Early swelling kinetics of chitosan hydrogels under different acidity conditions for designing controlled-release fertilizers
-
DOI:
https://doi.org/10.61511/aes.v4i1.2026.3710Keywords:
biodegradable, chitosan, hydrogel, pH, swellingAbstract
Background: Nutrient losses from conventional fertilization have increased the need for biodegradable hydrogel matrices that improve water retention and support controlled-release fertilizer (CRF) systems. This study investigated the effects of pH on the early-stage swelling kinetics of chitosan-based hydrogels, identified the most stable formulation, and examined the relationship between the degree of deacetylation (DD) and swelling performance. Methods: A quantitative experimental design was applied to four formulations, namely ChGu, ChG, ChPu, and ChP, under acidic, neutral, and alkaline conditions. Swelling was measured over 120 minutes with replicate measurements. The analysis included the swelling ratio (SR), maximum swelling ratio (Max SR), area under the curve (AUC), net swelling change (ΔSR), means, standard deviations, statistical comparisons, and regression analysis. Findings: pH markedly influenced the swelling behavior of all formulations. Neutral conditions produced the highest average SR values, with ChP showing the best performance (86.4), followed by ChG (67.6), ChGu (63.8), and ChPu (30.4). ChP also recorded the highest Max SR (124) and AUC (11,100), while ChG reached a Max SR of 110 and an AUC of 9,150. These findings indicate that both formulations had greater expansion capacity and more sustained swelling. In contrast, alkaline conditions caused deswelling in most samples, as indicated by negative SR values. The relationship between DD and swelling performance was weak (R² = 0.14), indicating that hydrogel structure, formulation composition, environmental pH, and early kinetic transitions were more influential than DD alone. Conclusion: Neutral pH provided the most favorable swelling conditions, and ChP demonstrated the strongest overall performance. Novelty/Originality of this article: This study proposes Max SR, AUC, ΔSR, and dynamic transition intervals as integrated early-stage indicators for screening biodegradable chitosan hydrogels for CRF applications.
References
Ahmad, D. F. B. A., Wasli, M. E., Tan, C. S. Y., et al. (2023). Eco-friendly cellulose-based hydrogels derived from wastepapers as a controlled-release fertilizer. Chemical and Biological Technologies in Agriculture, 10(36): 1-10. https://doi.org/10.1186/s40538-023-00407-6
Ardean, C., Davidescu, C. M., Nemeş, N. S., Negrea, A., Ciopec, M., Duteanu, N., Negrea, P., Duda-Seiman, D., & Musta, V. (2021). Factors influencing the antibacterial activity of chitosan and chitosan modified by functionalization. International Journal of Molecular Sciences, 22(14), 7449. https://doi.org/10.3390/ijms22147449
Badan Penelitian dan Pengembangan Pertanian. (2020). Location-specific recommendations for N, P, and K fertilizers for rice, maize, and soybean in paddy fields (by district): Book I: Rice. Ministry of Agriculture. Retrieved from: https://repository.pertanian.go.id/server/api/core/bitstreams/6c2d7931-53fa-46ea-ad60-cbfab9181fae/content
Budianto, E., & Amalia, A. (2020). Swelling behavior and mechanical properties of chitosan-poly(N-vinyl-pyrrolidone) hydrogels. Journal of Polymer Engineering, 40(7), 551–560. https://doi.org/10.1515/polyeng-2019-0169
Carpa, R., Remizovschi, A., Culda, C. A., & Butiuc-Keul, A. L. (2022). Inherent and composite hydrogels as promising materials to limit antimicrobial resistance. Gels, 8(2), Article 70. https://doi.org/10.3390/gels8020070
