Polímeros: Ciência e Tecnologia
https://www.revistapolimeros.org.br/article/doi/10.1590/0104-1428.20250108
Polímeros: Ciência e Tecnologia
Original Article

Harnessing natural monoterpenes: cold plasma polymerization of citronellol

Erick Osvaldo Martínez-Ruiz; José Abraham González-López; Claudia Gabriela Cuellar-Gaona; María del Carmen Rodríguez-Aranda; Adán Reyes-Reyes; Juan Andrés Reyes-Reyes; Alejandra Ortiz-Dosal; María Esther Treviño-Martínez; María Guadalupe Neira-Velázquez

http://dx.doi.org/10.1590/0104-1428.20250108 Polímeros: Ciência e Tecnologia, vol.36, n3, e20260027, 2026
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Abstract

This study presents the cold plasma polymerization of citronellol, a natural monoterpene, as a route to obtain antibacterial polymeric films. A 10 µL volume of citronellol was polymerized under argon plasma at 100 Pa, yielding a solid film (Pcit). SEM analysis revealed a heterogeneous, branched surface with a roughness Ra of 7.53 ± 2.19 µm and Rz of 50.57 ± 24.26 µm. Water contact angle measurements indicated moderate hydrophilicity (62°). XPS and FTIR analyses confirmed the presence of oxygen-containing functional groups, while OES detected reactive carbon- and oxygen-containing species generated during plasma operation. Hemolysis tests showed excellent blood compatibility (<5%), and antimicrobial assays revealed inhibition zones of 12 ± 1 mm for E. coli and 10 ± 1 mm for S. aureus. Overall, these results indicate that plasma-polymerized citronellol yields functional surfaces with promising potential for biomedical and antibacterial applications.

 

 

Keywords

citronellol, cold plasma, green chemistry, monoterpenes, polymerization

References

1 Dufour, T. (2023). From basics to frontiers: a comprehensive review of plasma-modified and plasma-synthesized polymer films. Polymers, 15(17), 3607. https://doi.org/10.3390/polym15173607. PMid:37688233.

2 Mosquera, M. E. G., Jiménez, G., Tabernero, V., Vinueza-Vaca, J., García-Estrada, C., Kosalková, K., Sola-Landa, A., Monje, B., Acosta, C., Alonso, R., & Valera, M. A. (2021). Terpenes and terpenoids: building blocks to produce biopolymers. Sustainable Chemistry, 2(3), 467-492. https://doi.org/10.3390/suschem2030026.

3 Loesch‐Zhang, A., Geissler, A., & Biesalski, M. (2023). Plasma polymerization of biogenic precursors. Plasma Processes and Polymers, 20(10), e2300016. https://doi.org/10.1002/ppap.202300016.

4 Kumar, A., Grant, D. S., Bazaka, K., & Jacob, M. V. (2018). Tailoring terpenoid plasma polymer properties by controlling the substrate temperature during PECVD. Journal of Applied Polymer Science, 135(5), 45771. https://doi.org/10.1002/app.45771.

5 Levchenko, I., Xu, S., Baranov, O., Bazaka, O., Ivanova, E., & Bazaka, K. (2021). Plasma and polymers: recent progress and trends. Molecules, 26(13), 4091. https://doi.org/10.3390/molecules26134091. PMid:34279431.

6 Thomsett, M. R., Storr, T. E., Monaghan, O. R., Stockman, R. A., & Howdle, S. M. (2016). Progress in the synthesis of sustainable polymers from terpenes and terpenoids. Green Materials, 4(3), 115-134. https://doi.org/10.1680/jgrma.16.00009.

7 Milchev, A., & Binder, K. (2020). Semiflexible Polymers interacting with planar surfaces: weak versus strong adsorption. Polymers, 12(2), 255. https://doi.org/10.3390/polym12020255. PMid:31978981.

8 Martínez-Ruiz, E. O., González-López, J. A., Cuellar-Gaona, C. G., González-López, M. Á., Torres-Lubián, J. R., Treviño-Martínez, M. E., Gallardo-Vega, C., Soria-Arguello, G., & Neira-Velázquez, M. G. (2024). Cold plasma oligomerization in argon atmosphere from carvacrol: product formation and characterization. Revista Mexicana de Ingeniería Química, 23(3), Poly24405. https://doi.org/10.24275/rmiq/Poly24405.

9 Ghalkhani, M., Beheshtian, J., & Salehi, M. (2016). Electrochemical and DFT study of an anticancer and active anthelmintic drug at carbon nanostructured modified electrode. Materials Science and Engineering C, 69, 1345-1353. https://doi.org/10.1016/j.msec.2016.08.031. PMid:27612835.

