纺织学报 ›› 2025, Vol. 46 ›› Issue (04): 255-263.doi: 10.13475/j.fzxb.20240805502

• 综合述评 • 上一篇    下一篇

卤胺抗菌剂及其改性纤维的应用研究进展

郭洁琰, 徐颖雯, 丁放, 任学宏()   

  1. 武汉纺织大学 纺织科学与工程学院, 湖北 武汉 430200
  • 收稿日期:2024-08-28 修回日期:2025-02-07 出版日期:2025-04-15 发布日期:2025-06-11
  • 通讯作者: 任学宏(1971—),男,教授,博士。主要研究方向为抗菌纺织品和高分子材料。E-mail:xuehongr@hotmail.com
  • 作者简介:郭洁琰(2000—),女,硕士生。主要研究方向为纺织品抗菌整理。
  • 基金资助:
    湖北省中央引导地方科技发展专项(2022BGE253)

Research progress in the applications of N-halamine antibacterial agents and their modified fibers

GUO Jieyan, XU Yingwen, DING Fang, REN Xuehong()   

  1. College of Textile Science and Engineering, Wuhan Textile University, Wuhan, Hubei 430200, China
  • Received:2024-08-28 Revised:2025-02-07 Published:2025-04-15 Online:2025-06-11

摘要:

为拓展和促进卤胺抗菌材料在不同领域的应用,综述了近年来卤胺改性纤维与纺织品的研究进展。简要介绍了卤胺抗菌剂的结构、特点及抗菌机制。卤胺的结构根据卤素原子的不同,可分为氯胺、溴胺和碘胺3类;根据分子结构的不同,可分为胺类、酰胺类和亚酰胺类。卤胺抗菌剂可通过接触杀菌、释放杀菌和转移杀菌3种方式使微生物死亡。同时,详细综述了卤胺抗菌剂的制备方法,分别是表面改性技术和共混改性技术。阐述了卤胺抗菌剂在抗菌纺织品、水处理、医用材料、食品包装和空气过滤领域的应用。最后,对卤胺抗菌剂存在的问题进行了分析,并对其未来发展趋势进行了展望。

关键词: 卤胺化合物, 杀菌, 改性, 抗菌机制, 功能纤维, 功能纺织品

Abstract:

Significance Microorganisms such as bacteria, fungi and viruses can grow rapidly on fibrous carriers under suitable temperature and humidity conditions, which not only shortens the service life of textile materials, but also poses a fatal threat to human health. Therefore, the development of textile materials with effective antibacterial properties is crucial for public safety. Antibacterial textiles can effectively inhibit the growth of microorganisms and protect human health by reducing the risk of disease caused by pathogenic virus transmission. Several types of antibacterial agents have been developed, such as quaternary ammonium salts, chitosan, polyguanidine, metal ions/compounds and N-halamine compounds. Among these, N-halamine antibacterial agents have been widely used due to their excellent efficacy, broad-spectrum, long-lasting antibacterial properties as well as unique regenerability. The halogens in the N-X bond (X representing Cl, Br, I) in the N-halamine compounds can release bactericidal ions with oxidising properties to kill microorganisms.

Progress Herein, the structure, characteristics and antibacterial mechanism of N-halamine antibacterial agents were briefly described. N-halamine antibacterial agents are compounds that contain N-X covalent bonds in their structure, which are oxidised from N-H bonds by sodium hypochlorite and then endowed with antibacterial effect. The structure of N-halamine amines can be divided into chloramines, bromamines and iodamines according to the different halogen atoms, and divided into amines, amides and imides according to the different nitrogen compounds, respectively. The inactivation mechanism of N-halamine antibacterial agents can be classified into contact killing, release killing and transfer killing. Meanwhile, the preparation of N-halamine antibacterial materials were reviewed, which was based on the surface modification technology and co-modification technology, respectively. The surface modification technology included pad-dry-cure, grafting and coating, and the co-modification technology included electrostatic spinning, sol-gel and 3D printing technology. N-halamine compounds can be applied to various substrates through chemical modification and N-halamine antibacterial agents are under rapid development and are widely used in a variety of applications. The applications of N-halamine antibacterial materials in the fields of antibacterial textiles, water treatment, medical materials, food packaging and air filtration were described, with the prospect of further applications in the future.