Chandran, V., Shaji, H., & Mathew, L. (2021). Methods for controlled release of fertilizers. In Controlled release fertilizers for sustainable agriculture (pp. 79–93). Academic Press. https://doi.org/10.1016/B978-0-12-819555-0.00005-4
Chiaregato, C. G., França, D., Messa, L. L., Pereira, T. dos S., & Faez, R. (2022). A review of advances over 20 years on polysaccharide-based polymers applied as enhanced efficiency fertilizers. Carbohydrate Polymers, 279, Article 119014. https://doi.org/10.1016/j.carbpol.2021.119014
Dou, Z., Bini Farias, M. V., Chen, W., He, D., Hu, Y., & Xie, X. (2023). Highly degradable chitosan-montmorillonite (MMT) nano-composite hydrogel for controlled fertilizer release. Frontiers of Environmental Science & Engineering, 17, Article 53. https://doi.org/10.1007/s11783-023-1653-9
Eddarai, E. M., El Mouzahim, M., Ragaoui, B., Eladaoui, S., Bourd, Y., Bellaouchou, A., & Boussen, R. (2024). Review of current trends in chitosan based controlled and slow-release fertilizer: From green chemistry to circular economy. International Journal of Biological Macromolecules, 278(Part 4), Article 134982. https://doi.org/10.1016/j.ijbiomac.2024.134982
Firmanda, A., Fahma, F., Syamsu, K., Mahardika, M., Suryanegara, L., Munif, A., Gozan, M., Wood, K., Hidayat, R., & Yulia, D. (2024). Biopolymer-based slow/controlled-release fertilizer (SRF/CRF): Nutrient release mechanism and agricultural sustainability. Journal of Environmental Chemical Engineering, 12(2), Article 112177. https://doi.org/10.1016/j.jece.2024.112177
Flatian, A. N., Rachmadhani, A. F., & Suryadi, E. (2020). Efficiency of nitrogen fertilization in sweet corn due to different urea doses and application timing using the ¹⁵N isotope technique. Journal of Soil and Climate, 44(2), 93–100. https://doi.org/10.21082/jti.v44n2.2020.93-100
Govil, S., Long, N. V. D., Escribà-Gelonch, M., & Hessel, V. (2024). Controlled-release fertiliser: Recent developments and perspectives. Industrial Crops and Products, 219, Article 119160. https://doi.org/10.1016/j.indcrop.2024.119160
Hellmann, M. J., Gillet, D., Trombotto, S., Raetz, S., Moerschbacher, B. M., & Cord-Landwehr, S. (2024). Heterogeneously deacetylated chitosans possess an unexpected regular pattern favoring acetylation at every third position. Nature Communications, 15, Article 6695. https://doi.org/10.1038/s41467-024-50857-1
Hong, F., Qiu, P., Wang, Y., Ren, P., Liu, J., Zhao, J., & Gou, D. (2024). Chitosan-based hydrogels: From preparation to applications, a review. Food Chemistry: X, 21, Article 101095. https://doi.org/10.1016/j.fochx.2023.101095
Irfan, S. A., Azeem, B., Irshad, K., Algarni, S., KuShaari, K., Islam, S., & Abdelmohimen, M. A. H. (2020). Machine learning model for nutrient release from biopolymers coated controlled-release fertilizer. Agriculture, 10(11), Article 538. https://doi.org/10.3390/agriculture10110538
Jariwala, H., Santos, R. M., Lauzon, J. D., Dutta, A., & Chiang, Y. W. (2022). Controlled release fertilizers (CRFs) for climate-smart agriculture practices: A comprehensive review on release mechanism, materials, methods of preparation, and effect on environmental parameters. Environmental Science and Pollution Research, 29, 53967–53995. https://doi.org/10.1007/s11356-022-20890-y
Katchali, M., Richard, E., Tonnang, H. E. Z., Tanga, C. M., Beesigamukama, D., & Senagi, K. (2025). Mathematical and computational modeling for organic and insect frass fertilizer production: A systematic review. PLOS ONE, 20(1), Article e0292418. https://doi.org/10.1371/journal.pone.0292418
