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     

Synthesis and antimicrobial activity of Schiff base of chitosan and acylated chitosan

Chitosan, a biocompatible, biodegradable, nontoxic polymer, is prepared from chitin, which is the second most naturally occurring biopolymer after cellulose. Schiff base of chitosan, sorbyl chitosan, and p‐aminobenzoyl chitosan were synthesized working under high‐intensity ultrasound and their antimicrobial properties were analyzed against Escherichia coli, Staphylococcus aureus, and Aspergillus niger. The structures of the derivatives were characterized by FTIR spectroscopy and elemental analysis. The results of antimicrobial activities indicated that the antimicrobial activities of the derivatives increased with increasing the concentration. The antibacterial activity of schiff base of chitosan against E. coli was stronger, while acylated chitosan had better inhiting effect on S. aureus than others. It was also found that the antifungal activities of the derivatives were stronger than that of chitosan, and schiff base of chitosan was obviously superior to acylated chitosan. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Antibacterial effects of chitosan and its water‐soluble derivatives on E. coli,plasmids DNA,and mRNA

The antibacterial activities of chitosan and its water‐soluble derivatives on E. coli were studied according to four influencing factors in vitro. The antibacterial study showed that chitosan, O‐hydroxyethyl chitosan (O‐HECS), and O‐carboxymethyl chitosan (O‐CMCS) could inhibit the growth of the microbial. To study the antibacterial mechanism, plasmid DNA pBR322 and pUC18 were selected to be the probes to find out the binding abilities of chitosans. Results showed that raw chitosan had a high binding ability with the plasmids and the influencing degrees were stable. The effects of chitosan derivatives on plasmids might be affected by space effect and static effect. With appropriate concentrations and molecular weights, the derivatives might have strong abilities to combine with DNA. The degree of influence of chitosan and its derivatives on plasmids had nothing to do with time. The experiment focusing on the relationship between chitosans and mRNA showed that O‐CMCS would hinder the synthesis of mRNA, and this may give some proof to its antibacterial mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3521–3528, 2007     

Syntheses of novel chitosan derivative with excellent solubility,anticoagulation, and antibacterial property by chemical modification

The soluble and antibacterial chitosan derivative was prepared on the basis of the regioselective chemical modification. The N‐(2‐phthaloylation) chitosan was obtained via the reaction of chitosan with phthalic anhydride in N,N‐dimethylformamide (DMF) at 130°C, and O‐(3,6‐hydroxyethyl) chitosan was produced using chlorohydrins as grafting agent and hydrazine hydrate as reductant. The structure of hydroxyethyl chitosan (HC) was characterized by X‐ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC) respectively. The solubility, anticoagulation, and antibacterial property were assessed separately. The result shows that amine I of chitosan is replaced and the amide II disappears during chemical modification, and the functional groups of C6‐OH and ‐NH2 are also reacted. The water‐solubility of the novel chitosan derivative was enhanced relatively; it could even slightly soluble in methanol. The results of platelet adhesion and the activated partial thromboplastin times (APTTs) indicate that grafting hydroxyethyl could improve anticoagulation of chitosan. The antibacterial activity of HC against Enterococcus and E. coli had been much better owing to enhancing the degree of protonation. © 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     

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     

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     

Synthesis of 2‐hydroxypropyl dimethylbenzylammonium N,O‐(2‐carboxyethyl) chitosan chloride and its antibacterial activity

N,O‐(2‐carboxyethyl)chitosan (N,O‐2‐CEC) was prepared from chitosan with 3‐chloropropionic acid as modifying agent and NaOH as binding‐acid agent. 2‐Hydroxypropyl dimethylbenzylammonium N,O‐(2‐carboxyethyl) chitosan chloride (HPDMBA‐CEC) was obtained by the reaction of N,O‐2‐CEC with glycidyl dimethyl benzyl ammonium chloride (GDMBA) using NaOH as catalyst. The structures of chitosan derivatives were characterized by FTIR, ¹H NMR, and gel permeation chromatography. The antimicrobial activity of HPDMBA‐CEC was evaluated against a Gram‐negative bacterium Escherichia coli (E.coli) and a Gram‐positive bacterium Staphylococcus aureus (S. aureus). Compared with CTS, N,O‐2‐CEC, and HPDMBA‐CTS, HPDMBA‐CEC had much stronger antimicrobial activity, and this activity increased with increasing substitution degree of quaternary ammonium group (DQ). When the substitution degree of carboxyethylation (DS of CE) was 0.72 and DQ was 0.60, the minimum inhibitory concentrations (MICs) of HPDMBA‐CEC were 3.1 and 6.3 μg/mL against S. aureus and E. coli, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study of chitosan and its derivatives as preservatives for field natural rubber latex

