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.

Designing Antioxidant and Antimicrobial Polyethylene Films with Bioactive Compounds/Clay Nanohybrids for Potential Packaging Applications.

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.

Humidity-Responsive Antimicrobial Membranes Based on Cross-Linked Copolymers Functionalized with Ionic Liquid Moieties.

Humidity-responsive materials have attracted increasing attention for their potential use in various applications, e.g., sensors, soft robotics, and human-machine interfaces. Much effort has been focused on the use of ionic liquids for the construction of humidity-responsive sensors; yet, not enough attention has been paid on the susceptibility of the used poly(ionic liquid)s to microorganisms. This is especially relevant to the wide use of the polymers for biomedical applications, e.g., wearable body-condition sensors or healthcare control systems. We herein describe the development of dual functional, self-standing, monolayer antimicrobial membranes derived from cross-linked copolymers functionalized with ionic liquids. In a first step, random copolymers of poly(4-vinylbenzyl N-alkyl imidazolium chloride-co-acrylic acid), P(VBCImCn-co-AA20), were synthesized bearing aliphatic chains of different lengths (where n = 1, 4, 8, 12, 16 carbon atoms) to investigate the effect of hydrophobicity/hydrophilicity on the humidity-responsive properties of the copolymer and its antimicrobial activity. The aforementioned copolymers were later blended with the complementary reactive copolymers of poly(cetyl trimethylammonium 4-styrene sulfonate-co-glycidyl methacrylate), P(SSAmC16-co-GMA20), to provide highly stable films and coatings through thermal cross-linking. The membrane P(VBCImC12-co-AA20)/P(SSAmC16-co-GMA20) with a molar ratio of 3:1 (mol AA/mol GMA) exhibited immediate and high response to moisture through folding or flipping motions when placed on a wet filter paper or on the palm of a hand. The inhibition of growth for selected bacterial species (Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus) on the copolymer membranes was dependent on the length of the imidazolium alkyl chain and the species. Additionally, in the case of the cross-linked P(VBCImCn-co-AA20)/P(SSAmC16-co-GMA20) membranes, the overall efficacy was very high against all microorganisms tested, which, combined with their high humidity responsiveness, enables their potential application.

Environmentally Friendly Hybrid Organic-Inorganic Halogen-Free Coatings for Wood Fire-Retardant Applications.

Wood and wood-based products are extensively used in the building sector due to their interesting combination of properties. Fire safety and fire spread, however, are of utmost concern for the protection of buildings. Therefore, in timber structures, wood must be treated with fire-retardant materials in order to improve its reaction to fire. This article highlights the flame retardancy of novel hybrid organic-inorganic halogen-free coatings applied on plywood substrates. For this purpose, either a huntite-rich mineral (H5) or its modified nano-Mg (OH)2 type form (H5-m), acting as an inorganic (nano) filler, was functionalized with reactive oligomers (ROs) and incorporated into a waterborne polymeric matrix. A water-soluble polymer (P (SSNa-co-GMAx)), combining its hydrophilic nature with functional epoxide groups, was used as the reactive oligomer in order to enhance the compatibility between the filler and the matrix. Among various coating compositions, the system composed of 13% polymeric matrix, 73% H5 and 14% ROs, which provided the best coating quality and flame retardancy, was selected for the coating of plywood on a larger scale in one or two layers. The results indicated that the novel plywood coating systems with the addition of ecological coating formulations (WF-13, WF-14 and WF-15), prepared at two layers, reached Euroclass B according to EN13501-1, which is the best possible for fire systems applied to wood.

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.

Environmentally Friendly Cross-Linked Antifouling Coatings Based on Dual Antimicrobial Action.

The synthesis of environmentally friendly antimicrobial polymeric coatings, especially in the case of aquaculture, that inhibit the growth of bio-deposits is a very important issue that will contribute to the cost reduction of nets' cleaning process as well as the protection of the submarine wealth from the biostatic substances used so far. In the present work, the antimicrobial polymers P(SSAmC16-co-VBCHAMx) and the terpolymer P(SSAmC16w-co-VBCHAMx-co-GMAy) were synthesized, bearing quaternary ammonium compounds, electrostatically bound and covalently attached at the same polymer chain. The combination of the two types is of particular importance, as it can provide effective antimicrobial polymeric materials with self-polishing capabilities as a result of the released nature of the antimicrobial, in combination with the permanent local action of the immobilized species. The cross-linking reaction of the terpolymer P(SSAmC16w-co-VBCHAMx-co-GMAy) with the homopolymer polyacrylic acid (PAA) was tested at 120 °C in terms of the equivalent ratio between epoxy and carboxyl groups. The synthesized polymers were further used for the coating of aquaculture nets and tested in terms of antifouling efficiency in lab and scale-up conditions. Uncoated nets were also used in all applications for comparison reasons. The coated nets performed efficiently for 35 days in lab-scale and 66 days in scale-up conditions, showing a high antifouling activity in both fields compared to the uncoated nets.