{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,19]],"date-time":"2026-10-19T19:06:57Z","timestamp":1792436817436,"version":"4.5.0"},"reference-count":51,"publisher":"MDPI AG","issue":"10","license":[{"start":{"date-parts":[[2026,5,19]],"date-time":"2026-05-19T00:00:00Z","timestamp":1779148800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>This study investigates the oxidative degradation of polystyrene (PS) through a synergistic framework integrating UV-C-accelerated aging with Reactive Molecular Dynamics (ReaxFF) simulations. To bridge the gap between experimental and computational timescales, shock compression was employed in the simulations as an accelerator of degradation reactions. ATR-FTIR spectroscopy revealed the emergence of carbonyl (1717 cm\u22121) and peroxyester (1760 cm\u22121) bands, alongside dominant ether-type oxygen bridges (1260, 1209 cm\u22121). These experimental data, particularly the depletion of native aromatic bands (1492, 1451 cm\u22121), provide direct empirical validation of the ring-ring cross-linking and radical-mediated oxidation pathways predicted by the ReaxFF model. The results demonstrate that theory-guided diagnostics offer a robust mechanism for understanding the atomic-level restructuring of the polymer matrix. Significantly, the formation of hydrophilic oxygenated groups increases the bioavailability and environmental hazard potential of fragmented PS microplastics, providing critical insights into their long-term ecological fate.<\/jats:p>","DOI":"10.3390\/molecules31101730","type":"journal-article","created":{"date-parts":[[2026,5,19]],"date-time":"2026-05-19T13:11:31Z","timestamp":1779196291000},"page":"1730","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Accelerated Oxidative Degradation of Polystyrene: Correlating UV Aging with Reactive Molecular Dynamics"],"prefix":"10.3390","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1271-3089","authenticated-orcid":false,"given":"Sylwia","family":"Pasieczna-Patkowska","sequence":"first","affiliation":[{"name":"Department of Chemical Technology, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University in Lublin, pl. Maria Curie-Sklodowska 3, 20031 Lublin, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7217-2758","authenticated-orcid":false,"given":"Marcin","family":"Cichy","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University in Lublin, pl. Maria Curie-Sklodowska 3, 20031 Lublin, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Monika","family":"Panczyk","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University in Lublin, pl. Maria Curie-Sklodowska 3, 20031 Lublin, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4132-5499","authenticated-orcid":false,"given":"Krzysztof","family":"Nieszporek","sequence":"additional","affiliation":[{"name":"Department of Theoretical Chemistry, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University in Lublin, pl. Maria Curie-Sklodowska 3, 20031 Lublin, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5487-119X","authenticated-orcid":false,"given":"Tomasz","family":"Panczyk","sequence":"additional","affiliation":[{"name":"Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30239 Cracow, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,5,19]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Houssini, K., Li, J., and Tan, Q. (2025). Complexities of the Global Plastics Supply Chain Revealed in a Trade-Linked Material Flow Analysis. Commun. Earth Environ., 6.","DOI":"10.1038\/s43247-025-02169-5"},{"key":"ref_2","unstructured":"OECD (2022). OECD Global Plastics Outlook: Economic Drivers, Environmental Impacts and Policy Options, OECD Publishing."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Sekar, V., Rao, Y.R.S., Tyagi, V.K., Singh, R., and Sundaram, B. (2026). Microplastics in Landfill Leachate: Sources, Potential Impacts, and Remediation Technologies. Curr. Pollut. Rep., 12.","DOI":"10.1007\/s40726-026-00394-w"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1513","DOI":"10.1039\/C5EM00207A","article-title":"Pathways for Degradation of Plastic Polymers Floating in the Marine Environment","volume":"17","author":"Gewert","year":"2015","journal-title":"Environ. Sci. Process. Impacts"},{"key":"ref_5","doi-asserted-by":"crossref","unstructured":"Gazeau, B., Minunno, R., Zaman, A., and Shaikh, F. (2024). Elevating Recycling Standards: Global Requirements for Plastic Traceability and Quality Testing. Sustainability, 16.","DOI":"10.3390\/su16125122"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"179","DOI":"10.1016\/j.aca.2020.11.002","article-title":"Impact of Weathering on the Chemical Identification of Microplastics from Usual Packaging Polymers in the Marine Environment","volume":"1142","year":"2021","journal-title":"Anal. Chim. Acta"},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Trusler, M.M., Kent, M.S., Lomax, B.H., Vane, C.H., and Cook, S. (2025). The Use of ATR-FTIR to Track the Degradation of Single-Use Polystyrene Cup Lids during 24 Months of Temperate Outdoor Exposure. PLoS ONE, 20.","DOI":"10.1371\/journal.pone.0330354"},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Lee, Q.Y., and Li, H. (2021). Photocatalytic Degradation of Plastic Waste: A Mini Review. Micromachines, 12.","DOI":"10.3390\/mi12080907"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2183","DOI":"10.1007\/s00203-021-02228-3","article-title":"Synergistic Effect of UV and Chemical Treatment on Biological Degradation of Polystyrene by Cephalosporium Strain NCIM 1251","volume":"203","author":"Chaudhary","year":"2021","journal-title":"Arch. Microbiol."