Abstract
In this study, a chitosan-based high polymer antibacterial agent CS-g-DMC with high water solubility was synthesized via an environmentally friendly initiator system of H2O2 and ascorbic acid (Vc). The CS-g-DMC is used for the long-effective antibacterial finishing of cotton fabric. SEM, EDS, FTIR, XPS, and XRD were conducted to characterize the finished fabric. After the treatment, the CS-g-DMC were cross-linked with cellulose by 1,2,3,4-Butane tetracarboxylic acid BTCA thus immobilized on cotton fabrics. Results showed CS-g-DMC had linked with cellulose by stable chemical bond and uniformly distributed on the surface of cotton fiber. The antibacterial test shows that after treatment, the inhibition rates of the cotton fabric against E. coli and S. aureus are above 99.9%. Moreover, the inhibition rates of the two bacteria reach 94.3% and 95.3% after washing ten times, respectively. The finished cotton fabric had significantly improved hydrophily; its contact angle decreased from 107° to 104°. Its breaking force significantly increased from 173.38 to 219.33 N, while its breaking elongation and moisture transmission rate had no significant decrease. In general, CS-g-DMC-finished cotton fabrics achieve long-lasting antibacterial properties and higher mechanical properties while retaining a high degree of wearing comfort.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Adhikari HS, Yadav PN (2018) Anticancer activity of chitosan, chitosan derivatives, and their mechanism of action. Int J Biomater 2018:1–29. https://doi.org/10.1155/2018/2952085
Andra S, Balu SK, Jeevanandam J, Muthalagu M, Danquah MK (2021) Surface cationization of cellulose to enhance durable antibacterial finish in phytosynthesized silver nanoparticle treated cotton fabric. Cellulose 28:5895–5910. https://doi.org/10.1007/s10570-021-03846-2
Andreica B-I, Cheng X, Marin L (2020) Quaternary ammonium salts of chitosan. A critical overview on the synthesis and properties generated by quaternization. Eur Polym J 139:110016. https://doi.org/10.1016/j.eurpolymj.2020.110016
Bakshi PS, Selvakumar D, Kadirvelu K, Kumar NS (2020) Chitosan as an environment friendly biomaterial: a review on recent modifications and applications. Int J Biol Macromol 150:1072–1083. https://doi.org/10.1016/j.ijbiomac.2019.10.113
Barbosa M, Costa F, Monteiro C, Duarte F, Martins MCL, Gomes P (2019) Antimicrobial coatings prepared from Dhvar-5-click-grafted chitosan powders. Acta Biomater 84:242–256. https://doi.org/10.1016/j.actbio.2018.12.001
Bhuiyan MAR, Wang L, Ara ZA, Saha T, Wang X (2022) Omniphobic polyurethane—superabsorbent polymer—fluoropolymer surface coating on cotton fabric for chemical protection and thermal comfort. J Ind Text 51:6590–6611
Branca C, D’Angelo G, Crupi C, Khouzami K, Rifici S, Ruello G, Wanderlingh U (2016) Role of the OH and NH vibrational groups in polysaccharide-nanocomposite interactions: a FTIR-ATR study on chitosan and chitosan/clay films. Polymer 99:614–622. https://doi.org/10.1016/j.polymer.2016.07.086
Chang L, Duan W, Huang S, Chen A, Li J, Tang H, Pan G, Deng Y, Zhao L, Li D (2021) Improved antibacterial activity of hemp fibre by covalent grafting of quaternary ammonium groups. R Soc Open Sci. https://doi.org/10.1098/rsos.201904
Chen S, Yuan L, Li Q, Li J, Zhu X, Jiang Y, Sha O, Yang X, Xin JH, Wang J, Stadler FJ, Huang P (2016) Durable antibacterial and nonfouling cotton textiles with enhanced comfort via zwitterionic sulfopropylbetaine coating. Small 12:3516–3521. https://doi.org/10.1002/smll.201600587
