Development and evaluation of UV-curable methacrylate-based hydrogel coatings

Abstract

Project Number

2209-A project (11919B012211549)

Development and evaluation of UV-curable methacrylate-based hydrogel coatings

Abstract

The development of sustainable bioactive hydrogel coatings from renewable resources has gained significant attention as eco-friendly alternatives to petroleum-based systems. In this study, novel bio-based acrylate hydrogel coatings were successfully synthesized via UV- induced photopolymerization of citronella essential oil (CEO) with glycidyl methacrylate (GMA) using ethylene glycol dimethacrylate (EGDMA) as crosslinker and Irgacure 2959 as photoinitiator. GC-MS analysis of the native citronella oil identified citronellal (39.09%), geraniol (25.47%), citronellol (10.47%) and geranyl acetate (3.15%) as the major bioactive constituents. The crosslinked networks were extensively characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), swelling studies and antibacterial assays. FTIR spectra confirmed the presence of chemical interactions between GMA and citronellol fuctional groups in the samples with higher GMA content (GCE541 and GCE451), indicating successful incorporation of the essential oil into the polymer network. SEM revealed homogeneous surface morphology for optimized formulations, while swelling test demonstrated significant hydration capacity ranging from 9.23% to 77.1% depending on composition, indicating tunable hydrogel. Most notably, the optimized formulation (GCE541) exhibited potent broad-spectrum against Staphylococus aureus, and 6mm against Candida albicans (fungal strain). To our knowledge, this represents the first comprehensive study on UV-cured GMA/EGDMA hydrogel coatings incorporating CEO, demonstrating their potential as sustainable antimicrobial materials for biomedical and industrial applications.

Keywords

• Citronella essential oil;
• UV-curable hydrogels
• Photopolymerization
• Antimicrobial activity
• Hydrogel coatings

Supporting Institution

TÜBİTAK- 2209-A

Project Number

2209-A project (11919B012211549)

Ethical Statement

The authors of this article declare that the materials and methods used in this study did not require ethical committee approval and/or legal or special permissions.

Thanks

The author gratefully acknowledge Neriman Sinan for her kind help in the FTIR analysis of the hydrogels and Bursa Technical University Chemistry Department. This study was financially supported by TÜBITAK within the scope of the 2209-A project (1919B012211549).

References

1. Yu Y, Pérez MB, Cao C, de Beer S (2021) Switching (bio-)adhesion and friction in liquid by stimulus responsive polymer coatings. Eur Polym J 147:110298.
2. Sun A, He X, Ji X, Hu D, Pan M, Zhang L, Qian Z (2021) Current research progress of photopolymerized hydrogels in tissue engineering. Chin Chem Lett 32(7):2117–2126.
3. Liu J, Qu S, Suo Z, Yang W (2021) Functional hydrogel coatings. Natl Sci Rev 8(2):nwaa254.
4. Peng T, Shi Q, Chen M, Yu W, Yang T (2023) Antibacterial-based hydrogel coatings and their application in the biomedical field—a review. J Funct Biomater 14(5):243.
5. Miao J, Wu X, Fang Y, Zeng M, Huang Z, Ouyang M, Wang R (2023) Multifunctional hydrogel coatings with high antimicrobial loading efficiency and pH-responsive properties for urinary catheter applications. J Mater Chem B 11(15):3373–3386.
6. Löwenberg C, Julich-Gruner KK, Neffe AT, Lendlein A (2015) Influence of glycidylmethacrylate functional groups attached to gelatin on the formation and properties of hydrogels. MRS Online Proc Libr (OPL) 1718:103–108.
7. Alemdar N (2016) Synthesis of chitosan-based hydrogel by using photopolymerization technique. Anadolu Univ J Sci Technol A–Appl Sci Eng 17(2):391–400.
8. Wong BCF, Ahmad A, Hanifah SA, Hassan NH (2016) Effects of ethylene glycol dimethacrylate as cross-linker in ionic liquid gel polymer electrolyte based on poly(glycidyl methacrylate). Int J Polym Anal Charact 21(2):95–103.

