Durable antimicrobial treatment of cotton fabrics using N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride and polycarboxylic acids

N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), a water‐soluble chitosan quaternary ammonium derivative, was used as an antimicrobial agent for cotton fabrics. HTCC has a lower minimum inhibition concentration (MIC) against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli compared to that of chitosan; however, the imparted antimicrobial activity is lost on laundering. Thus crosslinking agents were utilized to obtain a durable antimicrobial treatment by immobilizing HTCC. Several crosslinkers such as dimethyloldihydroxyethylene urea (DMDHEU), butanetetracarboxylic acid (BTCA), and citric acid (CA) were used with HTCC to improve the laundering durability of HTCC treatment by covalent bond formation between the crosslinker, HTCC and cellulose. The polycarboxylic acid treatment was superior to the DMDHEU treatment in terms of prolonged antimicrobial activity of the treated cotton after successive laundering. Also, the cotton treated with HTCC and BTCA showed improved durable press properties without excessive deterioration in mechanical strength or whiteness when compared to the citric acid treatment. With the addition of only 0.1% HTCC to BTCA solutions, the treated fabrics showed durable antimicrobial activity up to 20 laundering cycles. The wrinkle recovery angle and strength retention of the treated fabrics were not adversely affected with the addition of HTCC. Therefore, BTCA can be used with HTCC in one bath to impart durability of antimicrobial activity along with durable press properties to cotton fabric. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1567–1572, 2003     

Preparation of nanoparticles composed of chitosan and its derivatives as delivery systems for macromolecules

Three different kinds of nanoparticles for paracellular transport were prepared using a simple and mild ionic‐gelation method. Sodium tripolyphosphate (TPP) as crosslinking agent was added into three kinds of solutions, which were chitosan solution, physical blending solution of chitosan, and glycidyl trimethylammonium chloride (GTMAC), and O‐(2‐hydroxyl) propyl‐3‐trimethyl ammonium chitosan chloride (O‐HTCC) solution respectively. O‐HTCC was synthesized by coupling of GTMAC to chitosan whose functional groups of the NH₂ groups were protected. The nanoparticles were characterized by transmission electron microscopy, atomic force microscopy, photon correlation spectroscopy, and zeta potential measurement. The results showed that increasing TPP concentration promoted the size of chitosan nanoparticles, a decrease in the size of O‐HTCC nanoparticles incurred on the contrary. The size of O‐HTCC nanoparticles is slightly bigger than that of pure chitosan nanoparticles, and smaller than that of physical blending nanoparticles (PBN). Bovine serum albumin (BSA), as a model protein drug, was incorporated into the nanoparticles. Compared with chitosan nanoparticles and PBN, high BSA loading efficiency (87.5%) and loading capacity (99.5%) are achieved by quaternized chitosan (O‐HTCC) nanoparticles, and the release profile of BSA from nanoparticles has an obvious burst effect and a slowly continuous release phase followed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of a quaternary ammonium derivative of chito‐oligosaccharide as antimicrobial agent for cellulosic fibers

A derivative of chito‐oligosaccharide (COS), N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium chito‐oligosaccharide chloride (HTACC), was synthesized using a reaction of glycidyltrimethylammonium chloride (GTMAC) and COS prepared by depolymerization of a fully deacetylated chitosan. COS and HTACC were applied to the cotton fabrics with a pad‐dry‐cure process using the reaction between the hydroxyl group of cellulose and terminal aldehyde group in COS and HTACC. Their minimum inhibition concentration (MIC) was evaluated, and the antimicrobial activity and durability to laundering of cotton fabrics treated with them were compared. The complete substitution of NH₂ groups in COS with GTMAC was obtained at a 4 : 1 mol ratio of GTMAC to NH₂ in 18 h at 80°C under the presence of acetic acid. MIC values of the 1.04 DS of HTACC and COS were 50 and 400 μg/mL, respectively. A cotton fabric treated with 0.2% of HTACC and 1.8% of COS exhibited 100% reduction of bacteria. At the 50th laundering cycle, 0.3% of HTACC and 2.4% of COS indicated 100% bacterial reduction. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2009–2015, 2000     

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     

Characterization of novel quaternary chitosan derivative nanoparticles loaded with protein