Cheng W, Liu W, Wang Q, Wang P, Zhou M, Yu Y (2022) Durable hydrophobic and antibacterial textile coating via PDA/AgNPs/ODA in situ assembly. Cellulose 29:1175–1187. https://doi.org/10.1007/s10570-021-04339-y
Choi C, Nam J-P, Nah J-W (2016) Application of chitosan and chitosan derivatives as biomaterials. J Ind Eng Chem 33:1–10. https://doi.org/10.1016/j.jiec.2015.10.028
Dai T, Tanaka M, Huang Y-Y, Hamblin MR (2011) Chitosan preparations for wounds and burns: antimicrobial and wound-healing effects. Expert Rev Anti-Infect Ther 9:857–879. https://doi.org/10.1586/eri.11.59
Diksha, Singh R, Khanna L (2021) Glebionis coronaria (L.) Cass. ex Spach (Asteraceae): a new fabric dye with potential antibacterial properties. J Indian Chem Soc 98:100193. https://doi.org/10.1016/j.jics.2021.100193
Ding X, Wang Y, Xu R, Qi Q, Wang W, Yu D (2019) Layered cotton/rGO/NiWP fabric prepared by electroless plating for excellent electromagnetic shielding performance. Cellulose 26:8209–8223. https://doi.org/10.1007/s10570-019-02669-6
Doan VK, Ly KL, Tran NM-P, Ho TP-T, Ho MH, Dang NT-N, Chang C-C, Nguyen HT-T, Ha PT, Tran QN, Tran LD, Vo TV, Nguyen TH (2021) Characterizations and antibacterial efficacy of chitosan oligomers synthesized by microwave-assisted hydrogen peroxide oxidative depolymerization method for infectious wound applications. Materials 14:4475. https://doi.org/10.3390/ma14164475
Duan P, Xu Q, Zhang X, Chen J, Zheng W, Li L, Yang J, Fu F, Diao H, Liu X (2020) Naturally occurring betaine grafted on cotton fabric for achieving antibacterial and anti-protein adsorption functions. Cellulose 27:6603–6615. https://doi.org/10.1007/s10570-020-03228-0
French AD (2017) Glucose, not cellobiose, is the repeating unit of cellulose and why that is important. Cellulose 24:4605–4609. https://doi.org/10.1007/s10570-017-1450-3
Ganan M, Carrascosa AV, Martínez-Rodríguez AJ (2009) Antimicrobial activity of chitosan against Campylobacter spp. and other microorganisms and its mechanism of action. J Food Prot 72:1735–1738. https://doi.org/10.4315/0362-028X-72.8.1735
Ganewatta MS, Tang C (2015) Controlling macromolecular structures towards effective antimicrobial polymers. Polymer 63:A1–A29. https://doi.org/10.1016/j.polymer.2015.03.007
Gao S, Su J, Wang W, Fu J, Wang H (2021) Highly efficient and durable antibacterial cotton fabrics finished with zwitterionic polysulfobetaine by one-step eco-friendly strategy. Cellulose 28:1139–1152. https://doi.org/10.1007/s10570-020-03542-7
Gu J, Yuan L, Zhang Z, Yang X, Luo J, Gui Z, Chen S (2018) Non-leaching bactericidal cotton fabrics with well-preserved physical properties, no skin irritation and no toxicity. Cellulose 25:5415–5426. https://doi.org/10.1007/s10570-018-1943-8
Hassan MM (2018) Enhanced antimicrobial activity and reduced water absorption of chitosan films graft copolymerized with poly(acryloyloxy)ethyltrimethylammonium chloride. Int J Biol Macromol 118:1685–1695. https://doi.org/10.1016/j.ijbiomac.2018.07.013
Hong KH (2016) Crosslinking phenolic compounds with cotton fabrics using succinic acid to develop functional clothing materials. Fiber Polym 17:705–711. https://doi.org/10.1007/s12221-016-5845-9
Hong S, Choi H, Jo S, Kim M, Lee S, Ahn S, Lee J (2019) Modification of chitosan using hydrogen peroxide and ascorbic acid and its physicochemical properties including water solubility, oil entrapment and in vitro lipase activity. Int J Food Sci Technol 54:2300–2308. https://doi.org/10.1111/ijfs.14146
