Antimicrobial N-halamine Research Articles

Antimicrobial N-Halamine incorporated Poly(Vinyl alcohol-co-ethylene) films for reducing cross-contamination of fresh produce

Cross-contamination of fresh produce can lead to nationwide foodborne outbreaks. Despite using current sanitation practices, several studies have shown that reusable plastic containers used during the harvest and postharvest processing can be contaminated with pathogenic bacteria. These contaminated surfaces of plastic containers can lead to cross-contamination of fresh produce. The overall objective of this study was to develop a rechargeable antimicrobial plastic film that could be used to reduce cross-contamination of fresh produce in a dynamic postharvest processing environment. An N-halamine precursor incorporated poly(vinyl alcohol-co-ethylene) film was used to charge chlorine via immersion in a dilute bleach to achieve a chlorine-charged plastic film. Cross-contamination was simulated using baby spinach inoculated with 5-log CFU cm−2Listeria innocua to contact a non-contaminated film, which was then contacted by another non-contaminated leaf at different contact times (5–1200 s) and applied forces (1 and 9.8 N). Bacteria on different surfaces were quantified, and quality attributes of leaves such as color, texture, and total phenolic content were measured. The active chlorine content in the charged plastic films reached 445.8 ± 7.2 nmol cm−2 after 1 h chlorination in a 10% diluted bleach solution and remained constant for at least 3 recharging cycles. The self-cleaning activity of the charged plastic films was demonstrated (>2 log reduction of inoculated bacteria) after a 20-min contact and reduced approximately 2 logs of inoculated L. innocua on leaves. The charged plastic films were also effective for reducing cross-contamination of leaves, preventing bacterial transfer from contaminated leaves to non-contaminated leaves without causing a significant quality loss. Thus, the antimicrobial plastic films used in this study can effectively reduce cross-contamination of leafy greens and be potentially used as a liner material or moldable plastic for reusable containers during harvesting and postharvest processing.

Mechanically Robust and Transparent N-Halamine Grafted PVA-co-PE Films with Renewable Antimicrobial Activity.

Antimicrobial polymeric films that are both mechanically robust and function renewable would have broad technological implications for areas ranging from medical safety and bioengineering to foods industry; however, creating such materials has proven extremely challenging. Here, a novel strategy is reported to create high-strength N-halamine incorporated poly(vinyl alcohol-co-ethylene) films (HAF films) with renewable antimicrobial activity by combining melt radical graft polymerization and reactive extrusion technique. The approach allows here the intrinsically rechargeable N-halamine moieties to be covalently incorporated into polymeric films with high biocidal activity and durability. The resulting HAF films exhibit integrated properties of robust mechanical strength, high transparency, rechargeable chlorination capability (>300 ppm), and long-term durability, which can effectively offer 3-5 logs CFU reduction against typical pathogenic bacterium Escherichia coli within a short contact time of 1 h, even at high organism conditions. The successful synthesis of HAF films also provides a versatile platform for exploring the applications of antimicrobial N-halamine moieties in a self-supporting, structurally adaptive, and function renewable form.

Antimicrobial N-halamine modified polyethylene: characterization, biocidal efficacy, regeneration, and stability.

Development of antimicrobial materials that regenerate antimicrobial activity represents a novel technology in preventing microbial cross-contamination. We report a method for the application of regenerably antimicrobial N-halamines onto the surface of polyethylene (PE) materials through layer-by-layer (LbL) assembly of polyethyleneimine and poly(acrylic acid). A total of 5, 10, 15, and 20 bilayers were applied. Modified PE had from 49.3 to 293.5 nmol cm(-2) antimicrobial N-halamines from 5 to 20 bilayers after 10 min of chlorination. Each variant of N-halamine modified PE was able to reduce by >5 logarithmic cycles Listeria monocytogenes. The stability of N-halamine modified PE was characterized after extended exposure to chlorine, acidic solutions, and an alkaline cleaner. After an initial conditioning period, materials generated more than double the quantity of N-halamines present on as prepared materials, retaining regenerability for up to 100 chlorination cycles. After the equivalent of 300 washing cycles by buffers (pH values 3, 5, and 7) or a commercial alkaline detergent, there was no change in the number of antimicrobial N-halamines on the modified materials. These results indicate that the reported LbL deposition technique results in antimicrobial N-halamine materials capable of long-term reuse and exposure to harsh chemicals as expected in a food-processing environment. Such robust, regenerably antimicrobial materials could be an effective technology in the food industry to prevent cross-contamination of pathogenic and spoilage microorganisms. The food contact surface of polyethylene was modified by layer-by-layer deposition of 2 polymers, resulting in a rechargeably antimicrobial surface. Repeated exposure to chlorine regenerated its antimicrobial activity, resulting in greater than 99.999% reduction in Listeria monocytogenes. Materials were stable against repeated washing and exposure to acidic environments. These food contact materials could support current cleaning and sanitization protocols in improving food safety in the processing environment.