The objective of this work was to characterize a novel quaternary chitosan derivative [O‐(2‐hydroxyl) propyl‐3‐trimethyl ammonium chitosan chloride (O‐HTCC)] nanoparticle system. O‐HTCC nanoparticles were prepared with a simple and mild ionic gelation method upon the addition of a sodium tripolyphosphate solution to a low‐molecular‐weight O‐HTCC solution. Highly cationic chitosan nanoparticles were prepared. Bovine serum albumin (BSA), a model protein drug, was incorporated into the nanoparticles. The physicochemical properties of the nanoparticles were determined with transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared analysis, differential scanning calorimetry, and X‐ray diffraction (XRD) patterns. The results showed that increasing the BSA concentration from 1.5 to 2.5 mg/mL promoted the BSA encapsulation efficiency from 57.3% to 87.5% and the loading capacity from 70.2% to 99.5%. Compared with the chitosan nanoparticles, the O‐HTCC nanoparticles had lower burst release. TEM revealed that the BSA‐loaded O‐HTCC nanoparticles were smaller than the O‐HTCC nanoparticles when the BSA concentration was 1.5 mg/mL; SEM showed that the size of the BSA‐loaded O‐HTCC nanoparticles was mostly affected by the BSA concentration, and the increase in size occurred with the concentration increasing. Thermograms and XRD of the BSA‐loaded nanoparticles suggested that polyelectrolyte–protein interactions increased with the BSA concentration increasing and greater chain realignment in the BSA‐loaded nanoparticles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Antimicrobial finishing of regular and modified polyethylene terephthalate fabrics

An effective two-stage method has been developed for imparting antimicrobial properties to regular polyethylene terephthalate (R-PET), polyethylene glycol modified polyethylene terephthalate (PEG-M-PET), R-PET/Cotton blend (R-PET/C) and PEG-M-PET/Cotton blend (PEG-M-PET/C) fabrics. The method consists of partial hydrolysis of the fabrics to create carboxylic groups in PET macromolecules followed by subsequent reaction with dimethylalkylbenzyl ammonium chloride (DMABAC) under alkaline conditions. The reaction conditions such as pH, reaction temperature and time, carboxylic content, and DMABAC concentration were studied. Characterization of the finished fabrics was carried out through scanning electron microscopy (SEM) and Fourier transform infrared spectra (FTIR). All the modified PET fabrics showed excellent antibacterial activity towards Gram-positive (Bacillus mycoides), Gram-negative (Escherichia coli), and nonfilamentous fungus (Candida albicans). The achieved antimicrobial functions on the PET fabrics are durable in repeated laundering processes. Even after laundering 10 times the fabrics could still provide more than 85% of its antimicrobial activity against B. mycoides, E. coli, and C. albicans. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of polyacrylonitrile-N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride blend films and fibers

A water-soluble chitosan derivative namely, N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride (HTCC) was synthesized by the reaction of chitosan with glycidyltrimethyl ammonium chloride in a neutral aqueous condition and solution blended with polyacrylonitrile (PAN) in an organic solvent. Polymeric films were made by casting, and they were dyed with an acid dye, a basic dye, and mixture of them. Results obtained from differential scanning calorimetry, scanning electron microscopy, and dyeing show that these polymers are immiscible even at low percentage of HTCC (lower than 20%). However, at higher ratio, the phase separation takes place. Fibers obtained from this blend system by wet-spinning technique show a good mechanical properties and increasing the amount of HTCC causes an increment in the mechanical strength of the fibers up to 20% of HTCC and beyond that due to phase separation mechanical strength reduces. Blending PAN with HTCC improves the dyeing behavior of the films and fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cationic starch iodophores

Cross‐linked cationic starches N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium starch chloride (CQS chloride), N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium starch iodide (CQS iodide), and N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium starch iodide–iodine (CQS triiodide) with the degree of substitution (DS) according to cationic groups from 0.04 to 0.62, as well as cross‐linked starch–iodine complexes were synthesized and tested as potential antibacterial agents. Cationic starch iodine derivatives were obtained during ion exchange reaction between CQS chloride and iodide or iodide–iodine anions in aqueous solutions. CQS_DS≤0.3 chloride can form several types of iodine complexes, such as the blue amylose–iodine inclusion complex and ionic CQS⁺I^?·(I₂)_m complex (m ≥ 1). The antibacterial activity of modified starches–iodine samples against different pathogenic bacterial cultures and contaminated water microorganisms was evaluated. CQS chloride and CQS iodide were found to be bacteriostatic. A strong antibacterial activity was characteristic of CQS triiodides in which molecular iodine is present in both ionic and inclusion complexes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Atmospheric plasma‐aided biocidal finishes for nonwoven polypropylene fabrics. I. Synthesis and characterization

