited reduced crystallinity for compatibilized blends. Biodegradation studies revealed increased biodegradability with increase in chitosan loading. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Antibacterial and biodegradable properties of polyhydroxyalkanoates grafted with chitosan and chitooligosaccharides via ozone treatment

Acrylic acid was grafted to ozone‐treated poly(3‐hydroxybutyric acid) (PHB) and poly(3‐hydroxybutyric acid‐co‐3‐hydroxyvaleric acid) (PHBV) membranes. The resulting membranes were further grafted with chitosan (CS) or chitooligosaccharide (COS) via esterification. These CS‐ or COS‐grafted membranes showed antibacterial activity against Escherichia coli, Pseudomonas aeruginosa, methicilin‐resistant Staphylococcus aureus (MRSA), and S. aureus. The antibacterial activity to E. coli was the highest, whereas the antibacterial activity to MRSA was the lowest among these four bacteria tested. Acrylic acid grafting can increase the biodegradability with Alcaligens faecalis, whereas CS and COS grafting can reduce the biodegradability. In addition, CS‐grafted PHBV membrane showed higher antibacterial activity and lower biodegradability than COS‐grafted PHBV membrane. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2797–2803, 2003     

Tunable wettability and tensile strength of chitosan membranes using keratin microparticles as reinforcement

Keratin particles with microscale are prepared by ball mill and its influences on the chitosan membrane is evaluated. Composite membranes with various content of keratin are fabricated, and their physical and chemical properties such as morphology, wettability, crystallization, thermal stability, tensile strength, and break elongation are investigated. Optical microscope and situ topographic scan mode of nano‐test system are used to examine the dispersion and aggregation of keratin on the surface of chitosan membrane. The result of contact angle (CA) and mechanical testing show that the incorporation of keratin particles decrease the CA from 98.1° to 58.2°. Tensile strength and break elongation of the composite membrane reaches a maximum of 65 ± 8 MPa and 15% when the keratin content is 6%, an increase of 80% and 88% compared with the pristine chitosan membrane. Both the increase in tensile strength and break elongation is result of the incorporation of keratin particles known for their excellent compatibility between keratin and chitosan matrix. These kind of composite material combines the antibacterial properties of chitosan with cell culture preference of keratin which may have potential biomedical application. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44667.     

Research on the preparation and characterization of chitosan grafted polyvinylpyrrolidone gel membrane with iodine

The chitosan grafted polyvinylpyrrolidone gel membrane with iodine (CS‐PVP‐I₂‐G‐M) was prepared by chitosan–polyvinylpyrrolidone–iodine complex liquid (CS‐PVP‐I₂‐L) mixed with gelatin. The intermediate product CS‐PVP‐I₂‐L was prepared by CS grafted PVP in the protection of N₂ with dimethyl 2,2′‐azobis (2‐methylpropionate) (AIBME) as initiator, then a certain amounts of iodine in ethanol solution was added. The properties of CS‐PVP‐I₂‐G‐M were characterized by IR, UV–Vis, SEM, XRD, DSC, and so forth. The iodine release results coherent with the release kinetic model—Fick diffusion laws, has a burst effect first, and then spread, and the emission of iodine was maintained within a certain range and kept at a stable level permanently, showed a sustained‐release effect of iodine. The inhibition zone diameters of CS‐PVP‐I₂‐G‐M against Staphylococcus aureus and Escherichia coli were both greater than 16 mm, it demonstrated significant antibacterial activity. Double effects sustained‐release effect of iodine and the significant antibacterial activity made CS‐PVP‐I₂‐G‐M highly potential for applications as a novel natural biomedical sterilization materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41797.     

Sonochemical synthesis and stabilization of concentrated antimicrobial silver‐chitosan nanoparticle dispersions

This work reports on a green synthetic route to produce concentrated aqueous dispersions of silver nanoparticles (AgNP) employing high‐intensity ultrasound (US) and chitosan (CS) as a nontoxic reducing agent for Ag⁺ salts and AgNP stabilizer. The sonication simultaneously boosted the synthesis and improved the stability of the AgNP, capping them with CS. Hybrid AgNP‐CS antimicrobial dispersions, stable for at least 6 months, were synthesized in a simple single step process. The use of US allowed for applying relatively mild processing temperatures (60 °C) and reaction time between 30 min and 3 h to obtain concentrated dispersions of AgNP that otherwise could not be obtained even after 72 h under mechanical stirring at the same reaction conditions. Upon sonication spherical AgNP‐CS with a size between 60 and 100 nm were generated, in contrast to the average diameter of ～200 nm of the particles obtained by stirring. The antibacterial efficiency of the AgNP‐CS hybrids was evaluated against the medically relevant pathogens Staphylococcus aureus and Escherichia coli. The US‐synthesized AgNP‐CS showed more than three fold higher antibacterial activity compared to the particles obtained under stirring, due to their higher concentration and smaller size. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45136.     