In this study, the chitosan and its derivatives were tested for their preservative activities for field natural rubber (NR) latex. A series of chitosans with different molecular weights were obtained by nitrous acid depolymerization. The chemically modified chitosans, N‐carboxymethyl chitosan (NCMCh), N‐sulfated chitosan (NSCh), and N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (NHTACh), were prepared from high and low‐molecular weight chitosans. Preservative activities for field NR latex of these chitosans were investigated based on the measurement of volatile fatty acids (VFA) number of the treated latex. The preservative activities of chitosan increased with decreasing molecular weights. The low‐ molecular weight NSCh and NHTACh exhibited good preservative activity for the latex. By the use of low‐molecular weight NHTACh in combination with octylphenol poly (ethyleneglycolether) (Nonidet P40), the latex was successfully preserved for more than 1 month in the low‐ammonia condition. The results showed an attractive feature to develop the preservative system, which was possible to reduce the concentrations of ammonia and carcinogenic nitrosamine in the NR latex. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface grafting of polyester fiber with chitosan and the antibacterial activity of pathogenic bacteria

Three polyesters—poly(ethylene terephthalate), poly(2‐methyl‐1,3‐propylene terephthalate‐co‐ethylene terephthalate), and poly(1,4‐cyclohexylene terephthalate‐co‐ethylene terephthalate)—were preirradiated with ⁶⁰Co‐γ‐rays. Then, acrylic acid and N‐vinylformamide were grafted to these irradiated fibers. Fibers grafted with N‐vinylformamide were further hydrolyzed with acid so that the amide groups would convert into amino groups, and they were treated with glutaraldehyde so that aldehyde groups would be introduced. Chitosan or chitooligosaccharide was then grafted to these fibers via either esterification or imine formation. Four pathogenic bacteria—methicillin‐resistant Staphylococcus aureus‐1 (MRSA), Staphylococcus aureus‐2, Escherichid coli, and Pseudomonas aeruginosa—were tested to determine the antibacterial activities of chitosan‐grafted and chitooligosaccharide‐grafted fibers. The results showed that grafting chitosan via imine formation could achieve a higher surface density for amino groups and give higher antibacterial activity to those four bacteria tested. The antibacterial activity for E. coli was the highest and that for MRSA was the lowest among the four bacteria tested. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2977–2983, 2002     

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.     

Preparation and antibacterial activity of C2-benzaldehyde-C6-aniline double Schiff base derivatives of chitosan

C₂-benzaldehyde-C₆-aniline double Schiff base derivatives of chitosan were synthesized with positioning protection method for the first time. The structures and properties of the new synthesized products were characterized by Fourier transform infrared spectroscopy, ¹³C nuclear magnetic resonance, scanning electron microscope image, X-ray diffraction, and elemental analysis. The elemental analysis results indicated that the degrees of substitution of the products were from 39.6% to 48.2%. The synthesized compounds exhibited an excellent solubility in organic solvents. The antibacterial activities of all of the derivatives were tested in the experiment, and the results showed that the prepared chitosan derivatives had significantly improved antibacterial activity of chitosan and C₂-benzaldehyde Schiff bases of chitosan toward Staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC 35218). Antibacterial activity of the Schiff bases against E. coli differs from the substituent at the same position of different anilines and increases as the sequence aniline?>?p-toluidine?>?o-toluidine, and the antibacterial activity of the Schiff bases against S. aureus increases as the sequence p-toluidine?>?aniline?>?o-toluidine. The I_C50 of the C₂-benzaldehyde-C₆-aniline double Schiff base derivatives of chitosan against E. coli and S. aureus is 0.0035 and 0.0031?mg?L^?1, respectively, much lower than that of chitosan (0.0064?mg?L^?1) and C₂-benzaldehyde Schiff bases of chitosan (0.0054?mg?L^?1). The cytotoxicity test showed that compared with chitosan and C₂-benzaldehyde Schiff bases of chitosan, the prepared chitosan derivatives had lower cytotoxicity against SCG-7901. This paper provided a new method for the synthesis of Schiff bases of chitosan, which was enlightening.     

Effect of immobilized neutral protease on the preparation and physicochemical properties of low molecular weight chitosan and chito‐oligomers

Neutral protease was immobilized on glutaraldehyde‐pretreated N‐succinyl chitosan hydrogel beads and the biocatalyst obtained was used for the preparation of low molecular weight chitosan and chito‐oligomers with molecular weight of 1.9–23.5 kDa from commercial chitosan. Factors affecting the chitinolytic hydrolysis were described. The degradation was monitored by gel permeation chromatography. The structure of degraded chitosan was characterized by Fourier transform infrared, X‐ray diffraction and liquid chromatography‐mass spectrometry. Immobilized neutral protease showed optimal depolymerization at pH 5.7 and 50°C. The degree of deacetylation of the hydrolysates did not change compared to that of the initial chitosan. The decrease of molecular weight led to transformation of crystal structure but the chemical structures of residues were not modified. The degree of polymerization of chito‐oligomers was mainly from 3 to 8. The method allows cyclic procedures of immobilized enzyme and N‐succinyl chitosan support utilization, and is suitable for a large‐scale production of the low molecular weight chitosan and chito‐oligomers free of protein admixtures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4185–4193, 2006     

