季铵盐类抗菌聚合物的研究现状

季铵盐类聚合物（PQACs）是高分子抗菌剂的典型代表。本文介绍了PQACs的两种较为普遍认可的抗菌机理,即“穿透型机理”和“离子交换机理”,指出PQACs有良好的结构稳定性,能重复持久地抗菌,归纳了分子量、取代烷基链长度、抗衡阴离子、间隔长度这四种结构因素对PQACs与细菌间的静电和疏水作用的影响,建立其构效关系。最后展望了PQACs的发展前景,认为应加强其构效关系和应用技术的研究。     

Study on antibacterial behavior of insoluble quaternary ammonium

Insoluble crosslinked polystyrenes (PS) grafted with different quaternary ammonium groups were synthesized as antibacterial agents. Their antibacterial activities against Staphylococcus aureus were investigated by a colony count method. It was found that when the concentration of the insoluble antibacterial agent was low, the antibacterial activity was different from that of the typical soluble antibacterial agent. The antibacterial activity was bacteriostatic rather than bactericidal. A model for explanation of the antibacterial activity of the insoluble ammonium salt was set up. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis and antibacterial activity of copolymers having a quaternary ammonium salt side group

Copolymers with a quaternary ammonium salt side group have been prepared from vinylbenzyl–cetyldimethylammonium chloride and acrylonitrile and their antibacterial activity has been examined with Bacillus subtilis, Staphylococcus aureus, and Escherichia coli. Growth inhibitory effect has been found to increase with the increase in the quaternary ammonium salt concentration in the copolymer. The effect is small on gram-negative bacteria and large on gram-positive bacteria.     

新型吡唑啉衍生物合成与抑菌活性实验研究

根据α,β-不饱和醛酮亲核加成反应原理合成化合物L{[3-(4-N,N-dimethyl-pyenyl)-5-Anthracen-9-yl]-Pyrazoline}和化合物M[3-ferroceny-5-(Anthracen-9-yl)-Pyrazoline]。利用~1H NMR和~(13)C NMR对化合物进行结构表征,通过抑菌实验研究化合物抑菌生物活性。探析新型吡唑啉衍生物对革兰氏阳性菌、革兰氏阴性菌和真菌的抑菌效果,研究其结构变化对活性的影响。结果表明,化合物L和M对典型革兰氏阳性菌和典型革兰氏阴性菌有一定的抑菌效果,对真核细胞型微生物作用不明显。通过比较两者对细菌的作用结果(抑菌圈直径的大小),化合物L的抑菌作用明显强于化合物M,化合物L吡唑啉环连接N、N-二甲基苯环可能增强了抑菌生物活性。     

Development of non-leaching antibacterial coatings through quaternary ammonium salts of styrene based copolymers

Non-leaching antibacterial coatings through quaternary ammonium salts containing polymers were successfully produced in a facile way to provide infection resistant surfaces against multi drug resistant bacteria such as B. licheniformis. In order to do so, a series of random copolymers of styrene (S) and vinyl benzyl chloride (VBC) were synthesized by free radical polymerization technique and subsequently, VBC (V) was functionalized with N,N-dimethylhexadecylamine to introduce quaternary ammonium (QA) salts in the backbone of the copolymers. The copolymers showed an excellent film forming ability, thereby providing an ultrathin coating on various substrates such as metal (stainless steel), glass, polyethylene and polystyrene, as observed by SEM.The coatings were found to be uniform, non leachable in aqueous medium and exhibit good adhesion to various substrates. The antibacterial and antibiofilm activity of the non-leachable coating of random copolymers were screened against B. licheniformis. Among, the copolymer containing 75% quaternized VBC (75VSQA) having 16-C long alkyl chain was found to show maximum antibacterial and antibiofilm activity owing to an appropriate hydrophobic /hydrophilic balance. Their non-leachable antibacterial and antibiofim activity make these coatings suitable for many applications, e.g. marine paints, textile/hospital coatings etc.     

