Manufacture and properties of chitosan/N,O‐carboxymethylated chitosan/viscose rayon antibacterial fibers

Chitosan/N,O‐carboxymethylated chitosan/viscose rayon antibacterial fibers (CNVFs) were prepared by blending chitosan emulsion, N,O‐carboxymethylated chitosan (N,O‐CMC), and viscose rayon together for spinning. The fibers were characterized by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). TEM micrographs showed that chitosan microparticles dispersed uniformly along the oriented direction with the mean size ranging from 0.1 to 0.5 μm. DSC spectra of these fibers showed that no significant change in thermal property was caused by adding chitosan and N,O‐CMC into the viscose rayon. TGA spectra showed that the good moisture retentivity was not affected by the addition of chitosan and N,O‐CMC. Both DSC and TGA suggested that the decomposing tendency of the viscose rayon above 250°C seemed to be weakened by the chitosan. The fibers' mechanical properties and antibacterial activities against Escherchia coli, Staphylococcus aureus, and Candida albicans were measured. Although the addition of chitosan slightly reduced the mechanical properties, the antibacterial fibers' properties were obtained and were found to meet commercial requirements. CNVF exhibited excellent antibacterial activity against E. coli, S. aureus, and C. albicans. The antibacterial activity increased along with the chitosan concentration and was not greatly affected by 15 washings in water. Scanning electron microscopy (SEM) was used to observe the morphology of bacteria cells incubated together with the antibacterial or reference fibers. SEM micrographs demonstrated that greater amounts of bacteria could be adsorbed by the antibacterial fiber than by the reference fiber; these bacteria were overwhelmingly destroyed and killed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2049–2059, 2002; DOI 10.1002/app.10501     

Blend membranes from carboxymethylated chitosan/alginate in aqueous solution

The blend membranes were satisfactorily prepared by coagulating a mixture of O‐carboxymethylated chitosan (CM‐chitosan) and alginate in aqueous solution with 5 wt % CaCl₂, and then by treating with 1 wt % HCl aqueous solution. Their structure and miscibility were characterized by scanning electron micrograph, X‐ray diffraction, infrared spectra, differential thermal analysis, and atomic absorption spectrophotometer. The results indicated that the blends were miscible, when the weight ratio of CM‐chitosan to alginate was in the range from 1 : 1 to 1 : 5. The polymers interpenetration including a Ca²⁺ crosslinked bridge occurred in the blend membrane, and leads to high separation factor for pervaporation separation of alcohol/water and low permeation. The tensile strength in the wet state (σ_b = 192 kg cm⁻² for CM‐chitosan/alginate 1 : 1) and thermostability of the blend membranes were significantly superior to that of alginic acid membrane, and cellulose/alginate blend membranes, owing to a strong electrostatic interaction caused by —NH₂ groups of CM‐chitosan with —COOH groups of algic acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 610–616, 2000     

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     

Antibacterial activity of cationically modified cotton fabric with carboxymethyl chitosan

A water‐soluble carboxymethyl chitosan was prepared with a view to develop a multifunctional finish on cotton. Carboxymethyl chitosan (CMCTS) was synthesized by chemical reaction of chitosan with monochloroacetic acid under alkaline condition. The water soluble CMCTS was applied to cationized cotton with different concentrations. The treated fabrics were characterized through monitoring the textile physical properties and for the antibacterial activity against Escherichia coli DSMZ 498 and Micrococcus luteus ATCC 9341. The results obtained show that the physical properties of the treated fabrics are improved by increasing the CMCTS concentration, as well as the antibacterial activity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

壳聚糖抗菌活性研究进展

壳聚糖具有无毒、良好的生物相容性、生物可降解性、广谱抗菌性等优良性能,作为新型抗菌剂越来越受学者的青睐。本文主要综述了21世纪以来影响壳聚糖抗菌性能的因素、壳聚糖的抗菌机理以及壳聚糖衍生物抗菌性能等方面的内容。     

Rheological study on O−carboxymethylated chitosan/cellulose polyblends from LiCl/N,N‐dimethylacetamide solution

