Polymeric Antimicrobial Coatings Based on Quaternary Ammonium Compounds

Biocidal coatings that are based on quaternized ammonium copolymers were developed after blending and crosslinking and studied as a function of the ratio of reactive groups and the type of biocidal groups, after curing at room temperature or 120 °C. For this purpose, two series of copolymers with complementary reactive groups, poly(4-vinylbenzyl chloride-co-acrylic acid), P(VBC-co-AAx), and poly(sodium 4-styrenesulfonate-co-glycidyl methacrylate), P(SSNa-co-GMAx), were synthesized via free radical copolymerization and further modified resulting in covalently bound (4-vinylbenzyl dimethylhexadecylammonium chloride, VBCHAM) and electrostatically attached (hexadecyltrimethylammonium 4-styrene sulfonate, SSAmC16) units. The crosslinking reaction between the carboxylic group of acrylic acid (AA) and the epoxide group of glycidyl methacrylate (GMA) of these copolymers led to the stabilization of the coatings through reactive blending. The so developed coatings were cured at room temperature and 120 °C, and then immersed in ultra-pure water and aqueous NaCl solutions at various concentrations for a time period up to three months. Visual inspection of the integrity of the materials coated onto glass slides, gravimetry, scanning electron microscopy (SEM) characterization, as well as the determination of total organic carbon (TOC) and total nitrogen (TN) of the solutions, were used to investigate the parameters affecting the release of the materials from the coatings based on these systems. The results revealed that curing temperature, complementary reactive groups’ content, and type of antimicrobial species control the release levels and the nature of releasable species of these environmentally-friendly antimicrobial coatings

Development of Antifouling Coatings Based on Quaternary Ammonium Compounds through a Multilayer Approach

The development of polymeric materials as antifouling coatings for aquaculture nets is elaborated in the present work. In this context, cross-linked polymeric systems based on quaternary ammonium compounds (immobilized or releasable) prepared under mild aqueous conditions were introduced as a more environmentally friendly methodology for coating nets on a large scale. To optimize the duration of action of the coatings, a multilayer coating method was applied by combining the antimicrobial organo-soluble copolymer poly(cetyltrimethylammonium 4-styrenesulfonate-co-glycidyl methacrylate) [P(SSAmC16-co-GMA20)] as the first layer with either the water-soluble copolymer poly(vinylbenzyl trimethylammonium chloride-co-acrylic acid) [P(VBCTMAM-co-AA20)] or the water-soluble polymers poly(acrylic acid) (PAA) and poly(hexamethylene guanidine), PHMG, as the second layer. The above-mentioned approach, followed by thermal cross-linking of the polymeric coatings, resulted in stable materials with controlled release of the biocidal species. The coated nets were studied in terms of their antifouling efficiency under accelerated biofouling conditions as well as under real conditions in an aquaculture field. Resistance to biofouling after three water-nutrient replenishments was observed under laboratory accelerated biofouling conditions. In addition, at the end of the field test (day 23) the uncoated nets were completely covered by marine contaminants, while the coated nets remained intact over most of their extent

Preparation of Antimicrobial Coatings from Cross-Linked Copolymers Containing Quaternary Dodecyl-Ammonium Compounds

One of the concerns today’s societies face is the development of resistant pathogenic microorganisms. The need to tackle this problem has driven the development of innovative antimicrobial materials capable of killing or inhibiting the growth of microorganisms. The present study investigates the dependence of the antimicrobial activity and solubility properties on the hydrophilicity/hydrophobicity ratio of antimicrobial coatings based on quaternary ammonium compounds. In this line, suitable hydrophilic and hydrophobic structural units were selected for synthesizing the antimicrobial copolymers poly(4-vinylbenzyl dimethyldodecylammonium chloride-co-acrylic acid), P(VBCDDA-co-AA20) and poly(dodecyltrimethylammonium 4-styrene sulfonate-co-glycidyl methacrylate), P(SSAmC12-co-GMA20), bearing an alkyl chain of 12 carbons either through covalent bonding or through electrostatic interaction. The cross-linking reaction of the carboxylic group of acrylic acid (AA) with the epoxide group of glycidyl methacrylate (GMA) of these two series of reactive antimicrobial copolymers was explored in blends, obtained through solution casting after curing at various temperatures. The release of the final products in pure water and NaCl 1 M solutions (as analyzed by gravimetry and total organic carbon, TOC/total nitrogen, TN analyses), could be controlled by the coating composition. The cross-linked polymeric membranes of composition 60/40 w/w % ratios led to 97.8 and 99.7% mortality for Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), respectively, whereas the coating 20/80 w/w % resulted in 96.6 and 99.8% cell reduction. Despite the decrease in hydrophobicity (from a 16- to a 12-carbon alkyl chain), the new materials maintained the killing efficacy, while at the same time resulting in increased release to the aqueous solution