Studies in the development of antibacterial surfactants. I. institutional use of antibacterial fabric softeners

Summary It has been determined that the incorporation of a highly active antibacterial agent, phenylmercuric propionate, into an aqueous solution of a fabric softener of the quaternary ammonium type results in a most effective antibacterial laundry rinse additive. The presence of the quaternary ammonium compound appears to enhance the antibacterial activity of the mercurial. When applied at a level of 63 parts of available mercurial to one million parts of fabric, the treated cloth is rendered bacteriostatic to several strains ofS. aureus and to ammonia-producing organisms of theProteus group, also mildewstatic toChaetomium globosum. The formulated antibacterial softener as well as the treated linens appear to be entirely safe to humans. In longer-term application tests in a hospital laundry the total bacterial load carried by the soiled treated linens is practically zero. There is no excessive build-up of antibacterial agent on fabric upon repeated applications, and it is readily washed out of the fabric by conventional laundering.     

Polymeric phosphonium salts as a novel class of cationic biocides. VII. Synthesis and antibacterial activity of polymeric phosphonium salts and their model compounds containing long alkyl chains

Various polymeric phosphonium salts containing long alkyl chains (C₁₀? C₁₈) and their corresponding model compounds were prepared, which possess the same hydrophobic structure as that of the common disinfectants (quaternary ammonium salts), and their antibacterial activities were evaluated by means of the viable cell counting method against Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative). The polymer with the decyl group exhibited a higher activity than that of the corresponding model compound, particularly against the Gram-positive strain. Furthermore, antibacterial activity of the polymers was found to decrease as the chain length increased. In contrast with the polymers, the antibacterial activity of the corresponding model compounds increased as hydrophobicity of the substituents increased. The antibacterial activity was strongly dependent on the structure, particularly on the length of the alkyl chain. © 1994 John Wiley & Sons, Inc.     

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。     

Polymerized ionic liquids-based hydrogels with intrinsic antibacterial activity: Modern weapons against antibiotic-resistant infections

In this study, the inherent antibacterial activity of 11 different polymerized ionic liquids (PILs)-based hydrogels as well as their corresponding monomers was examined in an extensive screening. The methicillin-resistant Staphylococcus aureus Xen 30 (MRSA Xen 30) and Pseudomonas aeruginosa Xen 5 (P. aeruginosa Xen 5) were chosen as test microorganisms. Both are typical representatives of gram-positive and gram-negative bacteria, respectively. Six of the 11 tested monomers were able to eradicate more than 80% of P. aeruginosa Xen 5 cells in suspension. Unfortunately, the anionic, neutral and zwitterionic representatives lost their function after polymerization. However, the cationic gels retained their antibacterial activity with nearly 100% eradication of selected microorganisms - even at the smallest amount tested. Bactericidal activity against gram-positive MRSA Xen 30 was high when the bacteria were treated with the imidazolium-based monomers. Five of the tested compounds showed rather limited bactericidal activity <50% killed bacteria. The weak antibacterial activities could be significantly increased by crosslinking them to three-dimensional networks. As a result, all the hydrogels possessed strong killing efficiencies of at least 68% and were able to maintain this activity even at low hydrogel volume fractions. These findings are very promising for the development of new antibacterial materials for medical applications, for example, stent coatings.     

生物抗菌用壳聚糖及其金属粒子复合材料研究进展

由细菌、真菌等微生物感染引起的疾病一直是公共卫生中存在的问题，可高效杀死病菌且没有副作用的抗菌材料的开发成为当前研究的热点和重点之一。但微生物对现有抗生素广泛出现耐药性，成为微生物感染治疗的难点。近年来，壳聚糖作为抗菌活性高、生物相容性好和来源广的绿色材料一直备受关注。壳聚糖与Ag、Au和Zn等金属粒子复合后会产生协同抗菌效果，且微生物很难对其产生耐受性，可用于伤口敷料薄膜、敷料抗菌添加剂等领域。该文结合壳聚糖的抗菌性质，总结其抗菌机制和抗菌活性的影响因素，综述了壳聚糖与Ag、Au和Zn等纳米粒子复合后的生物抗菌材料的研究现状，展望此类材料在抗菌领域的发展趋势，为进一步研究生物抗菌材料提供信息支撑。     

季铵盐型抗菌树脂合成及其漆膜的抗菌性能

采用聚合反应合成了一种季铵盐型抗菌树脂,通过漆膜的抑菌圈测试、抗菌率测试以及模拟不同环境对漆膜抗菌效果的影响测试对抗菌树脂的抗菌性能进行了评价,并考察了抗菌树脂漆膜的力学性能。结果表明:季铵盐抗菌剂的含量为6%时,漆膜对金黄色葡萄球菌及大肠杆菌的抗菌率均能达到99%以上。在此含量下,对漆膜的力学性能影响不大,且漆膜具有良好的抵抗恶劣环境的能力,漆膜被擦拭1000次后,其抗菌率仍能达到95%以上,具有良好的抗菌持效性能。     