Conclusion and Prospect With the growing concern for public health and the environment, the demand for antibacterial agents and safe materials is increasing. N-halamine antibacterial agents have been widely used due to their good stability, remarkable regenerability, broad-spectrum and efficient antibacterial properties, which play an important role in promoting the development of antibacterial materials. However, the N—Cl bonds in N-halamine compounds are tend to degradation under UV light, which can lead to problems such as aging and degradation of antibacterial materials. N-halamine antibacterials contain chemicals that may pose toxicity risks if used in excess, which may also have a negative impact on the ecosystem. The manufacturing process of antibacterial agents is also complicated and costly. Therefore, the research and development of new N-halamine antibacterial agents that are friendly to the environment and human body and have good compatibility with materials, is one of the directions for future development of N-halamine antibacterial agents. At present, the development of N-halamine antibacterial agents is still in progress, and its in-depth study is of great significance.

Key words: N-halamine, antibacterial, modification, antibacterial mechanism, functional fiber, functional textile

中图分类号: 

  • TS195.2

图1

卤胺化合物的杀菌及再生过程"

图2

卤胺化合物的杀菌机制"

[1] 刘畅, 石荣金, 韩璐怡, 等. 卤胺抗菌材料的研究进展[J]. 印染, 2023, 49(6): 74-81.
LIU Chang, SHI Rongjin, HAN Luyi, et al. Research progress of N-halamine antibacterial materials[J]. China Dyeing & Finishing, 2023, 49(6): 74-81.
[2] 计烨, 杨建军, 吴庆云, 等. 卤胺类抗菌材料的现状及进展[J]. 塑料, 2024, 53(3): 131-136, 142.
JI Ye, YANG Jianjun, WU Qingyun, et al. Current status and progress of haloamine antibacterial materials[J]. Plastics, 2024, 53(3): 131-136, 142.
[3] MORANDINI A, SPADATI E, LEONETTI B, et al. Sustainable triazine-derived quaternary ammonium salts as antibacterial agents[J]. RSC Advances, 2021, 11(45): 28092-28096.
[4] ARDEAN C, DAVIDESCU C M, NEMEŞ N S, et al. Factors influencing the antibacterial activity of chitosan and chitosan modified by functionalization[J]. International Journal of Molecular Sciences, 2021, 22(14): 1-28.
[5] NGUYEN D T, PHAM L T, LE H T T, et al. Synthesis and antibacterial properties of a novel magnetic nanocomposite prepared from spent pickling liquors and polyguanidine[J]. RSC Advances, 2018, 8(35): 19707-19712.
[6] HUANG X, WANG D R, HU L Y, et al. Preparation of a novel antibacterial coating precursor and its antibacterial mechanism[J]. Applied Surface Science, 2018, 465: 478-485.
[7] DING F, ZHANG S M, REN X H, et al. Development of pet fabrics containing n-halamine compounds with durable antibacterial property[J]. Fibers and Polymers, 2022, 23(2): 413-422.
[8] BU D L, ZHOU Y, YANG C, et al. Preparation of quaternarized N-halamine-grafted graphene oxide nanocomposites and synergetic antibacterial proper-ties[J]. Chinese Chemical Letters, 2021, 32(11): 3509-3513.
[9] DONG A, WANG Y J, GAO Y, et al. Chemical insights into antibacterial N-halamines[J]. Chemical Reviews, 2017, 117(6): 4806-4862.
doi: 10.1021/acs.chemrev.6b00687 pmid: 28252944
[10] 夏金兰, 王春, 刘新星. 抗菌剂及其抗菌机理[J]. 中南大学学报(自然科学版), 2004, 35(1): 31-38.
XIA Jinlan, WANG Chun, LIU Xinxing. Research on antibacterial agents and their mechanisms of actions[J]. Journal of Central South University (Natural Science), 2004, 35(1): 31-38.
[11] 马维. 基于纳米ZnO/卤胺抗菌复合材料的构筑及应用研究[D]. 无锡: 江南大学, 2020: 60-86.
MA Wei. Construction and application of antibacterial composites based on ZnO nanoparticles/N-halamine[D]. Wuxi: Jiangnan University, 2020: 60-86.
[12] SUN Y Y, SUN G. Durable and refreshable polymeric N-halamine biocides containing 3-(4'-vinylbenzyl)-5,5-dimethylhydantoin[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2001, 39: 3348-3355.