Hu Q, Wang T, Zhou M, Xue J, Luo Y (2016) In vitro antioxidant-activity evaluation of gallic-acid-grafted chitosan conjugate synthesized by free-radical-induced grafting method. J Agric Food Chem 64:5893–5900. https://doi.org/10.1021/acs.jafc.6b02255
Hussein SS, Ibrahim SS, Toma MA, Alsalhy QF, Drioli E (2020) Novel chemical modification of polyvinyl chloride membrane by free radical graft copolymerization for direct contact membrane distillation (DCMD) application. J Membr Sci 611:118266. https://doi.org/10.1016/j.memsci.2020.118266
Ibrahim HM, Zaghloul S, Hashem M, El-Shafei A (2021) A green approach to improve the antibacterial properties of cellulose based fabrics using Moringa oleifera extract in presence of silver nanoparticles. Cellulose 28:549–564. https://doi.org/10.1007/s10570-020-03518-7
Jia Z, Shen D, Xu W (2001) Synthesis and antibacterial activities of quaternary ammonium salt of chitosan. Carbohydr Res 333:1–6. https://doi.org/10.1016/S0008-6215(01)00112-4
Kapanya A, Somsunan R, Molloy R, Jiranusornkul S, Leewattanapasuk W, Jongpaiboonkit L, Kong Y (2020) Synthesis of polymeric hydrogels incorporating chlorhexidine gluconate as antibacterial wound dressings. J Biomater Sci J Biomater Sci-Polym Ed 31:895–909. https://doi.org/10.1080/09205063.2020.1725862
Kenawy E-R, Abdel-Hay FI, El-Shanshoury AE-RR, El-Newehy MH (2002) Biologically active polymers. V. Synthesis and antimicrobial activity of modified poly(glycidyl methacrylate-co-2-hydroxyethyl methacrylate) derivatives with quaternary ammonium and phosphonium salts. J Polym Sci Pol Chem 40:2384–2393. https://doi.org/10.1002/pola.10325
Khan MZ, Baheti V, Ashraf M, Hussain T, Ali A, Javid A, Rehman A (2018) Development of UV protective, superhydrophobic and antibacterial textiles using ZnO and TiO2 nanoparticles. Fiber Polym 19:1647–1654. https://doi.org/10.1007/s12221-018-7935-3
Khan F, Pham DTN, Oloketuyi SF, Manivasagan P, Oh J, Kim Y-M (2020) Chitosan and their derivatives: antibiofilm drugs against pathogenic bacteria. Colloid Surf B-Biointerfaces 185:110627. https://doi.org/10.1016/j.colsurfb.2019.110627
Kong M, Chen XG, Xing K, Park HJ (2010) Antimicrobial properties of chitosan and mode of action: a state of the art review. Int J Food Microbiol 144:51–63. https://doi.org/10.1016/j.ijfoodmicro.2010.09.012
Kostic MM, Milanovic JZ, Baljak MV, Mihajlovski K, Kramar AD (2014) Preparation and characterization of silver-loaded hemp fibers with antimicrobial activity. Fiber Polym 15:57–64. https://doi.org/10.1007/s12221-014-0057-7
Kritchenkov AS, Kurasova MN, Godzishevskaya AA, Mitrofanova ES, Egorov AR, Yagafarov NZ, Ballesteros Meza MJ, Tskhovrebov AG, Artemjev AA, Andrusenko EV, Khrustalev VN (2021) High antibacterial activity and low toxicity of pyridoxal derivatives of chitosan and their nanoparticles. Mendeleev Commun 31:504–506. https://doi.org/10.1016/j.mencom.2021.07.022
Kumar S, Deepak V, Kumari M, Dutta PK (2016) Antibacterial activity of diisocyanate-modified chitosan for biomedical applications. Int J Biol Macromol 84:349–353. https://doi.org/10.1016/j.ijbiomac.2015.12.027
Kumar D, Gihar S, Shrivash MK, Kumar P, Kundu PP (2020) A review on the synthesis of graft copolymers of chitosan and their potential applications. Int J Biol Macromol 163:2097–2112. https://doi.org/10.1016/j.ijbiomac.2020.09.060