Preparation of nylon-6/chitosan composites by nanospider technology and their use as candidate for antibacterial agents

Electrospun nylon-6/chitosan (nylon-6/Ch) nanofibers were prepared by nanospider technology. Quaternary ammonium salts as antibacterial agent were immobilized onto electrospun nylon-6/Ch nanofibers via surface modification by soaking the mat in aqueous solution of glycidyltrimethylammonium chloride (GTMAC) at room temperature overnight to give nylon-6/N-[(2-hydroxy-3-trimethylammonium)propyl] chitosan chloride (nylon-6/HTCC). The morphological, structural and thermal properties of the nylon-6/ch nanofibers were studied by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). Biological screening has demonstrated the antibacterial activity of the electrospun nanofibers against Gram negative bacteria, Escherichia coli 35218, and Pseudomonas aeruginosa and Gram positive bacteria, Staphylococcus aureus 24213 among the tested microbes. Thus, the study ascertains the value of the use of electrospun nanofibers, which could be of considerable interest to the development of new antibacterial materials for biomedical applications.     

The synthesis,characterization and antibacterial activity of quaternized poly(2,6-dimethyl-1,4-phenylene oxide)s modified with ammonium and phosphonium salts

A new class of antimicrobial polymers consisting of PPO (polyphenylene oxide) was synthesized, and the antimicrobial activities of these polymers were investigated. This was accomplished by selective α-bromination of PPO (BPPO) followed by quaternization reactions with various tertiary amines or phosphines. Two types of BPPO were prepared, and the antimicrobial activities of the quaternized polymers were tested against Gram-positive bacteria (S. Epidermidis) and Gram-negative bacteria (Escherichia. coli). The triphenylphosphonium-modified polymer showed excellent antibacterial activity against both types of bacteria. Generally, the thermal stability of phosphonium-modified BPPO was superior to that of the ammonium analog, and the increase in the functionalization of the polymer backbone resulted in improved antimicrobial activity.     

Evaluation of the antibacterial activity of cellulose nanofibers/polylactic acid composites coated with ethanolic extract of propolis

This work has focused on developing cellulose nanofibers (CNFs)/polylactic acid (PLA) coated with ethanolic extract of propolis (EEP). First, the chemical composition of EEP was studied in order to determine the major compounds. Composites were then prepared using solvent casting method, with the goal of making green composites. The effectiveness of EEP was evaluated for its antibacterial and antifungal properties, using standard protocol of disc diffusion method (DDM). Chemical analysis of EEP indicated that the propolis samples had high concentrations of the aromatic acids, phenolics, esters, and other derivatives, which are responsible for the antibacterial and antifungal properties of propolis. Experimental results indicated that EEP had a considerable antibacterial activity against most of tested pathogen strains. In general, the surface of modified CNFs/PLA films showed antibacterial activity against Gram‐positive bacteria, even at very low concentrations of EEP. The addition of EEP to the tested films drastically increased the antibacterial effect against Gram‐positive, such as Bacillus anthracis, Staphylococcus aureus , and Salmonella enteric , while there was no effect on Gram‐negative bacteria. Moreover, the results pointed out the inhibitory action of EEP on Candida albicans . POLYM. COMPOS., 38:13–19, 2017. © 2015 Society of Plastics Engineers     

3,5-二溴水杨醛类缩氨基硫脲的合成和抑菌活性研究

设计合成了3种3,5－二溴水杨醛的缩氨基硫脲衍生物,经元素分析,红光谱确证了其结构,并对化合物的抑制活性进行了测试。     

Activity of antibacterial compounds immobilised on montmorillonite

The activities of antibacterial compounds, such as cetylpyridinium (CP), cetyltrimethylammonium (CTA), silver ions and metallic silver, immobilised on montmorillonite (MMT), were tested in Escherichia coli and Enterococcus faecium bacteria. The results of bacterial growth tests were confirmed by determination of the minimum inhibition concentrations (MICs). Unlike CP and CTA, the intercalated silver ions were easily released from MMT by ion-exchange with Na⁺ and acted as very effective antibacterial substances in the long term. Their bactericidal and bacteriostatic effects were determined. Generally, antibacterial compounds are effective when they are released from an inorganic carrier. Metallic silver was prepared by reduction of intercalated Ag⁺ with sodium borohydride. Antibacterial effects of metallic silver were not observed.     