[13] LUO J, CHEN Z B, SUN Y Y. Controlling biofilm formation with an N-halamine-based polymeric additive[J]. Journal of Biomedical Materials Research Part A, 2006, 77A(4): 823-831.
[14] LI C H, XUE L Y, CAI Q, et al. Design, synthesis and biocidal effect of novel amine N-halamine microspheres based on 2,2,6,6-tetramethyl-4-piperidinol as promising antibacterial agents†[J]. RSC Advances, 2014, 4: 47853-47864.
[15] CAO Z B, SUN Y Y. N-halamine-based chitosan: preparation, characterization, and antibacterial function[J]. Journal of Biomedical Materials Research Part A, 2008, 85A(1): 99-107.
[16] AHMED A E-S I, HAY J N, BUSHELL M E, et al. Biocidal polymers (II): determination of biological activity of novel N-halamine biocidal polymers and evaluation for use in water filters[J]. Reactive & Functional Polymers, 2008, 68(10): 1448-1458.
[17] 刘桂芝, 王英沣, 殷茂力. 季铵/卤胺化壳聚糖对棉织物的抗菌整理研究[J]. 棉纺织技术, 2023, 51(6): 68-72.
LIU Guizhi, WANG Yingfeng, YIN Maoli. Study on antibacterial finishing of cotton fabric treated by quaternarized/N-halamine chitosan[J]. Cotton Textile Technology, 2023, 51(6): 68-72.
[18] 孙萍, 张淑敏, 刘颖, 等. 亚麻织物的新型卤胺抗菌整理[J]. 印染, 2022, 48(3): 21-25.
SUN Ping, ZHANG Shumin, LIU Ying, et al. Antibacterial finish of linen fabrics with new N-halamine agent[J]. China Dyeing & Finishing, 2022, 48(3): 21-25.
[19] PENG P P, ZHANG Z W, YANG J J, et al. Grafted antibacterial cotton fabrics with N-halamine groups via atom transfer radical polymerization[J]. Cellulose, 2021, 28(13): 8855-8866.
[20] MA Y, HUANG C, ZHANG Z, et al. Controlled surface radical graft polymerization of n-halamine monomers on polyester fabrics and potential application in bioprotective medical scrubs[J]. ACS Applied Polymer Materials, 2022, 4(9): 6760-6769.
[21] WAN J S, LI H, CAI X Y, et al. Developing the functional cotton fabric with N-halamine antibacterial structure based on DA/PEI[J]. Cellulose, 2022, 29(18): 9953-9967.
[22] WANG Y F, YIN M L, MA W, et al. N-halamine modified mesoporous silica coated cotton as multipurpose protective fibrous materials[J]. Cellulose, 2020, 27: 10461-10471.
[23] LUO H, YIN X Q, TAN P F, et al. Engineering an antibacterial nanofibrous membrane containing N-Halamine for recyclable wound dressing application[J]. Materials Today Communications, 2020. DOI: 10.1016/j.mtcomm.2020.100898.
[24] QU H H, WANG C, GUO Y X, et al. Electrospun N-halamine/ZnO-based platform eradicates bacteria through multimodal antibacterial mechanism of action[J]. Rare Metals, 2023, 42(1): 222-233.
[25] MA W, LI J, LIU Y, et al. Preparation and characterization of excellent antibacterial TiO2/N-halamines nanoparticles[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2016, 506: 284-290.
[26] LIU C, SHAN H R, CHEN X X, et al. Novel inorganic-based N-halamine nanofibrous membranes as highly effective antibacterial agent for water disin-fection[J]. ACS Applied Materials & Interfaces, 2018, 10(51): 44209-44215.
[27] YANG Z M, REN X H, LIU Y. N-halamine modified ceria nanoparticles: antibacterial response and accelerated wound healing application via a 3D printed scaffold[J]. Composites Part B: Engineering, 2021. DOI: 10.1016/j.compositesb.2021.109390.
[28] YANG Z M, REN X H, LIU Y. Multifunctional 3D printed porous GelMA/xanthan gum based dressing with biofilm control and wound healing activity[J]. Materials Science & Engineering C, 2021. DOI: 10.1016/j.msec.2021.112493.
[29] 王舒. 卤胺抗菌剂的制备及其在纺织品上的应用研究[D]. 深圳: 深圳大学, 2020: 5-10.
WANG Shu. Preparation of N-halamine antibacterial agent and its application on textiles[D]. Shenzhen: Shenzhen University, 2020: 5-10.
[30] TANG X, ZHANG Z X, JING L X, et al. Synthesis and antibacterial activity of Schiff base-pyridine quaternary ammonium salt-halamine compounds on cotton fabrics[J]. Cellulose, 2023, 30(16): 10519-10531.