Novel biocidal fabrics were synthesized by the graft copolymerization of glycidyl methacrylate (GMA) onto plasma‐treated nonwoven polypropylene (PP) to produce PP/GMA grafts. Atmospheric oxygenated helium plasma was used to enhance the PP fabrics' initiation before GMA grafting. The grafted PP/GMA epoxide group was reacted with β‐cyclodextrin, monochlorotrizynyl‐β‐cyclodextrins, or a quaternary ammonium chitosan derivative [N‐(2 hydroxy propyl) 3‐trimethylammonium chitosan chloride]. Some interesting biocidal agents were complexed into the cyclodextrin (CD) cavity of PP/GMA/CD grafted fabrics. Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and optical and scanning electron microscopies were used to characterize the grafted complexed fabrics. These synthesized biocidal fabrics proved to be antistatic, antimicrobial, and insect‐repelling (see part II of this study). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1900–1910, 2007     

Antimicrobial activity of cotton fabrics treated with curcumin

Curcumin, a yellow pigment known to have various biological activities, was applied onto cotton as an antimicrobial agent. Curcumin could provide both color and antimicrobial activity to cotton and can be dyed using a batch or continuous process. However, curcumin and cotton have low affinity and therefore the ability of curcumin to impart durable antimicrobial activity on cotton needs to be studied. In this research, the ability of curcumin dyed onto cotton fabrics to inhibit the growth of Escherichia coli and Staphylococcus aureus was studied. Relationships that can predict the rate of inhibition based on the curcumin concentration or shade depth (K/S values) were developed without the need for an antimicrobial test. Durability of antimicrobial activity to laundering and to light was also studied. Curcumin was more effective in inhibiting S. aureus than E. coli. The reduction of bacteria and durability of antimicrobial activity of curcumin to laundering was inferior on cotton fabrics compared with wool. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modification of polyacrylonitrile (PAN) fiber by blending with N‐(2‐hydroxy)propyl‐3‐trimethyl‐ ammonium chitosan chloride

N‐(2‐Hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC) was synthesized by the reaction of glycidyltrimethylammonium chloride (GTMAC) and chitosan. The reaction product was a water‐soluble chitosan derivative, and showed excellent antimicrobial activity. HTCC was blended with polyacrylonitrile (PAN) using an NaSCN aqueous solution as a common solvent. The blend solution was transparent and stable up to 6 months without phase separation. The PAN/HTCC blend fibers were prepared via a wet spinning and drawing process. Thermal, electrical, and mechanical properties as well as antimicrobial activity were investigated. It was found that the antistatic property and antimicrobial activity of the blend fibers could be achieved by adding only a small amount of HTCC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2258–2265, 1999     

Blend fibers of polyacrylonitrile and water‐soluble chitosan derivative prepared from sodium thiocyanate solution

A water‐soluble chitosan derivative of N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), synthesized by the reaction of chitosan and glycidyltrimethyl ammonium chloride, and polyacrylonitrile (PAN) were blended using 46% (w/w) NaSCN aqueous solution as a common solvent. The total polymer concentration of blend solution was fixed at 12% (w/w), and the relative composition of PAN/HTCC in the blend solution varied from 0/100 to 80/20 by weight. The PAN/HTCC blend fibers with the appropriate physical property were prepared by a wet spinning and drawing process. The effect of HTCC content on the structural change, miscibility, and ability to be dyed of the blend fibers was investigated. The optical and scanning electron microscopic observation gave no indication of phase separation up to 20% HTCC content. Differential scanning calorimetry and dynamic mechanical measurements of the blend fibers show single glass transition temperatures that increase with increasing blend ratio of HTCC. All the experimental results exhibit that the blends are miscible on the molecular scale. The blend fibers could be dyed with an acid dye. This enhanced ability of the blend fibers to be dyed with acid dyes could be useful for one‐step dyeing when mixed with other fibers, such as wool and nylon. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1620–1629, 2001     

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     

A facile dip‐coating approach to prepare SiO2/fluoropolymer coating for superhydrophobic and superoleophobic fabrics with self‐cleaning property

In this study, a facile, two‐step dip‐coating approach was reported for the fabrication of the superhydrophobic and superoleophobic cotton fabrics. It was confirmed that the superhydrophobic and superoleophobic composite thin film containing modified‐SiO₂ nanoparticles and fluoropolymer had been successfully fabricated on the cotton fabrics surface, the results demonstrated that the treated cotton fabrics showed good performances, such as superhydrophobicity and superoleophobicity, low water and oil absorption ability, self‐cleaning property and good laundering durability, so forth. The above approach can be applied to potentially advance superhydrophobic and superoleophobic fabrics materials for a variety of applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41458.     