Eco-friendly synthesis of regenerable antimicrobial polymeric resin with N-halamine and quaternary ammonium salt groups

An effective macroporous cross-linked antimicrobial polymeric resin containing N-halamine and quaternary ammonium salt moieties was synthesized in an eco-friendly and economical way. Commercially available macroporous crosslinked chloromethylated polystyrene (CMPS) resin reacted with the salt of 5,5-dimethylhydantoin (DMH) and trimethylamine (TMA) in water to produce a polymeric resin containing hydantoinyl and quaternary ammonium salt moieties, poly(p-methylstyrene)-3-(5,5-dimethylhydantoin)-co-trimethyl ammonium chloride (PSHTMA). The hydantoinyl groups in PSHTMA were converted to an antimicrobial N-halamine structure by a facile chlorination reaction in dilute NaOCl solution. The as-synthesized antimicrobial polymeric resin (Cl-PSHTMA) was characterized by FT-IR, X-ray photoelectron spectroscopy, and zeta-potential measurement. The antimicrobial tests showed that the as-synthesized antimicrobial polymeric resin was capable of 7-log inactivation of S. aureus and 8-log inactivation of E. coli within 1 minute contact time. Moreover, the N-halamine moieties in Cl-PSHTMA exhibited excellent regenerability.

Synthesis of novel reactive N-halamine precursors and application in antimicrobial cellulose

2,4,6-Trichloro-s-triazine has been used as one of the important linkers of reactive dyes for textiles such as cellulosic fibers. N-Halamine precursors could be bonded to a triazine-based linker by the chloride displacement reaction, and the synthesized compounds could attach to cotton fabrics by covalent bonds through a reactive dyeing process. In this study, two novel antimicrobial N-halamine precursors, 2,2,6,6-tetramethyl-4-piperidinol-s-trizine (TMPT) and 4-(4-(2,2,6,6-tetramethyl-4-piperidinol)-6-chloro-1,3,5-triazinylamino)-benzenesulfonate (BTMPT), were synthesized and used to coat cotton fabrics. The synthesized s-triazine-based N-halamine precursors react with cellulose to produce biocidal cellulosic fibers upon exposure to diluted household bleach. The coated fabrics were characterized by FT-IR and SEM. The chlorinated treated cotton swatches demonstrated excellent antimicrobial properties against S. aureus (Gram-positive) and E. coli O157:H7 (Gram-negative) with short contact times. Washing test and UVA light test showed that chlorinated BTMPT-coated cotton fabrics were more stable than TMPT-coated cotton fabrics. Compared to the traditional pad-dry-cure technique to produce antimicrobial textiles, the novel process in this study has advantages of saving energy and maintaining tensile strength of fabrics.

AntimicrobialN-Halamine Polymers and Coatings: A Review of Their Synthesis, Characterization, and Applications

Antimicrobial N-halamine polymers and coatings have been studied extensively over the past decade thanks to their numerous qualities such as effectiveness toward a broad spectrum of microorganisms, long-term stability, regenerability, safety to humans and environment and low cost. In this review, recent developments are described by emphasizing the synthesis of polymers and/or coatings having N-halamine moieties. Actually, three main approaches of preparation are given in detail: polymerization, generation by electrochemical route with proteins as monomers and grafting with precursor monomers. Identification and characterization of the formation of the N-halamine bonds (>N-X with X = Cl or Br or I) by physical techniques such as Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and by chemical reactions are described. In order to check the antimicrobial activity of the N-halamine compounds, bacterial tests are also described. Finally, some examples of application of these N-halamines in the water treatment, paints, healthcare equipment, and textile industries are presented and discussed.