[31] LI H Y, WEN D J, WANG S J, et al. Durable multifunctional cotton fabric with superior biocidal efficacy and flame retardancy based on an ammonium phosphate N-halamine[J]. International Journal of Biological Macromolecules, 2023. DOI: 10.1016/j.ijbiomac.2023.126812.
[32] 马宗敏, 闫子硕, 斯阳, 等. 水消毒用卤胺改性EVOH纳米纤维膜的制备及性能表征[J]. 产业用纺织品, 2022, 40 (4): 7-12.
MA Zongmin, YAN Zishuo, SI Yang, et al. Preparation and characterization of N-halamine-modified EVOH nanofibrous membranes for water disinfection[J]. Technical Textiles, 2022, 40 (4): 7-12.
[33] NAHHAL I M E, AQAD M A, KODEH F S, et al. N-Halamine-modified mesoporous silica for water disinfection[J]. Materials Chemistry and Physics, 2023. DOI: 10.1016/j.matchemphys.2022.126936.
[34] MA Y, WISUTHIPHAET N, NITIN N, et al. A novel N-halamine biocidal nanofibrous membrane for chlorine rechargeable rapid water disinfection applications[J]. ACS Applied Materials & Interfaces, 2021, 13(34): 41056-41065.
[35] ZHANG Y, YIN M L, LI L, et al. Construction of aerogels based on nanocrystalline cellulose and chitosan for high efficient oil/water separation and water disinfection[J]. Carbohydrate Polymers, 2020. DOI: 10.1016/j.carbpol.2020.116461.
[36] 熊坦平, 谭飞, 黄成, 等. 氯胺接枝涤纶/锦纶超细纤维针织物的抗菌性能[J]. 纺织学报, 2022, 43(8): 101-106.
XIONG Tanping, TAN Fei, HUANG Cheng, et al. Antibacterial properties of chloramine-grafted polyester/ppolyamide microfibre knitted fabrics[J]. Journal of Textile Research, 2022, 43 (8): 101-106.
[37] CHEN W J, ZHU Y N, ZHANG Z, et al. Engineering a multifunctional N-halamine-based antibacterial hydrogel using a super-convenient strategy for infected skin defect therapy[J]. Chemical Engineering Journal, 2020. DOI: 10.1016/j.cej.2019.122238.
[38] WANG Z M, TANG Y C, WANG P, et al. Dynamical integration of antibacterial, anti-inflammatory, and pro-osteogenic activities on polyetheretherketone via a porous N-halamine polymeric coating[J]. Advanced Functional Materials, 2023. DOI: 10.1002/adfm.202307286.
[39] MA W, LI L, LIN X H, et al. Novel ZnO/N-halamine-mediated multifunctional dressings as quick antibacterial agent for biomedical applications[J]. ACS Applied Materials & Interfaces, 2019, 11(34): 31411-31420.
[40] 范晓燕, 刘颖, 潘能宇, 等. 应用电子束辐射技术的抗菌改性聚酯纳米纤维膜[J]. 纺织学报, 2017, 38(6): 157-162.
FAN Xiaoyan, LIU Ying, PAN Nengyu, et al. Antibacterial modification of polyester nanofibrous membranes by electron beam irradiation technique[J]. Journal of Textile Research, 2017, 38 (6): 157-162.
[41] SHI Y Q, HE Y J, LIU J R, et al. High-efficacy antibacterial acyclic N-halamine-grafted polyvinyl alcohol film[J]. Polymer Bulletin, 2022, 80(11): 11845-11859.
[42] ZHANG G Q, ZHANG Y L, ZHENG K C, et al. Durable and biocompatible antibacterial N-halamine membranes based on cellulose carbamate[J]. Industrial Crops and Products, 2022. DOI: 10.1016/j.indcrop.2022.115518.
[43] ZHANG L, LI L F, WANG L C, et al. Multilayer electrospun nanofibrous membranes with antibacterial property for air filtration[J]. Applied Surface Science, 2020. DOI: 10.1016/j.apsusc.2020.145962.
[44] WANG F, SI Y, YU J Y, et al. Tailoring nanonets-engineered superflexible nanofibrous aerogels with hierarchical cage-like architecture enables renewable antibacterial air filtration[J]. Advanced Functional Materials, 2021. DOI: 10.1002/adfm.202107223.
[45] SHAO W L, LI J L, ZHANG Y T, et al. Polyvinylidene fluoride multi-scale nanofibrous membrane modified using N-halamine with high filtration efficiency and durable antibacterial properties for air filtration[J]. Journal of Colloid and Interface Science, 2022, 628: 627-636.
doi: 10.1016/j.jcis.2022.08.077 pmid: 36027773
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