Le CV, Ly NG, Postle R (1995) Heat and moisture transfer in textile assemblies: part I: steaming of wool, cotton, nylon, and polyester fabric beds. Text Res J 65:203–212. https://doi.org/10.1177/004051759506500403
Li J, Zhuang S (2020) Antibacterial activity of chitosan and its derivatives and their interaction mechanism with bacteria: current state and perspectives. Eur Polym J 138:109984. https://doi.org/10.1016/j.eurpolymj.2020.109984
Li Z, Yang F, Yang R (2015) Synthesis and characterization of chitosan derivatives with dual-antibacterial functional groups. Int J Biol Macromol 75:378–387. https://doi.org/10.1016/j.ijbiomac.2015.01.056
Li J, Zhao L, Wu Y, Rajoka MSR (2019) Insights on the ultra high antibacterial activity of positionally substituted 2′-O-hydroxypropyl trimethyl ammonium chloride chitosan: a joint interaction of -NH2 and -N+(CH3)3 with bacterial cell wall. Colloid Surf B-Biointerfaces 173:429–436. https://doi.org/10.1016/j.colsurfb.2018.09.077
Li J, Fang T, Yan W, Zhang F, Xu Y, Du Z (2020) Structure and properties of oxidized chitosan grafted cashmere fiber by amide covalent modification. Molecules 25:3812. https://doi.org/10.3390/molecules25173812
Li L, Yu P, Li Y, Wu X, Li W, Cheng X (2021) A facile approach to fabricating antibacterial textile with high efficiency and compact process. Adv Mater Interfaces 8:2101197. https://doi.org/10.1002/admi.202101197
Liu J, Wen X, Lu J, Kan J, Jin C (2014) Free radical mediated grafting of chitosan with caffeic and ferulic acids: structures and antioxidant activity. Int J Biol Macromol 65:97–106. https://doi.org/10.1016/j.ijbiomac.2014.01.021
Liu J, Pu H, Chen C, Liu Y, Bai R, Kan J, Jin C (2018) Reaction mechanisms and structural and physicochemical properties of caffeic acid grafted chitosan synthesized in ascorbic acid and hydroxyl peroxide redox system. J Agric Food Chem 66:279–289. https://doi.org/10.1021/acs.jafc.7b05135
Liu Y, Qiao M, Lv C, Ren X, Buschle-Diller G, Huang T-S (2020) N-halamine polyelectrolytes used for preparation of antibacterial polypropylene nonwoven fabrics and study on their basal cytotoxicity and mutagenicity. Int J Polym Mater Polym Biomat 69:971–978. https://doi.org/10.1080/00914037.2019.1636250
Mohamed NA, Abd El-Ghany NA (2019) Synthesis, characterization and antimicrobial activity of novel aminosalicylhydrazide cross linked chitosan modified with multi-walled carbon nanotubes. Cellulose 26:1141–1156. https://doi.org/10.1007/s10570-018-2096-5
Mohammed H, Sukumar N (2021) Water penetration and abrasion resistance of functional nonwoven fabrics produced using recycled cotton and acrylic fibers. J Nat Fibers. https://doi.org/10.1080/15440478.2021.1993476
Moreno-Vásquez MJ, Valenzuela-Buitimea EL, Plascencia-Jatomea M, Encinas-Encinas JC, Rodríguez-Félix F, Sánchez-Valdes S, Rosas-Burgos EC, Ocaño-Higuera VM, Graciano-Verdugo AZ (2017) Functionalization of chitosan by a free radical reaction: characterization, antioxidant and antibacterial potential. Carbohydr Polym 155:117–127. https://doi.org/10.1016/j.carbpol.2016.08.056
Motaghi Z (2018) An economical dyeing process for cotton and wool fabrics and improvement their antibacterial properties and UV protection. J Nat Fibers 15:777–788. https://doi.org/10.1080/15440478.2017.1364204
Munir MU, Ashraf M, Abid HA, Javid A, Riaz S, Khanzada H, Rehman A, Iqbal K (2022) Coating of modified ZnO nanoparticles on cotton fabrics for enhanced functional characteristics. J Coat Technol Res 19:467–475. https://doi.org/10.1007/s11998-021-00533-6