Inactivation of Listeria monocytogenes on a polyethylene surface modified by layer-by-layer deposition of the antimicrobial N-halamine

Modification of food contact surfaces to be antimicrobial represents an approach to address the problem of cross-contamination in the food industry. The effect of increasing levels of surface modification on low density polyethylene (LDPE) through application of N-halamines on the inactivation kinetics of Listeria monocytogenes Scott A was evaluated. Increasing levels of modification were applied through layer by layer deposition on LDPE surface (1–5 double layers of polyethyleneimine and poly(acrylic acid)). Surface modification was achieved and confirmed through Fourier Transform Infrared Spectroscopy (FTIR). From 1 to 5 double layers, the N-halamine content ranged from 3.42±1.2 to 27.30±3.5nmolcm−2. More than four logarithmic cycles (>99.99%) reduction was reached against L. monocytogenes Scott A after different contact times depending on the level of modification, that varied from 50 to 110min (from 5 to 2 double layers). Inactivation kinetics followed a sigmoidal behavior.

Mechanism of Photolytic Decomposition of N-Halamine Antimicrobial Siloxane Coatings

Generally, antimicrobial N-halamine siloxane coatings can be rehalogenated repetitively upon loss of their biocidal efficacies, a marked advantage over coatings containing other antimicrobial materials. However, the N-halamine materials tend to slowly decompose upon exposure to ultraviolet irradiation as in direct sunlight. In this work the mechanism of photolytic decomposition for the N-halamine siloxanes has been studied using spectroscopic and theoretical methods. It was found that the N-chlorinated coatings slowly decomposed upon UVA irradiation, whereas the unhalogenated coatings did not. Model compound evidence in this work suggests that upon UVA irradiation, the N-Cl bond dissociates homolytically, followed by a Cl radical migration to the alkyl side chain connected to the siloxane tethering group. An alpha and/or beta scission then occurs causing partial loss of the biocidal moiety from the surface of the coated material, thus precluding complete rechlorination. NMR, FTIR, GCMS, and computations at the DFT (U)B3LYP/6-311++G(2d,p) level of theory have been employed in reaching this conclusion.

Rechargeable Antimicrobial Surface Modification of Polyethylene

Polyethylene films were surface modified, to incorporate amine and amide functionalities, and subsequently were evaluated for their ability to recharge the antimicrobial N-halamine structures after contact with sodium hypochlorite, a common food-approved sanitizer. Surfaces were tested for chlorine retention and release, as well as antimicrobial activity against microorganisms relevant to food quality and food safety, including Escherichia coli K-12, Pseudomonas fluorescens, Bacillus cereus, and Listeria monocytogenes. N-Halamine functionalized polyethylene exhibited chlorine rechargeability, maintaining 5 to 7 nmol/cm2N-halamine structures for six successive charges. The N-halamine functionalized films achieved a 4-log reduction for all organisms tested and maintained a greater than 3-log reduction for four successive uses, suggesting that the modified polyethylene films are capable of providing rechargeable antimicrobial activity. The modified films exhibited antimicrobial activity in aqueous suspensions (P < 0.05) and reduced microbial growth in diluted broth (P < 0.05), suggesting the potential for biocidal action even in the presence of organic matter. Such a rechargeable antimicrobial surface could supplement existing cleaning and sanitation programs in food processing environments to reduce the adhesion, growth, and subsequent cross-contamination of food pathogens, as well as food spoilage organisms.

Novel antimicrobial N-halamine polymer coatings generated by emulsion polymerization

A new class of N-halamine polymers has been synthesized. These polymers can be emulsified in water to produce coatings which, once chlorinated, act as contact disinfectants. The surfaces inactivate bacterial organisms efficiently, requiring relatively brief contact times of several minutes. The latexes can be formed by copolymerization of a N-halamine precursor monomer with other monomers in water with the aid of a surfactant, or by chemically grafting the N-halamine precursor monomer onto an emulsified polymer backbone, followed by chlorination.