Durable antibacterial finish on cotton fabric by using chitosan‐based polymeric core‐shell particles

Cotton fabric with excellent antibacterial durability was obtained when treated with chitosan‐containing core‐shell particles without any chemical binders. These amphiphilic nanosized particles with antibacterial chitosan shells covalently grafted onto polymer cores were prepared via a surfactant‐free emulsion copolymerization in aqueous chitosan. Herein, two core‐shell particles, one with poly(n‐butyl acrylate) soft core and another with crosslinked poly(N‐isopropylamide) hard core, were synthesized and applied to cotton fabric by a conventional pad‐dry‐cure process. Antimicrobial activity was evaluated quantitatively using a Shake Flask Method in which the reduction of the number of Staphylococcus aureus cells was counted. The results showed that treated fabric had an excellent antibacterial property with bacterial reduction higher than 99%. The antibacterial activity maintained at over 90% reduction level even after 50 times of home laundering. The fabric surface morphology as well as the effect of latex particles with different core flexibilities on fabric hand, air permeability, break tensile strength, and elongation was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1787–1793, 2006     

Soil burial test for poly(ethylene‐co‐vinyl alcohol)‐graft‐polycaprolactone

The ring‐opening polymerization of ε‐caprolactone was carried out with poly(ethylene‐co‐vinyl alcohol) as a macroinitiator to synthesize poly(ethylene‐co‐vinyl alcohol)‐graft‐polycaprolactone (EVOH‐g‐PCL). A simple low‐density polyethylene (LDPE)/polycaprolactone (PCL) (64/36) blend lost 5.3 wt % of its original weight after 90 days of a soil burial test. However, the elongation at break of the LDPE/PCL blend remained almost invariable even after the solid burial test because the tensile properties depended mostly on the LDPE phase on account of the poor interaction between the continuous LDPE matrix and the dispersed PCL phase. For EVOH‐g‐PCL, the elongation at break decreased drastically as a result of the soil burial test, and the reduction of the elongation at break was more pronounced for EVOH‐g‐PCL with a higher PCL concentration, even though the weight loss of EVOH‐g‐PCL after the soil burial test was as low as 1.2–1.3% and was nearly independent of the PCL concentration. Few holes were observed in EVOH‐g‐PCL when the PCL concentration was less than 26 wt % after an accelerated hydrolysis experiment at 60°C for 7 days in a 0.1M KOH solution. In contrast, the hydrolysis formed small holes in EVOH‐g‐PCL with a PCL concentration of 36 wt %. The LDPE/PCL blend was much better percolated, as a result of the hydrolysis, than EVOH‐g‐PCL with the same PCL concentration; the soil burial test showed the same results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1064–1071, 2005     

Biocompatibility and antibacterial activity of chitosan and hyaluronic acid immobilized polyester fibers

Poly(ethylene terephthalate) (PET) fibers were treated with ⁶⁰Co‐γ‐ray and grafted with acrylic acid. The resulting fibers were further grafted with chitosan (CS) via esterification. Afterward, hyaluronic acid (HA) was immobilized onto CS‐grafting fibers. The antibacterial activity of CS against S. aureus, E. coli, and P. aeruginosa was preserved after HA‐immobilization. After immobilizing HA, the L929 fibroblasts cell proliferation was improved forCS‐grafting PET fiber. The results indicate that by grafting with CS and immobilizing with HA, PET fibers not only exhibit antibacterial activity, but also improve the cell proliferation for fibroblast. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 220–225, 2007     

Preparation and characterization of antimicrobial films based on nanocrystalline cellulose