Kaya, M., Mujtaba, M., Ehrlich, H., Salaberria, A. M., Baran, T., Amemiya, C. T., Galli, R., Akyuz, L., Sargin, I., & Labidi, J. (2017). On chemistry of γ-chitin. Carbohydrate Polymers, 176, 177–186. https://doi.org/10.1016/j.carbpol.2017.08.076
Klein, M., & Poverenov, E. (2020). Natural biopolymer-based hydrogels for use in food and agriculture. Journal of the Science of Food and Agriculture, 100(6), 2337–2347. https://doi.org/10.1002/jsfa.10274
Kumar, A., Sood, A., Agrawal, G., Thakur, S., Thakur, V. K., Tanaka, M., Mishra, Y. K., Christie, G., Mostafavi, E., Boukherroub, R., Hutmacher, D. W., & Han, S. S. (2023). Polysaccharides, proteins, and synthetic polymers based multimodal hydrogels for various biomedical applications: A review. International Journal of Biological Macromolecules, 247, Article 125606. https://doi.org/10.1016/j.ijbiomac.2023.125606
Lawrencia, D., Wong, S. K., Low, D. Y. S., Goh, B. H., Goh, J. K., Ruktanonchai, U. R., Soottitantawat, A., Lee, L. H., & Tang, S. Y. (2021). Controlled release fertilizers: A review on coating materials and mechanism of release. Plants, 10(2), Article 238. https://doi.org/10.3390/plants10020238
Li, H., Wang, J., Luo, Y., Bai, B., & Cao, F. (2022). pH-responsive eco-friendly chitosan-chlorella hydrogel beads for water retention and controlled release of humic acid. Water, 14(8), Article 1190. https://doi.org/10.3390/w14081190
Lipin, A. A., Lipin, A. G., & Wójtowicz, R. (2023). Modelling nutrient release from controlled release fertilisers. Biosystems Engineering, 234, 81–91. https://doi.org/10.1016/j.biosystemseng.2023.08.015
Liu, H., Huang, Z., Shi, Y., Cai, T., Miao, Q., Gao, Z., & Cui, Z. (2024). Lightweight pH-responsive chitosan hydrogel iron fertilizer: Efficient performance, controlled-release, and tomato application. Journal of Environmental Chemical Engineering, 12(5), Article 113428. https://doi.org/10.1016/j.jece.2024.113428
Márton, P., Szolnoki, B., Nagy, N., Deák, A., Zámbó, D., Szabó, G. S., & Hórvölgyi, Z. (2024). Wetting and swelling behaviour of N-acetylated thin chitosan coatings in aqueous media. Heliyon, 10(1), Article e23201. https://doi.org/10.1016/j.heliyon.2023.e23201
Mikhailidi, A., Ungureanu, E., Tofanica, B.-M., Ungureanu, O. C., Fortună, M. E., Belosinschi, D., & Volf, I. (2024). Agriculture 4.0: Polymer hydrogels as delivery agents of active ingredients. Gels, 10(6), Article 368. https://doi.org/10.3390/gels10060368
Namli, S., Guven, O., Simsek, F. N., Gradišek, A., Sumnu, G., Yener, M. E., & Oztop, M. (2023). Effects of deacetylation degree of chitosan on the structure of aerogels. International Journal of Biological Macromolecules, 250, Article 126123. https://doi.org/10.1016/j.ijbiomac.2023.126123
Nunziata, G., Pollonio, D., Lacroce, E., & Rossi, F. (2025). Smart pH‑responsive polymers in biomedical applications: Nanoparticles, hydrogels, and emerging hybrid platforms. Materials Today Chemistry, 49, 103063. https://doi.org/10.1016/j.mtchem.2025.103063
Piccoli, I., Camarotto, C., Squartini, A., et al. (2024). Hydrogels for agronomical application: From soil characteristics to crop growth: A review. Agronomy for Sustainable Development, 44(22): 1-23. https://doi.org/10.1007/s13593-024-00958-4
Piroonpan, T., Huajaikaew, E., Kurantowicz, N., Potiyaraj, P., & Pasanphan, W. (2024). pH-responsive chitosan nanoparticles for controlled-release nitrogen fertilizer: Template-tampering free radical graft copolymerization under energetic radiation study. European Polymer Journal, 203, Article 112670. https://doi.org/10.1016/j.eurpolymj.2023.112670
Protsak, I. S., & Morozov, Y. M. (2025). Fundamentals and advances in stimuli-responsive hydrogels and their applications: A review. Gels, 11(1), Article 30. https://doi.org/10.3390/gels11010030