Negm NA, Hefni HHH, Abd-Elaal AAA, Badr EA, Abou Kana MTH (2020) Advancement on modification of chitosan biopolymer and its potential applications. Int J Biol Macromol 152:681–702. https://doi.org/10.1016/j.ijbiomac.2020.02.196
Nosheen A, Hussain MT, Khalid M, Javid A, Aziz H, Iqbal S, Ashraf M, Ali S (2022) Development of protective cotton textiles against biohazards and harmful UV radiation using eco-friendly novel fiber-reactive bioactive agent. Process Saf Environ Protect 165:431–444. https://doi.org/10.1016/j.psep.2022.07.035
Peng Y, Han B, Liu W, Xu X (2005) Preparation and antimicrobial activity of hydroxypropyl chitosan. Carbohydr Res 340:1846–1851. https://doi.org/10.1016/j.carres.2005.05.009
Rabea EI, Badawy ME-T, Stevens CV, Smagghe G, Steurbaut W (2003) Chitosan as antimicrobial agent: applications and mode of action. Biomacromol 4:1457–1465. https://doi.org/10.1021/bm034130m
Riaz S, Ashraf M, Hussain T, Hussain MT (2019) Modification of silica nanoparticles to develop highly durable superhydrophobic and antibacterial cotton fabrics. Cellulose 26:5159–5175. https://doi.org/10.1007/s10570-019-02440-x
Riaz S, Ashraf M, Aziz H, Younus A, Umair M, Salam A, Iqbal K, Hussain MT, Hussain T (2022) Cationization of TiO2 nanoparticles to develop highly durable multifunctional cotton fabric. Mater Chem Phys 278:125573. https://doi.org/10.1016/j.matchemphys.2021.125573
Sadeghi-Kiakhani M, Tehrani-Bagha AR, Safapour S (2018) Enhanced anti-microbial, anti-creasing and dye absorption properties of cotton fabric treated with chitosan-cyanuric chloride hybrid. Cellulose 25:883–893. https://doi.org/10.1007/s10570-017-1591-4
Sahariah P, Másson M (2017) Antimicrobial chitosan and chitosan derivatives: a review of the structure-activity relationship. Biomacromolcules 18:3846–3868. https://doi.org/10.1021/acs.biomac.7b01058
Sun L, Du Y, Fan L, Chen X, Yang J (2006) Preparation, characterization and antimicrobial activity of quaternized carboxymethyl chitosan and application as pulp-cap. Polymer 47:1796–1804. https://doi.org/10.1016/j.polymer.2006.01.073
Valle JAB, de Cássia Siqueira R, Valle C, Bierhalz ACK, Bezerra FM, Hernandez AL, Lis Arias MJ (2021) Chitosan microcapsules: methods of the production and use in the textile finishing. J Appl Polym Sci 138:50482. https://doi.org/10.1002/app.50482
Verma M, Gahlot N, Singh SSJ, Rose NM (2021) UV protection and antibacterial treatment of cellulosic fibre (cotton) using chitosan and onion skin dye. Carbohydr Polym 257:117612. https://doi.org/10.1016/j.carbpol.2020.117612
Wang Y, Xie M, Ma G, Fang Y, Yang W, Ma N, Fang D, Hu Q, Pei F (2019) The antioxidant and antimicrobial activities of different phenolic acids grafted onto chitosan. Carbohydr Polym 225:115238. https://doi.org/10.1016/j.carbpol.2019.115238
Xiao M, Guo Y, Zhang J, Liu Y, Ren Y, Liu X (2021) Diethylene triamine penta methylene phosphonic acid encountered silver ions: a convenient method for preparation of flame retardant and antibacterial lyocell fabric. Cellulose 28:7465–7481. https://doi.org/10.1007/s10570-021-04000-8
Xin Y, Zhao H, Xu J, Xie Z, Li G, Gan Z, Wang X (2020) Borneol-modified chitosan: antimicrobial adhesion properties and application in skin flora protection. Carbohydr Polym 228:115378. https://doi.org/10.1016/j.carbpol.2019.115378
Yan X, Zhu X, Ruan Y, Xing T, Chen G, Zhou C (2020) Biomimetic, dopamine-modified superhydrophobic cotton fabric for oil–water separation. Cellulose 27:7873–7885. https://doi.org/10.1007/s10570-020-03336-x