10 Kannan, M., Singh, S., & Prasad, R. R. (2022). The effect of processing parameters on the mechanical properties of Calcia-Stabilized Zirconia (CSZ) for dental use. Coatings, 13(1), 75. https://doi.org/10.3390/coatings13010075.

11 Gaglio, R., Botta, L., Garofalo, G., Miceli, A., Settanni, L., & Lopresti, F. (2021). Carvacrol activated biopolymeric foam: an effective packaging system to control the development of spoilage and pathogenic bacteria on sliced pumpkin and melon. Food Packaging and Shelf Life, 28, 100633. https://doi.org/10.1016/j.fpsl.2021.100633.

12 Bazaka, K., Jacob, M. V., Truong, V. K., Wang, F., Pushpamali, W. A. A., Wang, J. Y., Ellis, A. V., Berndt, C. C., Crawford, R. J., & Ivanova, E. P. (2010). Plasma-enhanced synthesis of bioactive polymeric coatings from monoterpene alcohols: a combined experimental and theoretical study. Biomacromolecules, 11(8), 2016-2026. https://doi.org/10.1021/bm100369n. PMid:20590150.

13 Bazaka, K., Ahmad, J., Oelgemöller, M., Uddin, A., & Jacob, M. V. (2017). Photostability of plasma polymerized γ-terpinene thin films for encapsulation of OPV. Scientific Reports, 7(1), 45599. https://doi.org/10.1038/srep45599. PMid:28358138.

14 Isobe, T., Ohkawara, S., Ochi, S., Tanaka-Kagawa, T., & Hanioka, N. (2019). S-equol glucuronidation in liver and intestinal microsomes of humans, monkeys, dogs, rats, and mice. Food and Chemical Toxicology : An International Journal Published for the British Industrial Biological Research Association, 131, 110542. https://doi.org/10.1016/j.fct.2019.05.050. PMid:31163218.

15 Jayaraj, R. L., Azimullah, S., Parekh, K. A., Ojha, S. K., & Beiram, R. (2022). Effect of citronellol on oxidative stress, neuroinflammation and autophagy pathways in an in vivo model of Parkinson’s disease. Heliyon, 8(11), e11434. https://doi.org/10.1016/j.heliyon.2022.e11434. PMid:36387498.

16 Iqbal, U., Malik, A., Sial, N. T., Mehmood, M. H., Nawaz, S., Papadakis, M., Fouad, D., Ateyya, H., Welson, N. N., Alexiou, A., & Batiha, G. E.-S. (2024). β-Citronellol: a potential anti-inflammatory and gastro-protective agent-mechanistic insights into its modulatory effects on COX-II, 5-LOX, eNOS, and ICAM-1 pathways through in vitro, in vivo, in silico, and network pharmacology studies. Inflammopharmacology, 32(6), 3761-3784. https://doi.org/10.1007/s10787-024-01569-x. PMid:39342545.

17 Puchalski, M., Szparaga, G., Biela, T., Gutowska, A., Sztajnowski, S., & Krucińska, I. (2018). Molecular and supramolecular changes in Polybutylene Succinate (PBS) and Polybutylene Succinate Adipate (PBSA) copolymer during degradation in various environmental conditions. Polymers, 10(3), 251. https://doi.org/10.3390/polym10030251. PMid:30966286.

18 Grant, D. S., Ahmed, J., Whittle, J. D., Michelmore, A., Vasilev, K., Bazaka, K., & Jacob, M. V. (2021). Comparative study of natural terpenoid precursors in reactive plasmas for thin film deposition. Molecules, 26(16), 4762. https://doi.org/10.3390/molecules26164762. PMid:34443354.

19 Fridman, A. (2008). Plasma chemistry. Cambridge: Cambridge University Press. https://doi.org/10.1017/CBO9780511546075

20 National Institute of Standards and Technology – NIST. (2024). NIST Atomic Spectra Database (Version 5.12) (NIST Standard Reference Database, No. 78). Gaithersburg: NIST. https://doi.org/10.18434/T4W30F

21 Martínez-Ruiz, E. O. (2017). Partial oxidation of methane in a dielectric barrier discharge plasma milli-reactor (Doctoral thesis). Université Pierre et Marie Curie - Paris VI, Paris.

22 Friedrich, J. (2011). Mechanisms of plasma polymerization-reviewed from a chemical point of view. Plasma Processes and Polymers, 8(9), 783-802. https://doi.org/10.1002/ppap.201100038.