Improved antimicrobial activity of polypropylene and cotton nonwoven fabrics by surface treatment and modification with chitosan

Nonwoven polypropylene and cotton fabrics were subjected to plasma pretreatment followed by flash evaporation and radiation crosslinking acrylate polymer coating, which is based on a vacuum deposition, solvent free, process that produces high quality, uniform fabrics with various thicknesses (0.05–5.0 μm). These treated fabrics were then dipped into chitosan, carboxymethyl chitosan, and carboxymethyl chitin solution. These polysaccharides form strong complexes with the modified surface. The antimicrobial activity of these treated samples was then evaluated for their antifungal and antibacterial properties. The antifungal activity for Fusarium oxysporum f. sp. lycopersici, Verticillium albo‐atrum, and Alternaria solani (A. alternata) were examined by the disc plate method. The antibacterial activities of the modified fabrics against Clavibacter michiganensis and Pseudomonas solanacearum were also examined by the viable cell counting method. The inhibition zone of the chitosan covered samples has increased by a factor of 2–3.1 over the original pretreated samples. The chitosan‐modified fabrics showed a good antibacterial activity in killing almost 10⁵ cells/mL within 18–23 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Pyromellitimide benzoyl thiourea cross-linked carboxymethyl chitosan hydrogels as antimicrobial agents

A series of novel hydrogels based on carboxymethyl chitosan (CMCS) has been synthesized by a cross-linking reaction between CMCS and various amounts of N,N′-bis [4-(isothiocyanate carbonyl)phenyl] pyromellitimide as a cross-linker to produce pyromellitimide benzoyl thiourea–CMCS hydrogels designated as PIBTU–CMCS (1–4). Hydrogel structures were identified by elemental analyses and FTIR and ¹H-NMR spectroscopy. The prepared hydrogels were characterized for their properties to understand the influence exerted by controlled structural variations in these hydrogels. All the hydrogels showed a greater antibacterial activity on Gram-positive than Gram-negative bacteria. They also exhibited higher antifungal activities. Their antimicrobial activity improved by increasing their cross-linking degree.     

Moisture retention and antibacterial activity of modified chitosan by hydrogen peroxide

A series of chitosans with various molecular weights from 1.2 × 10³ to 30.0 × 10⁴ were prepared by oxidative degradation with H₂O₂ and characterized by IR, ¹³C‐NMR, and gel permeation chromatography. Their carboxylic contents increased with a decrease in molecular weight (M_w). The moisture‐absorption and moisture‐retention capacities of resulting chitosans were dependent on both the molecular weight and the degree of deacetylation (DD). Microcalorimetry was first used to study the kinetics of action of the chitosans on a strain of Staphylococcus aureus at pH 7. The antibacterial activity of the water‐soluble chitosan against S. aureus, Escherichia coli, and Salmonella typhi was evaluated by the conventional agar plate method at pH 7. The water‐soluble product with M_w of 0.45 × 10⁴ from initial chitosan of DD of 90% showed high moisture‐absorption and moisture‐retention capacities, and <2% concentration can completely inhibit the growth of these bacteria. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1724–1730, 2002     

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     

Antibacterial and anti-mildew behavior of chitosan/nano-TiO2 composite emulsion

A novel chitosan/nano-TiO₂ composite emulsion (CTCE) was prepared by inverse suspension technology, and its multi-function properties were studied. As can be seen from the results, the gauze treated with chitosan/nano-TiO₂ composite emulsion showed excellent antibacterial activities against Escherichia coli, Aspergillus niger and Candida albicans that the bactericidal ratios could reach 99.96%, 100% and 78.3% after 24 h, respectively. At the same time, the chitosan/nano-TiO₂ composite emulsion could really kill the bacteria, not just inhibit its growth, and the bactericidal ratio for E. coli could reach 70.3% after 1 h. The bactericidal ratio for E. coli reached 98.8% at 27 °C compared with 58.7% at 18 °C after 8 h due to the activity of bacteria being weakened at low temperature. Furthermore, the antibacterial ability of antibacterial gauze was hardly influenced with the increase of storage time, which could be reused for up to 8 times without loss of antibacterial ability. This work was presented at 13 ^th YABEC symposium held at Seoul, Korea, October 20–22, 2007.     

Nanocomposite of chitosan and silver oxide and its antibacterial property

An aqueous emulsion of chitosan nanoparticles encapsulating silver oxide is prepared from silver nitrate and chitosan. The nanoparticles are positively charged with an average diameter of 300 nm. The dried particle has a spherical shape with a 100 nm diameter. The emulsion is applied onto cotton and delivers a durable antibacterial activity against S. aureus and E. coli, after 20 washings. The coefficient of friction of the treated fabric is similar to that of the untreated cotton fabric. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008