Antibacterial coatings based on quaternary ammonium compounds (QACs) have been widely investigated in controlled release applications. Quaternary ammonium compounds are low-cost and easily accessible disinfectants that have been extensively used, especially after the COVID-19 outbreak. There has been a growing interest in developing a clearer understanding of various aspects that need to be taken into account for the design of quaternary ammonium compounds to be used in the biomedical field. In this contribution, we outline the mechanism of action of those materials as well as the key design parameters associated with their structure and antibacterial activity. Moreover, emphasis has been placed on the type of antibacterial coatings based on QACs and their applications in the biomedical field. A brief outlook on future research guidelines for the development of dual-function antibacterial coatings is also discussed.

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.

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.

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.

Crosslinked polymeric materials based on a quaternary trimethylammonium compound were developed and evaluated as potential antifouling coatings. For this purpose, two water-soluble random copolymers, poly(4-vinylbenzyltrimethylammonium chloride-co-acrylic acid) P(VBCTMAM-co-AAx) and poly(N,N-dimethylacrylamide-co-glycidylmethacrylate) P(DMAm-co-GMAx), were synthesized via free radical polymerization. A water based approach for the synthesis of P(VBCTMAM-co-AAx) copolymer was used. Coatings of the complementary reactive copolymers in different compositions were obtained by curing at 120 °C for one day and were used to coat aquaculture nets. These nets were evaluated in respect to their release rate using Total Organic Carbon (TOC) and Total Nitrogen (TN) measurements. Finally, the antifouling efficacy of these newly-composed durable coatings was investigated for 14 days in accelerated conditions. The results showed that this novel polymeric material provides contact-killing antifouling activity for a short time period, whereas it functions efficiently in biofouling removal after high-pressure cleaning.

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.