Yang T-C, Chou C-C, Li C-F (2005) Antibacterial activity of N-alkylated disaccharide chitosan derivatives. Int J Food Microbiol 97:237–245. https://doi.org/10.1016/S0168-1605(03)00083-7
Yılmaz F, Bahtiyari Mİ (2020a) Antibacterial finishing of cotton fabrics by dyeing with olive tree leaves fallen during olive harvesting. J Clean Prod 270:122068. https://doi.org/10.1016/j.jclepro.2020.122068
Yılmaz F, Bahtiyari Mİ (2020b) Use of tea and tobacco industrial wastes in dyeing and antibacterial finishing of cotton fabrics. AATCC J Res 7:25–31. https://doi.org/10.14504/ajr.7.5.4
Yılmaz F, Koçak ÖF, Özgeriş FB, Şapçı Selamoğlu H, Vural C, Benli H, Bahtiyari Mİ (2020) Use of Viburnum Opulus L. (Caprifoliaceae) in dyeing and antibacterial finishing of cotton. J Nat Fibers 17:1081–1088. https://doi.org/10.1080/15440478.2019.1691118
Yin M, Li X, Liu Y, Ren X (2021) Functional chitosan/glycidyl methacrylate-based cryogels for efficient removal of cationic and anionic dyes and antibacterial applications. Carbohydr Polym 266:118129. https://doi.org/10.1016/j.carbpol.2021.118129
Yu W, Li X, He J, Chen Y, Qi L, Yuan P, Ou K, Liu F, Zhou Y, Qin X (2021) Graphene oxide-silver nanocomposites embedded nanofiber core-spun yarns for durable antibacterial textiles. J Colloid Interface Sci 584:164–173. https://doi.org/10.1016/j.jcis.2020.09.092
Yue L, Wang M, Khan IM, Niazi S, Wang B, Ma X, Wang Z, Xia W (2021) Preparation and characterization of chitosan oligosaccharide derivatives containing cinnamyl moieties with enhanced antibacterial activities. LWT 147:111663. https://doi.org/10.1016/j.lwt.2021.111663
Zeng A, Wang Y, Li D, Guo J, Chen Q (2021) Preparation and antibacterial properties of polycaprolactone/quaternized chitosan blends. Chin J Chem Eng 32:462–471. https://doi.org/10.1016/j.cjche.2020.10.001
Zheng J, Xiao N, Li Y, Xie X, Li L (2022) Free radical grafting of whey protein isolate with tea polyphenol: synthesis and changes in structural and functional properties. LWT 153:112438. https://doi.org/10.1016/j.lwt.2021.112438
Zhou J, Hu X, Zhu Y, Lyu H, Zhang L, Fu F, Liu X (2019) A hybrid binder of carboxymethyl chitosan and l-methionine enables a slight amount of Ag NPs to be durably effective on antibacterial cotton fabrics. Cellulose 26:9323–9333. https://doi.org/10.1007/s10570-019-02715-3
Zhou C, Ao H-Y, Han X, Jiang W-W, Yang Z-F, Ma L, Deng X-Y, Wan Y-Z (2021) Engineering a novel antibacterial agent with multifunction: protocatechuic acid-grafted-quaternized chitosan. Carbohydr Polym 258:117683. https://doi.org/10.1016/j.carbpol.2021.117683
Acknowledgments
The Authors would like to express their sincere gratitude to China National Key R&D Program (2019YFC0408400).
Funding
This work was supported by China National Key R&D Program (2019YFC0408400).
Author information
Authors and Affiliations
Contributions
Reviewing and Editing: HZ, YH, F.L.; Conceptualization, Writing-Original draft preparation and Methodology: S Supervision and Funding: Baoming Zhou.
Corresponding author
Ethics declarations
Conflict of interests
The authors have no relevant financial or non-financial interests to disclose.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhang, H., He, S., Hu, Y. et al. Preparation of chitosan based antibacterial agent CS-g-DMC and its long-effective antibacterial finishing for cotton fabric. Cellulose 30, 7373–7388 (2023). https://doi.org/10.1007/s10570-023-05214-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-023-05214-8