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.

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.

A novel concept for the use of an immiscible and non-meltable polymer, such as sodium polystyrene sulfonate (PSSNa), in order to prepare polyethylene non-woven breathable membranes is described. Membranes were fabricated by melt compounding of properly functionalized PE (P(E-co-AA)) and PSSNa (P(SSNa-co-GMA)) copolymers in the presence of water soluble polyethylene glycol (PEG). The inability of PSSNa derivatives to be melted was overcome by using PEG, which was easily meltable thus inducing PSSNa processability improvement. PEG was removed after membrane fabrication and therefore also acted as a porogen. Carbon nanotubes, functionalized with PSSNa moieties or alkyl groups, were also incorporated in the membranes with the aim of improving the porous connectivity and increasing the water vapor transmission rate. The morphology of the membranes was investigated through Scanning Electron Microscopy (SEM). Water vapor transmission rate (permeation) (WVTR) measurements for the porous membranes showed increased values in comparison with the neat PE ones. A further increase of WVTR was observed with the addition of CNTs to the polymer membranes.

Novel cross-linked hydrogels were synthesized as potential materials for the development of smart biofertilizers. For this purpose, hydrogels were prepared using collagen hydrolysate recovered from tannery waste. The water-soluble polymer poly(sodium 4-styrenesulfonate-co-glycidyl methacrylate) (P(SSNa-co-GMAx)) was among others used for the cross-linking reaction that combined hydrophilic nature with epoxide groups. The synthetic procedure was thoroughly investigated in order to ensure high percentage of epoxide groups in combination with water-soluble behavior. The copolymer did not show cytotoxicity against normal lung, skin fibroblasts, or nasal polyps fibroblasts. Through the present work, we also present the ability to control the properties of cross-linked hydrogels by altering copolymer’s composition and cross-linking parameters (curing temperature and time). Hydrogels were then studied in terms of water-uptake capacity for a period up to six days. The techniques Proton Nuclear Magnetic Resonance (¹H NMR), Thermogravimetric Analysis (TGA), Size Exclusion Chromatography (SEC), and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) were applied for the characterization of the synthesized copolymers and the cross-linked hydrogels. Three samples of biofertilizers based on collagen hydrolysate functionalized with P(SSNa-co-GMAx) and starch and having nutrients encapsulated (N, P, K) were prepared and characterized by physical–chemical analysis and Energy Dispersive X-ray analysis-Scanning Electron Microscope (EDAX-SEM) in terms of microstructure. Preliminary tests for application as fertilizers were performed including the release degree of oxidable organic compounds.

In the present work, direct incorporation of bioactive compounds onto the surface and interlayer of nanoclays before their incorporation into the final polymeric film was conducted, based on a green methodology developed by our group that is compatible with food packaging. This will lead to the higher thermal stability and the significant reduction of the loss of activity of the active ingredients during packaging configuration. On this basis, the essential oil (EO) components carvacrol (C), thymol (T) as well as olive leaf extract (OLE), which is used for the first time, were incorporated onto organo-modified montmorillonite (O) or inorganic bentonite (B) through the evaporation/adsorption method. The prepared bioactive nanocarriers were further mixed with low-density polyethylene (LDPE), via melt compounding, in order to prepare films for potential use as fresh fruit and vegetable packaging material. Characterization of the bioactive nanocarriers and films were performed through XRD, TGA, tensile, antimicrobial and antioxidant tests. Films with organically modified montmorillonite loaded with carvacrol (OC), thymol (OT) and olive leaf extract (OOLE) at 5% wt. showed better results in terms of mechanical properties. The films with polyethylene and organically modified montmorillonite loaded with carvacrol or thymol at 20% wt. (PE_OC20 and PE_OT20), as well as with olive leaf extract at 5 or 10 %wt., clay:bioactive substance ratio 1:0.5 and 10% compatibilizer (PE_OOLE5_MA10 and PE_OOLE10_MA10) exhibited the highest antioxidant activity. The resulting films displayed outstanding antimicrobial properties against Gram-negative Escherichia coli (E. coli) with the best results appearing in the films with 10% OC and OT.

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.