Rachmatpour, A., & Alizadeh, A. H. (2024). Biofilm hydrogel derived from physical crosslinking (self-assembly) of xanthan gum and chitosan for removing Cd2+, Ni2+, and Cu2+ from aqueous solution. International Journal of Biological Macromolecules, 266(Part 2), Article 131394. https://doi.org/10.1016/j.ijbiomac.2024.131394
Roas-Escalona, N., Becquart, F., Delair, T., & Dutertre, F. (2024). Chitosan-based hydrogels: Influence of crosslinking strategy on rheological properties. Carbohydrate Polymers, 341, Article 122329. https://doi.org/10.1016/j.carbpol.2024.122329
Rodríguez-Rodríguez, R., Carreón-Álvarez, C., Cruz-Medina, C. A., Knauth, P., López, Z., Fletes-Vargas, G., & Rodríguez Sahagún, M. (2025). A review of pH-responsive chitosan-based hydrogels for drug delivery applications. European Polymer Journal, 237, Article 114173. https://doi.org/10.1016/j.eurpolymj.2025.114173
Strotmann, U., Thouand, G., Pagga, U., Gartiser, S., & Heipieper, H. J. (2023). Toward the future of OECD/ISO biodegradability testing-new approaches and developments. Applied Microbiology and Biotechnology, 107(7–8), 2073–2095. https://doi.org/10.1007/s00253-023-12406-6
Tian, B., & Liu, J. (2023). Smart stimuli-responsive chitosan hydrogel for drug delivery: A review. International Journal of Biological Macromolecules. https://doi.org/10.1016/j.ijbiomac.2023.123902
Thirupathi, K., Raorane, C. J., Ramkumar, V., Ulagesan, S., Santhamoorthy, M., Raj, V., Krishnakumar, G. S., Phan, T. T. V., & Kim, S.-C. (2023). Update on chitosan-based hydrogels: Preparation, characterization, and its antimicrobial and antibiofilm applications. Gels, 9(1), Article 35. https://doi.org/10.3390/gels9010035
VanZanten, A., Chen, S.-Y., Driscoll, M. M., & Szczepanski, C. R. (2024). Unconstrained dynamic gel swelling generates transient surface deformations. Soft Matter, 20, 6742–6753. https://doi.org/10.1039/D4SM00762J
Wang, C., Yu, Y., Chen, H., Zhang, S., Wang, J., & Liu, C. (2019). Construction of cytokine reservoirs based on sulfated chitosan hydrogels for the capturing of VEGF in situ. Journal of Materials Chemistry B, 7(16), 2785–2793. https://doi.org/10.1039/C8TB02895H
Yang, H.-B., Xing, L.-Y., Liu, T.-F., Li, M., Geng, J., Zhang, Y., Zhang, Y.-B., Wang, R.-C., Sarsenbekuly, B., Kang, W.-L., & Zhang, L.-M. (2025). Swelling kinetics of polymer microspheres used for conformance control and their matching mechanisms with oil reservoir fractures. Petroleum Science, 22(12), 5203–5211. https://doi.org/10.1016/j.petsci.2025.11.011
Yıldırım, M., Poyraz, S., Acet, Ö., Önal Acet, B., Karakoç, V., & Odabaşı, M. (2025). Chitosan hydrogels: Versatile platforms for drug delivery in cancer treatment, wound dressing, and 3D bioprinting applications. International Journal of Biological Macromolecules. https://doi.org/10.1016/j.ijbiomac.2025.144367
Zhao, L., Zhou, Y., Zhang, J., Liang, H., Chen, X., & Tan, H. (2023). Natural polymer-based hydrogels: From polymer to biomedical applications. Pharmaceutics, 15(10), Article 2514. https://doi.org/10.3390/pharmaceutics15102514
Žigrayová, D., Mikušová, V., & Mikuš, P. (2024). Advances in chitosan derivatives: Preparation, properties and applications in pharmacy and medicine. Gels, 10(11), Article 701. https://doi.org/10.3390/gels10110701
Published
How to Cite
Issue
Section
Citation Check
License
Copyright (c) 2026 Sinta Ramadhania Putri Maresi, Tri Sutanti Budikania, Kartini Afriani, Achmad Nandang Roziafanto, Ahmad Dzaky Mualim, Fareka Kholidanata

This work is licensed under a Creative Commons Attribution 4.0 International License.