An O?carboxymethylated chitosan (O? CMCh) water solution (I) and N,N‐dimethylacetamide (DMAc) emulsion (II) were blended with a cellulose LiCl/DMAc solution, and corresponding polyblends (Polyblends I and II) were obtained. The rheology of the three fluids, that is, the cellulose solution and Polyblends I and II, was investigated. The cellulose solution was characterized by a power‐law fluid. When an O‐CMCh water solution or DMAc emulsion was added to the cellulose solution, the power‐law curve was preserved. The power‐law indexes (n) of all three fluids increased along with the temperature. Polyblend I displays an n close to but a little higher than that of the cellulose solution, while Polyblend II shows a much higher power index than those of the other two fluids. The values of the apparent viscosity (η_a) for all the three fluids are close and decrease along with an increase in the temperature. Adding O‐CMCh microparticles into Polyblends I and II results in a decrease in the structural viscosity index (Δη) in comparison to that of the cellulose solution, and this effect is very obvious for Polyblend I. A cellulose solution's Δη declines with the augmentation of temperature, while the Δη's of both Polyblends I and II show minimum values at about 323 K. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1719–1725, 2003     

Study of phase behavior on chitosan/viscose rayon blend film

A blend of chitosan and viscose rayon was investigated. A film was made from regenerating the blend of chitosan and viscose rayon. The film was characterized by various techniques, including Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). The phase behavior of the blend is influenced by its composition with or without carboxymeth-ylated chitosan (CM-Cs). Characterization of the chitosan/viscose rayon (Cs/VR) blend by DSC and DMA suggests partial compatibility of chitosan with VR and lack of compatibility in the remaining cases. Results of the TEM show that the addition of CM-Cs into the blend can improve the compatibility of Cs with VR. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1965–1972, 1998     

Preparation,Antibacterial and Physicochemical Behavior of Chitosan/Ofloxacin Complexes

A novel chitosan derivative with ofloxacin (OFX) has been successfully prepared. The IR and 1H-NMR results revealed that the chitosan/ofloxacin (CH-OFX) complex exhibited an electrostatic interaction. The crystalline and surface morphology were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The antimicrobial activity of the complexes against various micro-organisms viz. Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa and Staphylococcus aureus was tested. It was established that their antibacterial activity is up to four times greater than that of free quinolone drug and chitosan, probably due to the conjunction of favorable pharmacokinetics, excellent bacterial susceptibility and good stability towards metabolic degradation.     

Preparation and antibacterial activity of PET/chitosan nanofibrous mats using an electrospinning technique

The nanofiber deposition method, by electrospinning, was employed to introduce antibacterial activity and biocompatibility to the surface of poly (ethylene terephthalate) (PET) textiles. The polymer blends of PET and chitosan were electrospun on to the PET micro‐nonwoven mats for biomedical applications. The PET/chitosan nanofibers were evenly deposited on to the surface, and the diameter of the nanofibers was in the range between 500 and 800 nm. The surface of the nanofibers was characterized using SEM, ESCA, AFM, and ATR‐FTIR. The wettability of the PET nanofibers was significantly enhanced by the incorporation of chitosan. The antibacterial activity of the samples was evaluated utilizing the colony counting method against Staphylococcus aureus and Klebsiella pneumoniae. The results indicated that the PET/chitosan nanofiber mats showed a significantly higher growth inhibition rate compared with the PET nanofiber control. In addition, the fibroblast cells adhered better to the PET/chitosan nanofibers than to the PET nanofibers mats, suggesting better tissue compatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation,characterization, and antibacterial activities of para-biguanidinyl benzoyl chitosan hydrochloride

Para-biguanidinyl benzoyl chitosan hydrochloride (p-BGBC) is prepared with chitosan (CTS) and para-biguanidinyl benzoyl chloride, which is synthesized by acidchloride reaction of para-biguanidinyl benzonic acid hydrochloride (p-BGBA), as starting material in the medium consisted of MeSO₃H and dimethyl sulfoxide (DMSO). Structure of p-BGBC is characterized by FT-IR, ¹H NMR and gel permeation chromatography (GPC), and its antimicrobial activities are evaluated against a Gram-negative bacterium Escherichia coli (E. coli) and a Gram-positive bacterium Staphylococcus aureus (S. aureus). Compared with CTS hydrochloride, p-BGBC has much stronger antimicrobial activities, which increase with the increase of its degree of substitution (DS) of guanidinylation. When the DS of p-BGBC achieves or exceeds 36.8%, its antibacterial activities against the tested bacteria are higher than that of Bromo-Geramium. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

新型壳聚糖季铵盐抗菌剂的合成及其性能

先用两步法合成了无O-甲基化 N,N,N-三甲基壳聚糖季铵盐（TMC）,再通过相转移催化合成了N,N,N-三甲基O-辛基壳聚糖季铵盐（TMOC）,用 FTIR、1H NMR、EA、TG 等方法对产物进行表征,并研究其抗菌性能。结果表明,TMOC在pH值为5.5的抗菌活性优于pH值为7.2的抗菌活性;TMOC对革兰阳性菌S. aureus的抗菌活性比革兰阴性菌E. coli强。在不影响水溶性的前提下,O-烷基化改性能有效提高壳聚糖季铵盐的抗菌活性,并且抗菌活性随着O-烷基化度的提高而提高。研究结果为壳聚糖基抗菌剂的改性和制备提供了依据。     