Evaluation of Antimicrobial Efficiency of New Polymers Comprised by Covalently Attached and/or Electrostatically Bound Bacteriostatic Species, Based on Quaternary Ammonium Compounds

In the present work a detailed study of new bacteriostatic copolymers with quaternized ammonium groups introduced in the polymer chain through covalent attachment or electrostatic interaction, was performed. Different copolymers have been considered since beside the active species, the hydrophobic/hydrophilic nature of the co-monomer was also evaluated in the case of covalently attached bacteriostatic groups, aiming at achieving permanent antibacterial activity. Homopolymers with quaternized ammonium/phosphonium groups were also tested for comparison reasons. The antimicrobial activity of the synthesized polymers after 3 and 24 h of exposure at 4 and 22 °C was investigated on cultures of Gram-negative (P. aeruginosa, E. coli) and Gram-positive (S. aureus, E. faecalis) bacteria. It was found that the combination of the hydrophilic monomer acrylic acid (AA), at low contents, with the covalently attached bacteriostatic group vinyl benzyl dimethylhexadecylammonium chloride (VBCHAM) in the copolymer P(AA-co-VBCHAM88), resulted in a high bacteriostatic activity against P. aeruginosa and E. faecalis (6 log reduction in certain cases). Moreover, the combination of covalently attached VBCHAM units with electrostatically bound cetyltrimethylammonium 4-styrene sulfonate (SSAmC16) units in the P(SSAmC16-co-VBCHAMx) copolymers led to efficient antimicrobial materials, especially against Gram-positive bacteria, where a log reduction between 4.9 and 6.2 was verified. These materials remain remarkably efficient even when they are incorporated in polysulfone membranes

Polymeric Quaternary Ammonium-Containing Coatings with Potential Dual Contact-Based and Release-Based Antimicrobial Activity

In the present work, reactive blending of copolymers with complementary functional groups was applied to control their antimicrobial activity and antifouling action in real conditions. For this purpose, two series of copolymers, poly­(4-vinylbenzyl chloride-<i>co</i>-acrylic acid), P­(VBC-<i>co</i>-AAx), and poly­(sodium 4-styrenesulfonate-<i>co</i>-glycidyl methacrylate), P­(SSNa-<i>co</i>-GMAx), were synthesized via free radical copolymerization and further modified by the incorporation of biocidal units either covalently (4-vinyl benzyl dimethylhexadecylammonium chloride, VBCHAM) or electrostatically bound (cetyltrimethylammonium 4-styrenesulfonate, SSAmC₁₆). The cross-linking reaction of the carboxylic group of acrylic acid (AA) with the epoxide group of glycidyl methacrylate (GMA) of these two series of reactive antimicrobial copolymers was explored in blends obtained through solution casting after curing at various temperatures. The combined results from the ATR-FTIR characterization of the membranes, solubility tests, turbidimetry, and TEM suggest that the reaction occurs already at 80 °C, leading mostly to graft samples, while at higher curing temperatures (120 or 150 °C) insoluble cross-linked samples are usually obtained. Controlled release experiments of selected membranes were performed in pure water and aqueous 1 M NaCl solutions for a period of two months. The released material was followed through gravimetry and TOC/TN measurements, while the evolution of the integrity and the morphology of the membranes were followed visually and through SEM, respectively. Antimicrobial tests also revealed that the cross-linked membranes presented strong antimicrobial activity against <i>S. aureus</i> and <i>P. aeruginosa</i>. Finally, a specific blend combination was applied on aquaculture nets and cured at 80 °C. The modified nets, emerged in the sea for 15 and 35 days, exhibited high antifouling action as compared to blank nets