2025 (1) 4
https://doi.org/10.15407/polymerj.47.01.030
INVESTIGATION OF THE BIODEGRADATION OF POLYURETHANE-UREAS CONTAINING FRAGMENTS OF GRAFT COPOLYMER POLYVINYL ALCOHOL–POLYETHYLENE GLYCOL IN THE STRUCTURE UNDER MODEL CONDITIONS OF THE INFLAMMATORY PROCESS
TETIANA VISLOHUZOVA1* (ORCID: 0000-0002-4071-4329), RITA ROZHNOVA1** (ORCID: 0000-0003-3284-3435), TETIANA KISELOVA1 (ORCID: 0000-0001-5606-6904), GALYNA KOZLOVA1 (ORCID: 0000-0001-8114-4812), LILIIA PALONA2 (ORCID: 0009-0008-0358-4538)
1Institute of Macromolecular Chemistry of the NAS of Ukraine, 48, Kharkivske Shose, Kyiv, 02155, Ukraine
2National University of Kyiv-Mohyla Academy, 2, Skovorody Street, Kyiv 04070, Ukraine
*e-mail: rudenchyk@gmail.com
**e-mail: rozhnovarita@gmail.com
Polimernyi Zhurnal, 2025, 47, no. 1: 30-38
Section: Medical polymers.
Language: English.
Abstract:
The aim of this study was to investigate the biodegradation capacity of hydrophilic polyurethane-ureas (PUUs) containing fragments of 4,4′-diaminodiphenylmethane (DADPh) and a grafted copolymer polyvinyl alcohol–polyethylene glycol (PVA–PEG) in their structure under model conditions of the inflammatory process when in contact with blood. The biodegradation capability was evaluated by infrared (IR) spectroscopy, physical-mechanical testing, and differential scanning calorimetry (DSC) by monitoring changes in the structure, physical-mechanical, and thermophysical properties of the PUUs under the influence of the Fenton reagent over incubation periods of 1, 3, and 6 months. According to IR spectroscopy data, exposure to the Fenton reagent initiates an oxidative degradation process of the investigated PUUs, accompanied by the cleavage of specific chemical bonds, alterations in hydrogen bonding, and structural transformations of the polymer matrix. The physical-mechanical properties depend on the incubation duration in the Fenton reagent and change nonlinearly. After 6 months of incubation, compared to the control, an increase in strength and relative elongation at break was observed, which can be explained by the formation of new hydrogen bonds under the influence of the model medium. DSC results revealed that after incubation in the Fenton reagent, the PUU samples exhibited an increase in the glass transition temperature (Tg) and a jump in heat capacity (ΔCp) at the glass transition, indicating structural changes during the oxidative degradation process. Thus, the investigated materials demonstrate the process of oxidative biodegradation under the influence of a model medium. Therefore, PUUs containing fragments of the grafted copolymer PVA–PEG in their structure represent a promising polymer matrix for temporary medical applications.
Keywords: polyurethane-urea, grafted copolymer polyvinyl alcohol–polyethylene glycol, oxidative biodegradation, Fenton reagent.
References
1. Vislohuzova T., Rozhnova R., Kiselova T., Kozlova G. Development and research of composite materials with dacarbazine based on polyurethane-urea with fragments of polyvinyl alcohol-polyethylene glycol graft copolymer in the structure. Polimernyi Zhurnal. 2024, 46, 2: 135-144. https://doi.org/10.15407/polymerj.46.02.135
2. Makadia H.K., Siegel S.J. Poly lactic-co-glycolic acid (PLGA) as biodegradable controlled drug delivery carrier. Polymers (Basel). 2011, 3, 3: 1377–1397. https://doi.org/10.3390/polym3031377
3. Visan A.I., Popescu-Pelin G., Socol G. Degradation behavior of polymers used as coating materials for drug delivery — A Basic Review. Polymers (Basel). 2021, 13, 8: 1272. https://doi.org/10.3390/polym13081272
4.Ansary R.H., Awang M.B., Rahman M.M. Biodegradable Poly(D,L-lactic-co-glycolic acid)-Based Micro/Nanoparticles for Sustained Release of Protein Drugs – A Review. Tropical Journal of Pharmaceutical Research. 2014, 13, 7:1179-1190. http://dx.doi.org/10.4314/tjpr.v13i7.24
5. Alexis F. Factors affecting the degradation and drug-release mechanism of poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)]. Polymer International.2005, 54, 1: 36–46. https://doi.org/10.1002/pi.1697
6. Ruan C., Hu N., Hu Y., Jiang L., Cai Q., Wang H., Pan H., Lu W.W., Wang Y. Piperazine-based polyurethane-ureas with controllable degradation as potential bone scaffolds. Polymer, 2014, 55, 4: 1020–1027.http://dx.doi.org/10.1016/j.polymer.2014.01.011
7.Ruan C., Hu Y., Jiang L., Cai Q., Pan H., Wang H. Tunable degradation of piperazine-based polyurethane ureas. Journal of Applied Polymer Science, 2014, 131, 19: 40527. https://doi.org/10.1002/app.40527
8. Reddy T.T., Kano A., Maruyama A., Takahara A. Synthesis, Characterization and Drug Release of Biocompatible/Biodegradable Non-toxic Poly(urethane urea)s Based on Poly(ε-caprolactone)s and Lysine-Based Diisocyanate. Journal of Biomaterials Science, Polymer Edition, 2010, 21, 11: 1483–1502. https://doi.org/10.1163/092050609X12518804794785
9.Deepa T., Lakshmi E. B., Kayalvizhi M., Arun A. Biodegradable poly(urethane-urea-amide): Synthesis, characterization and mechanical studies. Journal of Thermoplastic Composite Materials, 2020, 35, 12: 1-14.https://doi.org/10.1177/0892705720963537
10. Vislohuzova T., Rozhnova R., Kiselova T., Kozlova G. In Vitro investigation of the biodegradation capacity of polyurethane-ureas with grafted copolymer fragments of polyvinyl alcohol-polyethylene glycol in structure. Polimernyi Zhurnal. 2024, 46, 3: 226–233. https://doi.org/10.15407/polymerj.46.03.226
11. Novo E., Parola M. Redox mechanisms in hepatic chronic wound healing and fibrogenesis. Fibrogenesis & Tissue Repair. 2008, 1: 5 https://doi.org/10.1186/1755-1536-1-5
12. Mamenko T.P., Kots S.Ya. Lipid peroxidation of cell membranes in the formation and regulation of plant protective reactions. Ukrainian Botanical Journal, 2020. 77, 4: 331–343. https://doi.org/10.15407/ukrbotj77.04.331
13. Kril Y., Havrylyuk A. M., Chopyak V. V., Kit Yu. Ya., Kotsiuruba A. V., Stoika R. S. The functional activity changes in rat’s neutrophils in experimental collagen arthritis. The Animal Biology. 2014, 16, 3: 60-67.
14. Smith B. C. Infrared Spectroscopy of Polymers XIII: Polyurethanes. Spectroscopy. 2023, 38, 7: 14–16. https://doi.org/10.56530/spectroscopy.fn3378a3
15. Tai N.L., Adhikari R., Shanks R., Adhikari B. Aerobic biodegradation of starch–polyurethane flexible films under soil burial condition: Changes in physical structure and chemical composition. International Biodeterioration & Biodegradation. 2019, 145, 104793. https://doi.org/10.1016/j.ibiod.2019.104793
16. Rozhnova R., Ostapenko S., Galatenko N. Investigation of biodegradation of biological active block-copolyurethane with amison in vitro. Naukovi Zapysky NaUKMa. 2010, 105: 32-36