Antibacterial and anticancer activity of loaded quinazolinone polypyrrole/chitosan silver chloride nanocomposite

Polypyrrole/chitosan-silver chloride core shell nanocomposite (AgCl@PPC) was prepared by in situ oxidative polymerization of pyrrole (Py) using ferric chloride in the presence of chitosan (CS) and silver nitrate to develop a carrier and controlled release system for 3-amino-2-phenyl-4(3H)-quinazolinone (I). For sake of comparison, polypyrrole chitosan core shell nanoparticles (PPC) were prepared and loaded by (I). Fourier transform infrared spectroscopy, X-ray diffraction and thermal gravimetric analysis confirm that I was loaded into PPC and AgCl@PPC core shell nanocomposites respectively, through physical interaction. Results revealed that loaded AgCl@PPC and PPC exhibited excellent antibacterial and anticancer efficacy against Ehrlich ascites carcinoma cells.     

Preparation of O‐diallylammonium chitosan with antibacterial activity and cytocompatibility

In this study, a derivative of chitosan, O‐hydroxy‐2,3‐propyl‐N‐methyl‐N,N‐diallylammonium chitosan methyl sulfate (O‐MDAACS), was synthesized by reacting chitosan with methyl diallyl ammonium. The O‐MDAACS was confirmed by Fourier transform infrared spectroscopy and ¹H NMR. Characterization was conducted including X‐ray diffraction, differential scanning calorimetry and thermogravimetry. The antibacterial activities of O‐MDAACS against Staphylococcus aureus and Klebsiella pneumoniae were evaluated. The minimum inhibitory concentrations on O‐MDAACS were 3.7% and 23% of those on chitosan against S. aureus and K. pneumonia, respectively. The minimum bactericidal concentrations on O‐MDAACS were 7% and 36% of those on chitosan against S. aureus and K. pneumonia, respectively. Thus the antibacterial activity of O‐MDAACS was higher than that of chitosan. The cytocompatibility was evaluated in vitro with L929 fibroblasts. The results showed that after 72 h incubation the cell viability on O‐MDAACS was about 12% and 59% higher than those on chitosan and on control, respectively. © 2012 Society of Chemical Industry     

Characteristics of cotton fabrics treated with epichlorohydrin and chitosan

Cotton fabrics treated with a crosslinking agent, epicholorohydrin, in the presence of chitosan (CEC) provide many possible reactive sites for reactive dyes and antimicrobial properties of the grafted chitosan to the cellulose structure. This process was applied by means of the conventional mercerizing process. The chitosan finishing and durable press finishing of the cotton fabrics occurred simultaneously in the mercerization bath. ECH is expected to react with hydroxyl groups in cellulose and chitosan or with amino groups in chitosan to form alcohol crosslinking by the Belfast process. The fixed chitosan content in the CEC was calculated by the nitrogen percentage of an Elemental Analyzer. The color strength (K/S) of the reactive dyes of the treated cotton fabrics did not significantly change with an increase of chitosan; however, the degree of swelling of the treated cotton fabrics decreased with an increase of chitosan and ECH. These performances were retained through 20 washing and tumble drying cycles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

壳聚糖与柠檬醛缩合反应产席夫碱及其抗菌活性

通过壳聚糖与柠檬醛在超声波振荡下反应制备了壳聚糖缩柠檬醛席夫碱。采用[L9（33）]正交实验探讨了反应时间、反应温度及反应物配比对壳聚糖席夫碱缩合率和取代度的影响。最佳条件为：反应物配比n（壳聚糖）∶n（柠檬醛）=1∶6,反应温度40～50 ℃,反应时间10 h,壳聚糖席夫碱的缩合率可达86%,取代度为0.82。红外光谱和X射线衍射光谱结果表明产物具有壳聚糖席夫碱的结构特征。对大肠杆菌、金黄色葡萄球菌和黑曲霉的抗菌实验表明,该产物对大肠杆菌、金黄色葡萄球菌和黑曲霉的最低抑菌浓度分别为1 g/L、1 g/L和5 g/L,其抗菌活性随浓度的增加而增加,且优于壳聚糖。     