纳米银的抗菌机理研究进展

纳米银因其高效、广谱、不易产生耐药性、安全性高等优点,成为当前抗菌材料的研究热点之一,但目前对纳米银的抗菌机理仍有不同的认识.本文首先综述了国内外纳米银抗菌机理的研究进展和主要成果,主要从影响细菌生活环境、破坏细菌的细胞壁和细胞膜、抑制DNA复制、抑制酶呼吸作用和抑制其他酶活性5个方面分析了纳米银的抗菌机理.并且纳米银的抗菌过程受多种因素影响,文中详细阐述了纳米银的尺寸分布、形貌以及稳定剂、活性氧、菌种和培养基等因素对纳米银抗菌性的影响.最后指出纳米银的抗菌过程复杂,进一步研究其具体作用方式和机理以及影响抗菌作用的主要因素都将有助于纳米银抗菌材料的广泛应用.     

Antimicrobial and Cytotoxic Properties of Bisquaternary Ammonium Bromides of Different Spacer Length

A group of cationic gemini surfactants (bisquaternary ammonium bromides) with different spacer chain lengths (8–6–8, 8–7–8, 8–8–8, 8–9–8) was investigated, paying special attention to antimicrobial and the cytotoxic properties as well as their antimicrobial activity during long‐term storage. It was shown that the compounds investigated exhibit excellent antimicrobial activity against Gram‐positive bacteria (Staphylococcus aureus) and Gram‐negative bacteria (Pseudomonas aeruginosa) as well as antifungal properties (Candida albicans). The gemini surfactants tested had the differential level of cytotoxicity against normal lymphocytes. It was shown that the spacer chain length plays an important role in antibacterial activity and influences the cytotoxicity. The gemini surfactants with shorter spacer chain length, that had higher critical micelle concentration, showed generally weaker antibacterial properties, but on the other hand, these exhibited lower level of cytotoxicity. Furthermore, the aqueous solution of gemini surfactants exhibited the same antimicrobial activity even after 3 months.     

Polymeric phosphonium salts as a novel class of cationic biocides. VIII. Synergistic effect on antibacterial activity of polymeric phosphonium and ammonium salts

Two types of homopolymers {poly[tributyl(4-vinylbenzyl)phosphonium chloride] and poly[tributyl(4-vinylbenzyl)ammonium chloride]} and copolymers, in which the compositional ratio of the phosphonium monomer to the ammonium monomer was altered, were prepared. The antibacterial activities of both the mixtures of the homopolymers in which the mixing ratio was altered and the copolymers containing positively charged phosphorus and nitrogen atoms in a single polymer chain were explored by the viable cell counting method in sterile distilled water. In the mixed system, a significant finding was the presence of an optimal mixing ratio for the antibacterial activity. The mixtures of polymeric phosphonium salt and polymeric ammonium salt clearly showed the synergistic effect on the antibacterial activity. On the other hand, the antibacterial activity of the copolymers with different cationic parts increased monotonously with increasing the phosphonium monomer units in the polymers, namely, the incorporation of two types of active moieties into a single molecule seems to be unfavorable for synergism on the antibacterial activity. © 1994 John Wiley & Sons, Inc.     

Preparation,characterization, and antibacterial activities of quaternarized N‐halamine‐grafted cellulose fibers

A viable method for coating of cellulose fiber with quaternarized N‐halamine is reported in this article. The use of quaternary ammonium salt group in combination with N‐halamine group can reinforce the antibacterial activity. The chemical structure of as‐synthesized N‐halamine precursor 4‐(Bromo‐acetic acid methylester)‐4‐ethyl‐2‐ oxazolidinone (BEO) was characterized by ¹H‐NMR. The cellulose fibers were characterized by Fourier transform infrared spectra and X‐ray photoelectron spectra. The spectra data confirmed that the quaternarized N‐halamine‐grafted cellulose fibers were successfully obtained. The antibacterial properties of functional fibers were challenged with both Gram positive and Gram negative bacteria. The antibacterial tests and showed that the as‐prepared antibacterial cellulose fibers exhibited powerful and rapid bactericidal performance against both Gram negative E. coli and Gram positive S. aureus. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42702.