Nanocrystalline cellulose (NCC) has great potential in applications in medical and food packaging due to its abundance, high specific surface area, biodegradability, biocompatibility, and reproducibility. N-Halamine is one of the most effective antibacterial agents, with broad-spectrum efficacy against microorganisms, good stability, and reproducibility. Due to the nanosize effect and high specific surface area of NCC, N-halamine-modified NCC is potentially an excellent biocidal compound. In this paper, an N-halamine precursor 1-hydroxymethyl-5,5-dimethylhydantoin (HDH) was used to modify NCC with cyanuric chloride (cych) as the bonding agent. After chlorination, the produced NCC-cych-HDH-Cl became antibacterial. The synthesized NCC-cych-HDH-Cl was added to a chitosan (CS) and polyvinyl alcohol (PVA) solution to prepare antibacterial films. The optimum mixing ratio of PVA and CS in the PVA/CS films and concentration of NCC-cych-HDH-Cl were investigated. The surface morphologies and mechanical properties of the antibacterial films were characterized with scanning electron microscopy, transmission electron microscopy, and mechanical strength tests. The results indicated that the film with 90/10 PVA/CS and 7.0% loading of NCC-cych-HDH-Cl exhibited excellent tensile strength. The antibacterial film with 5.91 × 10¹⁷ atoms/cm² of active chlorine displayed an excellent antibacterial property against Staphylococcus aureus (ATCC 6538) and Escherichia coli O157:H7 (ATCC 43895). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47101.     

Synthesis of chitosan derivative with dual‐antibacterial functional groups and its antibacterial activity

The O‐fumaryl ester (OFTMCS) of N,N,N‐trimethyl chitosan (TMCS) has been synthesized as a water‐soluble chitosan (CS) derivative bearing dual‐functional groups, with the aim of discovering novel CS derivatives with good water solubility and enhanced the antibacterial activity compared with unmodified CS. OFTMCS was characterized by FT‐IR, ¹³C NMR, XPS, XRD and Zeta potential analyses. The XPS results indicated that the degree of substitution (DS) on the C₂‐NH₂ group of the CS was 0.78, and that the DS on its C₆‐OH group was 0.31. The TGA results showed that the thermal stability of OFTMCS was lower than that of unmodified CS. The antibacterial activities of OFTMCS were investigated by assessing the mortality rates of the representative Gram‐positive and Gram‐negative bacteria Staphylococcus aureus and Escherichia coli, respectively. The results indicated that OFTMCS exhibited superior antibacterial activity to CS at a lower dosage. The synthesis of CS derivatives bearing dual‐functional groups could therefore be used as a promising strategy to enhance the antibacterial activity of CS. The antimicrobial mechanism of action of OFTMCS was discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42663.     

Silane grafting and moisture crosslinking of polyethylene: The effect of molecular structure

The silane grafting and moisture crosslinking of different grades of polyethylene have been investigated. Three types of polyethylene (HDPE, LLDPE, and LDPE) with different molecular structures and similar melt flow indices were selected. The initiator was dicumyl peroxide (DCP), and the silane was vinyltrimethoxysilane. The grafting reaction was carried out in an internal mixer. The extent of grafting and the degree of crosslinking were determined, and hot‐set tests were carried out to evaluate the crosslink structure of the different polyethylenes. The LLDPE had the highest degree of grafting, while the LDPE had the least. The rate of crosslinking for LDPE was higher than that of HDPE and LLDPE. The gel content of LDPE was higher than that of HDPE and LLDPE. Hot‐set elongation and the number‐average molecular weight between crosslinks (M_c) were lower for LLDPE and LDPE than for HDPE. Increasing the silane/DCP percentage led to peroxide crosslinking, thereby decreasing the M_c and hot‐set elongation. The number‐average molecular weight (M_n), molecular weight distribution, and number of chain branches were the most important parameters affecting the silane grafting and moisture crosslinking. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Antibacterial electrospun chitosan/poly(vinyl alcohol) nanofibers containing silver nitrate and titanium dioxide

Chitosan/poly(vinyl alcohol) (PVA) nanofibers with antibacterial activity were prepared by the electrospinning of a chitosan/PVA solution with a small amount of silver nitrate (AgNO₃) and titanium dioxide (TiO₂). Nanofibers with diameters of 270–360 nm were obtained. The yield of low‐viscosity chitosan (LCS)/PVA nanofibers was higher than that of high‐viscosity chitosan (HCS)/PVA, and the water content of the HCS/PVA nanofibers and the LCS/PVA nanofibers were 430 and 390%, respectively. The nanofibers developed in this study exhibited antibacterial activities of 99 and 98% against Staphylococcus aureus and Escherichia coli, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface modification of electrospun chitosan nanofibrous mats for antibacterial activity

