Marta Chrószcz-Porębska

The research hypothesis was that adjusting the content of the quaternary ammonium urethane dimethacrylate monomer bearing an N-dodecyl substituent (QAUDMA-12) would yield dental matrices with high antimicrobial activity, good biocompatibility, and favorable physicochemical properties. The research hypothesis was verified for six Bis-GMA, TEGDMA, and UDMA copolymers containing from 2.5 to 40 wt.% QAUDMA-12 by determining their degree of conversion, hardness, flexural properties, water behavior, antimicrobial activity against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Candida albicans, and cytotoxicity towards L929 mouse fibroblast cells. The research hypothesis was confirmed. Copolymers containing less than 30 wt.% QAUDMA-12 exhibited favorable polymerization efficiency, water sorption and solubility, and mechanical properties comparable to those of conventional Bis-GMA/TEGDMA systems. At the same time, they showed no cytotoxic effects toward mouse fibroblast cells. The results of antimicrobial tests show that the minimum QAUDMA-12 concentration providing sufficient antimicrobial activity was 20 wt.%. Therefore, it can be concluded that the 20 wt.% concentration of QAUDMA-12 makes it possible to obtain dental matrices that are non-toxic, exhibit antimicrobial activity, and possess the desired physico-mechanical performance.

Improving the hydrophilicity and tissue adhesion of polymers remains a significant challenge in tissue engineering and is often addressed by introducing functional groups that enhance polymer–tissue interactions. In this field, L-cysteine (Cys) and N-acetyl-L-cysteine (NAC) are particularly interesting due to their functional carboxyl and amine groups, which are prone to hydrogen bonding. Following this trend, this study (i) investigated the feasibility of grafting Cys or NAC onto the linear oligoitaconates via thio-Michael addition and (ii) examined the influence of amino acid incorporation on the material’s physicochemical properties. NMR-based calculations confirmed nearly 100% addition efficiency for Cys and a slightly lower, but still high, efficiency for NAC. FT-IR spectra confirmed thiol-based addition, as signal from the Cys/NAC S–H stretching vibrations was not observed in the adduct’s spectra. The obtained adducts showed thermal stability up to 200 °C and glass transition temperatures below −20 °C. They were soluble in common organic solvents, except for Cys adducts with oligo(propylene itaconate) and oligo(hexylene itaconate), which were water-soluble only. Due to the low molecular weight (below 1000 g/mol) of oligoitaconates, their adducts cannot serve as standalone scaffold components. However, they showed potential for use as modifiers for high-molecular-weight polylactide or poly(ɛ-caprolactone)-based scaffolds.

Ethylene–vinyl acetate (EVA) is a versatile polymer for applications in dental devices; however, its vulnerability to microbial colonization increases with long-term use. This study evaluates EVA composites modified with silver–sodium–hydrogen–zirconium phosphate (SP) particles, aimed at enhancing antimicrobial performance while preserving key functional properties. Composites containing 1–16 wt.% SP were prepared via solvent-based and mechanical compounding routes, with scanning electron microscopy confirming correct filler distribution across processing methods. Antimicrobial assays revealed a pronounced reduction in Streptococcus mutans and Candida albicans levels, reaching 88% and 98% antimicrobial efficacy, respectively, at 16 wt.% SP. Cytotoxicity testing with L-929 fibroblasts demonstrated maintained cell viability above the 70% threshold, confirming non-cytotoxicity. Mechanical characterization indicated marginal increases in hardness, slight tensile strength reduction at higher filler loadings, while other physicochemical and thermal analyses showed minimal impact on polymer performance. These findings indicate balanced antimicrobial activity with other biofunctional properties.

The modification of polymers towards increasing their biocompatibility gathers the attention of scientists worldwide. Several strategies are used in this field, among which chemical post-polymerization modification has recently been the most explored. Particular attention revolves around polymer-L-cysteine (Cys) conjugates. Cys, a natural amino acid, contains reactive thiol, amine, and carboxyl moieties, allowing hydrogen bond formation and improved tissue adhesion when conjugated to polymers. Conjugation of Cys and its derivatives to polymers has been examined mostly for hyaluronic acid, chitosan, alginate, polyesters, polyurethanes, poly(ethylene glycol), poly(acrylic acid), polycarbophil, and carboxymethyl cellulose. It was shown that the conjugation of Cys and its derivatives to polymers significantly increased their tissue adhesion, particularly mucoadhesion, stability at physiological pH, drug encapsulation efficiency, drug release, and drug permeation. Conjugates were also non-toxic toward various cell lines. These properties make Cys conjugation a promising strategy for advancing polymer applications in drug delivery systems and tissue engineering. This review aims to provide an overview of these features and to present the conjugation of Cys and its derivatives as a modern and promising approach for enhancing polymer tissue adhesion and its application in the medical field.

Dental caries are treated using dental composite restorative materials (DCRM). However, commercial DCRMs lack antibacterial activity. This research aimed to analyze the in vitro antibacterial activity of a series of copolymers consisting of a urethane–dimethacrylate monomer (UDMA), bisphenol A glycerolate dimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) and urethane–dimethacrylate monomer with two quaternary ammonium groups and a 1,3-bis(1-isocyanate-1-methylethyl)benzene core (QAn+TMXDI, where n = 8, 10, or 12 is the number of carbon atoms in the N-alkyl substituent). QAn+TMXDI contents in copolymers were 20 and 40 wt.%. The results of the Staphylococcus aureus and Escherichia coli adhesion test demonstrated that the logCFU/mL decreased as the length of the N-alkyl chain decreased and QAn+TMXDI content increased. The copolymers of QA8+TMXDI 40 wt.%, Bis-GMA 40 wt.%, and TEGDMA 20 wt.% showed the highest antibacterial activity, with a logCFU/mL of 2.39 for S. aureus and no viable E. coli cells.