对双胍基苯甲酰化壳聚糖盐酸盐的制备及其抗菌活性研究

在盐酸溶液中,对氨基苯甲酸与双氰胺反应合成了中间体对双胍基苯甲酸盐酸盐;该中间体再与氯化亚砜反应得双胍基苯甲酰氯。后者在甲磺酸体系中与壳聚糖进行酰化反应制得对双胍基苯甲酰壳聚糖盐酸盐。考察了酰化时间、温度及反应物投料比等对壳聚糖衍生物取代度的影响,并采用UV,IR,1HNMR对产物进行了表征。抗菌实验表明,该产物对大肠杆菌、金黄色葡萄球菌最低抑菌浓度分别为0.016和0.008 mg/mL,其抗菌活性优于壳聚糖和对双胍基苯甲酸盐酸盐,且随浓度的增大而增强。     

Preparation of water‐soluble chitosan derivatives and their antibacterial activity

Carboxymethyl chitosan sodium (CMCTS) was synthesized by chitosan and chloroacetic acid under an alkali catalyst. Acrylic acid sodium salt and methylacrylic acid sodium salt were grafted onto CMCTS to obtain copolymers with good water solubility. The graft reaction was carried out at 70°C for 2 h, and ammonium persulfate was used as an initiator. The structure changes of chitosan and its derivatives were investigated by the FTIR. The antibacterial activity of chitosan derivatives against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1357–1361, 2002     

Composite films of N,O‐carboxymethyl chitosan and bamboo fiber

To obtain an antibacterial chitosan derivative, composite films of N,O‐Carboxymethyl Chitosan (N,O‐CMCS) and bamboo fiber were prepared. A water‐soluble chitosan derivative‐N,O‐CMCS was synthesized from chitosan with chloroacetic acid in alkaline solution. Composite films with 1–5 wt % N,O‐CMCS content were prepared in NaOH/urea/thiourea solution. The DS of N,O‐CMCS reached 1.70 and the water solubility increased with the increasing of DS. The carboxymethyl group was introduced into chitosan, which led to the decrease of thermal stability and crystallinity. The structural characterization confirmed that N,O‐CMCS was adsorbed on the surface of bamboo fiber. The antibacterial performance of the composite films were enhanced with the increasing of N,O‐CMCS content. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39851.     

海因改性N-季铵化壳聚糖衍生物的合成及其抗菌性能

在酸性条件下,以壳聚糖与环氧季铵盐为原料反应得到水溶性良好的产物N-(2-羟丙基三甲基氯化铵)壳聚糖(HTCC),再用实验室自制的环氧海因改性,得到O-羟丙基(5,5-二甲基海因)-N-(2-羟丙基三甲基氯化铵)壳聚糖衍生物(GH-HTCC),用 FTIR、¹H NMR、UV-VIS和EA 等对产物进行表征。抗菌实验结果表明,产物对两种菌种都有一定的抗菌活性,对金黄色葡萄球菌的抗菌活性优于大肠杆菌;GH-HTCC的抗菌活性优于HTCC,并随环氧海因取代度的增加而增强;低浓度的乙二胺四乙酸(EDTA)增强了HTCC和GH-HTCC的抗菌活性,而高浓度的EDTA在一定程度上抑制了二者的抗菌活性。     

Factors Influencing the Antibacterial Activity of Chitosan and Chitosan Modified by Functionalization

The biomedical and therapeutic importance of chitosan and chitosan derivatives is the subject of interdisciplinary research. In this analysis, we intended to consolidate some of the recent discoveries regarding the potential of chitosan and its derivatives to be used for biomedical and other purposes. Why chitosan? Because chitosan is a natural biopolymer that can be obtained from one of the most abundant polysaccharides in nature, which is chitin. Compared to other biopolymers, chitosan presents some advantages, such as accessibility, biocompatibility, biodegradability, and no toxicity, expressing significant antibacterial potential. In addition, through chemical processes, a high number of chitosan derivatives can be obtained with many possibilities for use. The presence of several types of functional groups in the structure of the polymer and the fact that it has cationic properties are determinant for the increased reactive properties of chitosan. We analyzed the intrinsic properties of chitosan in relation to its source: the molecular mass, the degree of deacetylation, and polymerization. We also studied the most important extrinsic factors responsible for different properties of chitosan, such as the type of bacteria on which chitosan is active. In addition, some chitosan derivatives obtained by functionalization and some complexes formed by chitosan with various metallic ions were studied. The present research can be extended in order to analyze many other factors than those mentioned. Further in this paper were discussed the most important factors that influence the antibacterial effect of chitosan and its derivatives. The aim was to demonstrate that the bactericidal effect of chitosan depends on a number of very complex factors, their knowledge being essential to explain the role of each of them for the bactericidal activity of this biopolymer.