9. Karabıyık M, Cihanoğlu G, Ebil Ö (2023) CVD deposited epoxy copolymers as protective coatings for optical surfaces. Polymers 15(3):652.
10. Sharma R, Rao R, Kumar S, Mahant S, Khatkar S (2019) Therapeutic potential of citronella essential oil: a review. Curr Drug Discov Technol 16(4):330–339.
11. Mangalagiri NP, Panditi SK, Jeevigunta NLL (2021) Antimicrobial activity of essential plant oils and their major components. Heliyon 7(4):e06754.
12. Pontes EKU, Melo HM, Nogueira JWA, Firmino NCS, de Carvalho MG, Catunda Júnior FEA, Cavalcante TTA (2019) Antibiofilm activity of the essential oil of citronella (Cymbopogon nardus) and its major component, geraniol, on the bacterial biofilms of Staphylococcus aureus. Food Sci Biotechnol 28(3):633–639.
13. Pitterou I, Kalogeropoulou F, Tzani A, Tsiantas K, Gatou MA, Pavlatou E, Detsi A (2024) Development of alginate hydrogels incorporating essential oils loaded in chitosan nanoparticles for biomedical applications. Molecules 29(22):5318.
14. Low WL, Kenward MA, Amin MCIM, Martin C (2016) Ionically crosslinked chitosan hydrogels for the controlled release of antimicrobial essential oils and metal ions for wound management applications. Medicines 3(1):8.
15. Kusjuriansah K, Rodhiyah M, Syifa NA, Luthfianti HR, Waresindo WX, Hapidin DA, Khairurrijal K (2024) Composite hydrogel of poly(vinyl alcohol) loaded by Citrus hystrix leaf extract, chitosan, and sodium alginate with in vitro antibacterial and release test. ACS Omega 9(11):13306–13322.
16. Ensandoost R, Izadi-Vasafi H, Adelnia H (2022) Anti-bacterial activity of chitosan-alginate-poly(vinyl alcohol) hydrogel containing entrapped peppermint essential oil. J Macromol Sci Part B 61(2):225–237.
17. Almasi L, Radi M, Amiri S (2020) The release rate and antimicrobial activity of calcium–alginate films containing self-microemulsifying Thymus vulgaris essential oil against Escherichia coli and Staphylococcus aureus. J Food Saf 40(5):e12828.
18. Pereira dos Santos E, Nicácio PHM, Coêlho Barbosa F, Nunes da Silva H, Andrade ALS, Lia Fook MV, Farias Leite I (2019) Chitosan/essential oils formulations for potential use as wound dressing: physical and antimicrobial properties. Materials 12(14):2223.
19. Parın FN (2024) Synthesis of antibacterial PVA-AAM Pickering emulsion hydrogels (PEHs) for medical applications. J Eng Sci Des 12(2):384–391.
20. Mielczarek M, Marchewka J, Sitarz M, Cieniek Ł, Brzychczy-Włoch M, Gosiewski T, Moskalewicz T (2025) The application of citronella oil and citronellol as antibacterial ingredients in chitosan coatings for titanium surfaces. Metall Mater Trans A 56:1–23.
21. Sereia MOP, Santos EAD, Leite LP, Neves RC, Marin VR, Ferreira H, Sass DC (2025) Synergistic effect of essential oils and rhamnolipid on Xanthomonas citri subsp. citri. Microorganisms 13(5):1153.
22. Angane M, Swift S, Huang K, Butts CA, Quek SY (2022) Essential oils and their major components: an updated review on antimicrobial activities, mechanism of action and their potential application in the food industry. Foods 11(3):464.
23. Masyita A, Sari RM, Astuti AD, Yasir B, Rumata NR, Emran TB, Simal-Gandara J (2022) Terpenes and terpenoids as main bioactive compounds of essential oils, their roles in human health and potential application as natural food preservatives. Food Chem X 13:100217.
24. Bassolé IHN, Juliani HR (2012) Essential oils in combination and their antimicrobial properties. Molecules 17(4):3989–4006.
25. Jiang B, Zhang Y, Wang R, Wang T, Zeng E (2024) Innovative acrylic resin–hydrogel double-layer coating: achieving dual-anchoring, enhanced adhesion, and superior anti-biofouling properties for marine applications. Gels 10(5):320.