In this study, two novel quaternary ammonium urethane-dimethacrylates (QAUDMAs) were designed for potential use as comonomers in antibacterial dental composite restorative materials. QAUDMAs were synthesized via the reaction of 1,3-bis(1-isocyanato-1-methylethyl)benzene with 2-(methacryloyloxy)ethyl-2-decylhydroxyethylmethylammonium bromide (QA10+TMXDI) and 2-(methacryloyloxy)ethyl-2-dodecylhydroxyethylmethylammonium bromide (QA12+TMXDI). Their compositions with common dental dimethacrylates comprising QAUDMA 20 wt.%, urethane-dimethacrylate monomer (UDMA) 20 wt.%, bisphenol A glycerolate dimethacrylate (Bis-GMA) 40 wt.%, and triethylene glycol dimethacrylate (TEGDMA) 20 wt.%, were photocured. The achieved copolymers were characterized for their physicochemical and mechanical properties, including their degree of conversion (DC), glass transition temperature (T_g), polymerization shrinkage (S), water contact angle (WCA), flexural modulus (E), flexural strength (FS), hardness (HB), water sorption (WS), and water leachability (WL). The antibacterial activity of the copolymers was characterized by the minimum bactericidal concentration (MBC) and minimum inhibitory concentration (MIC) against Staphylococcus aureus and Escherichia coli. The achieved results were compared to the properties of a typical dental copolymer comprising UDMA 40 wt.%, Bis-GMA 40 wt.%, and TEGDMA 20 wt.%. The introduction of QAUDMAs did not deteriorate physicochemical and mechanical properties. The WS and WL increased; however, they were still satisfactory. The copolymer comprising QA10+TMXDI showed a higher antibacterial effect than that comprising QA12+TMXDI and that of the reference copolymer.

Composite restorative materials with dimethacrylathe matrices are commonly used as dental fillings. They have good usable properties; however, they lack antibacterial activity. They may also promote secondary caries. A solution to that problem could be the application of monomers with microbiologically active quaternary ammonium groups. This research aimed at the synthesis of a new urethane-dimethacrylate monomer with a 1,3-bis(2-isocyanatopropan-2-yl)benzene (TMXDI) core, as well as two arms with quaternary ammonium group with the decyl subsistent. The structure of the obtained monomer was confirmed via FTIR and ¹H and ¹³C NMR spectroscopies.

Using dental composite restorative materials with a copolymeric matrix chemically modified towards bioactive properties can help fight secondary caries. In this study, copolymers of 40 wt.% bisphenol A glycerolate dimethacrylate, 40 wt.% quaternary ammonium urethane-dimethacrylates (QAUDMA-m, where m represents 8, 10, 12, 14, 16 and 18 carbon atoms in the N-alkyl substituent), and 20 wt.% triethylene glycol dimethacrylate (BG:QAm:TEGs) were tested for (i) cytotoxicity on the L929 mouse fibroblast cell line; (ii) fungal adhesion, fungal growth inhibition zone, and fungicidal activity against C. albicans; and (iii) bactericidal activity against S. aureus and E. coli. BG:QAm:TEGs had no cytotoxic effects on L929 mouse fibroblasts because the reduction of cell viability was less than 30% compared to the control. BG:QAm:TEGs also showed antifungal activity. The number of fungal colonies on their surfaces depended on the water contact angle (WCA). The higher the WCA, the greater the scale of fungal adhesion. The fungal growth inhibition zone depended on the concentration of QA groups (x_QA). The lower the x_QA, the lower the inhibition zone. In addition, 25 mg/mL BG:QAm:TEGs suspensions in culture media showed fungicidal and bactericidal effects. In conclusion, BG:QAm:TEGs can be recognized as antimicrobial biomaterials with negligible biological patient risk.

Due to the questionable durability of dental restorations, there is a need to increase the lifetime of composite restoration. The present study used diethylene glycol monomethacrylate/4,4′-methylenebis(cyclohexyl isocyanate) (DEGMMA/CHMDI), diethylene glycol monomethacrylate/isophorone diisocyanate (DEGMMA/IPDI) monomers, and bis(2,6-diisopropylphenyl)carbodiimide (CHINOX SA-1) as modifiers of a polymer matrix (40 wt% urethane dimethacrylate (UDMA), 40 wt% bisphenol A ethoxylateddimethacrylate (bis-EMA), and 20 wt% triethyleneglycol dimethacrylate (TEGDMA)). Flexural strength (FS), diametral tensile strength (DTS), hardness (HV), sorption, and solubility were determined. To assess hydrolytic stability, the materials were tested before and after two aging methods (I-7500 cycles, 5 °C and 55 °C, water and 7 days, 60 °C, 0.1 M NaOH; II-5 days, 55 °C, water and 7 days, 60 °C, 0.1 M NaOH). The aging protocol resulted in no noticeable change (median values were the same as or higher than the control value) or a decrease in the DTS value from 4 to 28%, and a decrease in the FS value by 2 to 14%. The hardness values after aging were more than 60% lower than those of the controls. The used additives did not improve the initial (control) properties of the composite material. The addition of CHINOX SA-1 improved the hydrolytic stability of composites based on UDMA/bis-EMA/TEGDMA monomers, which could potentially extend the service life of the modified material. Extended studies are needed to confirm the possible use of CHINOX SA-1 as an antihydrolysis agent in dental composites.