Synthesis of sulfated β‐cyclodextrin/cotton/ZnO nano composite for improve the antibacterial activity and dyeability with Azadirachta indica

The sulfated β‐cyclodextrin (sb‐cd) was prepared from β‐cyclodextrin and the sb‐cd was crosslinked with cotton fabric using ethylenediaminetetraacetic acid (EDTA) as crosslinker. After crosslinking, the synthesized ZnO nanoparticles were padded on this fabric surface. Then, the treated fabrics were dyed with neem extract. The synthesized polymer, crosslinked and nanoparticle‐treated cotton fabrics were characterized using fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), particle sized analyzer, and transmission electron microscopy (TEM) studies. The antibacterial test was done against Staphylococcus aureus and Escherichia coli bacterium. The composite coated with neem dyed cotton fabric has exhibited 71% of dye uptake with 2–3 fastness grade and it has 99% of antibacterial efficiency for S. aureus and 97% for E. coli bacterium. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

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     

Cationization of cellulose/polyamide on UV protection,bio‐activity,and electro‐conductivity of graphene oxide‐treated fabric

In this work, cationized cotton/nylon fabric was treated with reduced graphene oxide (rGO) to produce highly conductive fabric. The fabric was cationized with 3‐chloro‐2‐hydroxy propyl trimethyl ammonium chloride to attract more anionic GO. The fabric was then treated with GO followed by reduction with sodium dithionite. The results of energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy indicated entire coverage of the fabric surface with rGO. The color of fabrics changed to gray‐black and the electrical resistance decreased to 0.6 × 103 Ω sq^?1. The washing fastness was measured according to ISO 105‐CO5 for color change and also electrical resistance of the samples demonstrated well stability of rGO on the fabric surface. The antibacterial activities of the treated fabrics improved against Gram‐negative bacteria including Escherichia coli (84.8%) and Pseudomonas aeruginosa (96.4%) and also Gram‐positive bacteria consisting Staphylococcus aureus (100%) and Enterococcus faecalis (98.4%). Further, the treated fabrics indicated an excellent UV reflectance of 100%. Finally heating of the cationized rGO fabric at 220 °C displayed a lower electrical resistance of 0.5 × 103 Ω sq^?1. The thermogravimetric analysis showed that heating has a slight effect on the dimensional thermal stability of the treated fabric as shrunk 2.43%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45493.     

Preparation of chitosan-based flocculant for high density waste drilling mud solid–liquid separation

High performance flocculant was prepared by chitosan (CS), ethacryloyloxyethyl trimethyl ammonium chloride (DMC), and acrylamide (AM). The optimum preparation conditions were determined by orthogonal test of four factors and three levels. The different factors affecting the flocculating ability of the prepared flocculants for waste drilling mud were studied, and optimal synthesis conditions were established: polymerization temperature was 60, reaction time was 4 h, DMC was 3 mL, w(AM) : w(CS) was 4, and the initiator was 0.4% of AM (wt %). The prepared CS–AM–DMC copolymer was characterized by Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM), and gel permeation chromatography (GPC). The results showed that AM, DMC were grafted to CS successfully. The solid–liquid separation properties were also investigated, and the prepared flocculant showed great advantages than commercial products for high density waste drilling mud use. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Wrinkle resistant properties and antibacterial efficacy of cotton fabrics treated with glyoxal system and with combination of glyoxal and chitosan system

This study examined the possibility of using glyoxal and chitosan in one‐step finishing to impart both durable press performance and antibacterial efficacy on cotton fabrics. Glyoxal treatment provided good wrinkle resistant property and fair antibacterial activity on the finished fabrics, but the loss of breaking strength retention of the finished fabrics was a main problem of this treatment. Chitosan added in the combination of glyoxal and chitosan system also provided comparable results in wrinkle resistant and antibacterial properties on the finished fabrics as the glyoxal did. The advantage of chitosan in the combination of glyoxal and chitosan system was the improvement of the breaking strength retention of the finished fabrics without affecting the durable press property of the finished fabrics. However, the yellowing of the finished fabric was still a problem when the finished fabrics were treated with the combination of glyoxal and chitosan system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1372–1377, 2006