Chitosan (CS) blended with poly(ethylene oxide) (PEO) was electrospun into nanofibrous mats. The spinning solution of 6.7 : 0.3 (% w/v) of CS : PEO was dissolved in a 70 : 30 (v/v) trifluoroacetic acid/dichloromethane solution. The obtained fibers were smooth without beads on their surfaces and average diameter of the fiber was 272 ± 56 nm. N‐(2‐hydroxyl) propyl‐3‐trimethyl ammonium chitosan chloride (HTACC) and N‐benzyl‐N,N‐dimethyl chitosan iodide (QBzCS) were each prepared from the CS/PEO mats. They were identified by Fourier‐transform infrared and X‐ray photoelectron spectroscopy and degree of swelling in water. Both quaternized electrospun chitosan mats exhibited superior antibacterial activity to the unmodified electrospun CS/PEO against Staphylococcus aureus and Escherichia coli at short contact times. After 4 h of contact, the reduction of both bacterial strains by CS/PEO, HTACC, and QBzCS was equal at about 99–100%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40981.     

The structure and properties of a novel nanocomposite films from chitosan and layered zirconium phosphonate

A new type of layered zirconium phosphonate (zirconium glycine‐N, N‐dimethylphosphonate, abbreviated as ZGDMP), with functional group of ‐COOH, has been successfully prepared and characterized by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). To confirm the effect of the functional group ‐COOH on the structure and properties of composites, a series of chitosan/zirconium phosphonate modified by n‐butylamine (BA‐ZGDMP) nanocomposite films were prepared by casting process. FTIR spectra suggested that strong interactions existed between BA‐ZGDMP and chitosan matrix. Compared to neat CS film, tensile strength (σ_b) and elongation at break (ε_b) of the nanocomposite film improved by 35.1% and 15.6%, respectively, with loading ratio of just 1.0 wt %. In addition, the BA‐ZGDMP also improved the water resistance of the nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of chitosan/KSF biocomposite film

Chitosan–clay biocomposites have been prepared in which KSF‐montmorillonite (KSF) is used as filler and diluted acetic acid is used as solvent for dissolving and dispersing chitosan and montmorillonite, respectively. The effect of KSF loadings in biocomposites has been investigated. The characterization with different methods (FTIR, DSC, TGA, SEM, and XRD) on chitosan/KSF biocomposites systems was examined. Morphology and properties of chitosan biocomposites have been studied compared with those of pure chitosan. The FTIR and SEM results indicated the formation of an intercalated‐and‐exfoliated structure at low KSF content and an intercalated‐and‐flocculated structure at high KSF content. The thermal stability and the mechanical properties of the composites were also examined by DSC, TGA/DTG, and tensile strength measurements, respectively. The dispersed clay improves the thermal stability of the matrix systematically with the increase of clay loading. Tensile strength of a chitosan film was enhanced until the clay ratio up to 2 wt% and elongation‐at break decreased with addition of clay into the chitosan matrix. The XRD results confirmed the intercalation of the biopolymer in the clay interlayer by the decrease of 2θ values while the chitosan–clayratio increases. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Structural characterization and antimicrobial activity of chitosan (CS‐40)/nisin complexes

A complex of chitosan (CS‐40) and nisin (CS‐40/nisin) was prepared and characterized with Fourier transform infrared spectroscopy and thermal analysis (thermogravimetry, differential thermogravimetry, and differential scanning calorimetry). The results show that the complex formed mainly by electrostatic interaction between the protonated amino group in CS‐40 backbone with the carboxylate ion of nisin. Minimum inhibitory concentrations (MICs) were evaluated against Gram‐positive bacteria (Staphylococcus aureus, Bacillus subtilis, and Bacillus stearothermophilus), Gram‐negative bacteria (Escherichia coli, Salmonella enteritidis, and Proteus vulgaris), and fungi (Fusarium oxysporum). The results show that the CS‐40/nisin solution did inhibit or even more strongly inhibited the growth of all the tested microorganisms, whereas CS‐40 did not inhibit the growth of F. oxysporum and nisin did not inhibit the growth of Gram‐negative bacteria (E. coli, S. enteritidis, and P. vulgaris). The relative inhibition times of CS‐40/nisin solutions with different concentrations and ratios of CS‐40 and nisin were also investigated against the seven microorganisms. The results showed that CS‐40/nisin solutions with CS‐40/nisin concentration ratios of 0.05/0.005, 0.05/0.0025, 0.05/0.00125, and 0.025/0.0001% had higher antimicrobial activity against all tested bacteria and fungi. The relationship between complex formation and antimicrobial activity is discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010