26. Mredha MTI, Le HH, Cui J, Jeon I (2020) Double-hydrophobic-coating through quenching for hydrogels with strong resistance to both drying and swelling. Adv Sci 7(6):1903145.
27. Maciejewska M (2025) Insight into the preparation, modification, and thermal characterization of porous poly(GMA-co-EGDMA) copolymers. J Therm Anal Calorim 147:1–13.
28. Mathers RT, McMahon KC, Damodaran K, Retarides CJ, Kelley DJ (2006) Ring-opening metathesis polymerizations in D-limonene: a renewable polymerization solvent and chain transfer agent for the synthesis of alkene macromonomers. Macromolecules 39(26):8982–8986.
29. Mangeon C, Michely L, Rios de Anda A, Thevenieau F, Renard E, Langlois V (2018) Natural terpenes used as plasticizers for poly(3-hydroxybutyrate). ACS Sustain Chem Eng 6(12):16160–16168.
30. Saabome SM, Yoon S (2020) A review on plasticizers and eco-friendly bioplasticizers: biomass sources and market. Int J Eng Res Technol (IJERT) 9:1–10.
31. Truzzi E, Durante C, Bertelli D, Catellani B, Pellacani S, Benvenuti S (2022) Rapid classification and recognition method of the species and chemotypes of essential oils by ATR-FTIR spectroscopy coupled with chemometrics. Molecules 27(17):5618.
32. Basak S, Saxena S, Raja ASM, Patil PG, Krishnaprasad G, Narkar R, Kambli N (2021) Development of cotton fibre-based fragrance pack and its characterization. Cellulose 28(11):7185–7200.
33. Aisyah Y, Sabilla AL, Yunita D (2022) Encapsulation of patchouli (Pogostemon cablin Benth), nutmeg (Myristica fragrans), and citronella (Cymbopogon nardus) essential oil using a combination of coating materials with complex coacervation method. In: IOP Conf Ser Earth Environ Sci 1116(1):012021. IOP Publishing, London.
34. Bayramoğlu G, Arıca MY (2009) Immobilization of laccase onto poly(glycidylmethacrylate) brush grafted poly(hydroxyethylmethacrylate) films: enzymatic oxidation of phenolic compounds. Mater Sci Eng C 29(6):1990–1997.
35. Saikia BJ, Dolui SK (2016) Designing semiencapsulation based covalently self-healable poly(methyl methacrylate) composites by atom transfer radical polymerization. J Polym Sci Part A Polym Chem 54(12):1842–1851.
36. Abdollahi H, Najafi V, Amiri F (2021) Determination of monomer reactivity ratios and thermal properties of poly(GMA-co-MMA) copolymers. Polym Bull 78(1):493–511.
37. Alven S, Peter S, Aderibigbe BA (2022) Polymer-based hydrogels enriched with essential oils: a promising approach for the treatment of infected wounds. Polymers 14(18):3772.
38. Wang R, Cheng C, Wang H, Wang D (2024) Swollen hydrogel nanotechnology: advanced applications of the rudimentary swelling properties of hydrogels. ChemPhysMater 3(4):357–375.
39. Parın FN, Gün A, İlhan R, Parın U (2025) Effects of essential oil on the properties of egg white/polyacrylamide (EW/PAAm) Pickering emulsion hydrogels (PEHs) via UV crosslinking. Polym Bull 150:1–24.
40. Vasconcelos PGS, Lee KM, Abuna GF, Costa EMMB, Murata RM (2024) Monoterpene antifungal activities: evaluating geraniol, citronellal, and linalool on Candida biofilm, host inflammatory responses, and structure–activity relationships. Front Pharmacol 15:1394053.
41. Zhang F, An Y, Roohpour N, Barber AH, Gautrot JE (2018) Hydration dependent mechanical performance of denture adhesive hydrogels. Dent Mater 34(10):1440–1448.
42. Guimarães AC, Meireles LM, Lemos MF, Guimarães MCC, Endringer DC, Fronza M, Scherer R (2019) Antibacterial activity of terpenes and terpenoids present in essential oils. Molecules 24(13):2471.
43. de Lira MP, Moraes GFQ, Santos GM, de Andrade Júnior FP, Pereira FDO, Lima IO (2020) Synergistic antibacterial activity of monoterpenes in combination with conventional antimicrobials against Gram-positive and Gram-negative bacteria. Rev Cienc Med Biol 19:258–265.