23 Chan, Y. W., Siow, K. S., Ng, P. Y., Gires, U., & Majlis, B. Y. (2016). Plasma polymerized carvone as an antibacterial and biocompatible coating. Materials Science and Engineering C, 68, 861-871. https://doi.org/10.1016/j.msec.2016.07.040. PMid:27524089.

24 Ruiz, E. O. M., Rao, X., García, A. F., Vega, C. G., Canche, C. N. A., López, J. A. G., Pérez, A. S. L., Medina, M. D. D., Gaona, C. G. C., Céspedes, R. I. N., Arguello, G. S., & Velázquez, M. G. N. (2023). Cold plasma copolymer with antimicrobial activity deposited on three different substrates. Polímeros, 33(4), e20230038. https://doi.org/10.1590/0104-1428.20220099.

25 Sun, P., Wu, H., Bai, N., Zhou, H., Wang, R., Feng, H., Zhu, W., Zhang, J., & Fang, J. (2012). Inactivation of Bacillus subtilis Spores in Water by a Direct‐Current, Cold Atmospheric‐Pressure Air Plasma Microjet. Plasma Processes and Polymers, 9(2), 157-164. https://doi.org/10.1002/ppap.201100041.

26 Desmet, T., Morent, R., De Geyter, N., Leys, C., Schacht, E., & Dubruel, P. (2009). Nonthermal Plasma Technology as a Versatile Strategy for Polymeric Biomaterials Surface Modification: A Review. Biomacromolecules, 10(9), 2351-2378. https://doi.org/10.1021/bm900186s. PMid:19655722.

27 Thompson, J. M. (2018). Infrared spectroscopy. Boca Raton: Jenny Stanford Publishing. https://doi.org/10.1201/9781351206037

28 Wang, B., Lu, C., Hu, J., & Lu, W. (2020). Property improvements of EVOH by enhancing the hydrogen bonding. Plastics. Plastics, Rubber and Composites, 49(1), 18-24. https://doi.org/10.1080/14658011.2019.1666465.

29 Larkin, P. (2011). Infrared and raman spectroscopy. Amsterdam: Elsevier. https://doi.org/10.1016/C2010-0-68479-3

30 Shenton, M. J., & Stevens, G. C. (2001). Surface modification of polymer surfaces: atmospheric plasma versus vacuum plasma treatments. Journal of Physics. D, Applied Physics, 34(18), 2761-2768. https://doi.org/10.1088/0022-3727/34/18/308.

31 Hochbaum, A. I., & Aizenberg, J. (2010). Bacteria Pattern Spontaneously on Periodic Nanostructure Arrays. Nano Letters, 10(9), 3717-3721. https://doi.org/10.1021/nl102290k. PMid:20687595.

32 American Society for Testing and Materials – ASTM. (2017). ASTM F756-17: Standard practice for assessment of hemolytic properties of materials. West Conshohocken: ASTM International.

33 Gonzalez-Prada, I., Borges, A., Santos-Torres, B., Magariños, B., Simões, M., Concheiro, A., & Alvarez-Lorenzo, C. (2024). Antimicrobial cyclodextrin-assisted electrospun fibers loaded with carvacrol, citronellol and cinnamic acid for wound healing. International Journal of Biological Macromolecules, 277(Pt 3), 134154. https://doi.org/10.1016/j.ijbiomac.2024.134154. PMid:39116822.

34 Pereira, R. L. S., Campina, F. F., Costa, M. S., Cruz, R. P., Freitas, T. S., Santos, A. T. L., Cruz, B. G., Sena Júnior, D. M., Lima, I. K. C., Xavier, M. R., Teixeira, A. M. R., Menezes, I. R. A., Quintans-Júnior, L. J., Araújo, A. A. S., & Coutinho, H. D. M. (2021). Antibacterial and modulatory activities of β-cyclodextrin complexed with (+)-β-citronellol against multidrug-resistant strains. Microbial Pathogenesis, 156, 104928. https://doi.org/10.1016/j.micpath.2021.104928. PMid:33957243.

35 Wu, Y., Hong, D., Qiu, S., Fang, Y., & Zhu, Y. (2024). Intrinsic antibacterial photopolymerization 3D-printed thermosets from citronellol and cinnamyl alcohol: synthesis and properties. Polymer Testing, 140, 108582. https://doi.org/10.1016/j.polymertesting.2024.108582.

36 Milovanovic, S., Markovic, D., Jankovic-Castvan, I., & Lukic, I. (2024). Cornstarch aerogels with thymol, citronellol, carvacrol, and eugenol prepared by supercritical CO2-assisted techniques for potential biomedical applications. Carbohydrate Polymers, 331, 121874. https://doi.org/10.1016/j.carbpol.2024.121874. PMid:38388060.
 

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