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"9978","DOI":"10.1021\/acssuschemeng.4c02871","article-title":"Efficient Photolytic Breakdown of Waste Polystyrene Foam Using an \u201cAll-in-One\u201d Photo-HAT Reagent at Ambient Conditions","volume":"12","author":"Cakir","year":"2024","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Yousif, E., and Haddad, R. (2013). Photodegradation and Photostabilization of Polymers, Especially Polystyrene: Review. SpringerPlus, 2.","DOI":"10.1186\/2193-1801-2-398"},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Pino-Ramos, V.H., Bucio, E., Daza-G\u00f3mez, L.-C., and D\u00edaz, D. (2025). Photocatalytic Degradation of Polystyrene under Mild Conditions by Nanostructured Bismuth Carbonate. Polym. Degrad. Stab., 235.","DOI":"10.1016\/j.polymdegradstab.2025.111271"},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Jyoti, A., Kumar, D., Rasane, P., Ercisli, S., and Singh, J. (2026). Health Implications of Microplastic Exposure and Sustainable Solutions. Environ. Sci. Eur., 38.","DOI":"10.1186\/s12302-025-01296-2"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"5973","DOI":"10.1021\/acsomega.4c09953","article-title":"Comparison of Computational Methods for Simulating Depolymerization Reaction","volume":"10","author":"Mieda","year":"2025","journal-title":"ACS Omega"},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Wang, J., Bai, M., Zhuang, W., Wang, S., Zhang, S., Cai, S., and Huo, E. (2025). ReaxFF Reactive Molecular Dynamic Simulation and Density Functional Theory Calculation of Pyrolysis Mechanism and Electronic Characteristic of Lignin with the Addition of Plastics. Comput. Theor. Chem., 1254.","DOI":"10.1016\/j.comptc.2025.115511"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"10702","DOI":"10.1021\/acscatal.5c01263","article-title":"Molecular-Level Mechanistic Insights into PETase-Catalyzed Plastics Hydrolysis from Accurate QM\/MM Free Energy Calculations","volume":"15","author":"Berselli","year":"2025","journal-title":"ACS Catal."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"5211","DOI":"10.1007\/s10924-022-02578-z","article-title":"Degradation of Polyethylene Terephthalate Microplastics by Mineral Acids: Experimental, Molecular Modelling and Optimization Studies","volume":"30","author":"Chowdhury","year":"2022","journal-title":"J. Polym. Environ."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"6991","DOI":"10.1103\/PhysRevB.37.6991","article-title":"New Empirical Approach for the Structure and Energy of Covalent Systems","volume":"37","author":"Tersoff","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Stuart, S.J., Tutein, A.B., and Harrison, J.A. (2000). A Reactive Potential for Hydrocarbons with Intermolecular Interactions. J. Chem. Phys., 112.","DOI":"10.1063\/1.481208"},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"O\u2019Connor, T.C., Andzelm, J., and Robbins, M.O. (2015). AIREBO-M: A Reactive Model for Hydrocarbons at Extreme Pressures. J. Chem. Phys., 142.","DOI":"10.1063\/1.4905549"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1040","DOI":"10.1021\/jp709896w","article-title":"ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation","volume":"112","author":"Chenoweth","year":"2008","journal-title":"J. Phys. Chem. A"},{"key":"ref_22","doi-asserted-by":"crossref","unstructured":"Panczyk, T., Nieszporek, K., and Wolski, P. (2024). Modeling the Degradation of Polypropylene and Polystyrene under Shock Compression and Mechanical Cleaving Using the ReaxFF Force Field. Chemosphere, 357.","DOI":"10.1016\/j.chemosphere.2024.142056"},{"key":"ref_23","doi-asserted-by":"crossref","unstructured":"Bai, M., Huo, E., Wang, J., Zhang, Q., Wang, S., Cai, S., and Zhang, S. (2024). ReaxFF Reactive Molecular Dynamic and Density Functional Theory Study on the Co-Pyrolysis Mechanism of Waste 1,1,1,2-Tetrafluoroethane and Waste Plastics to Produce High Value-Added Chemicals and Fuels. Energy, 299.","DOI":"10.1016\/j.energy.2024.131505"},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Chen, J., Gaan, S., Heuberger, M., and Gooneie, A. (2026). When PET Meets Phosphorus Flame Retardants: A ReaxFF Molecular Dynamics Study. Polym. Degrad. Stab., 245.","DOI":"10.1016\/j.polymdegradstab.2025.111876"},{"key":"ref_25","doi-asserted-by":"crossref","unstructured":"Wolf, M., and Salvato Vallverdu, G. (2024). Reactive Molecular Dynamics Simulations of Plastics Pyrolysis with Additives: Comparison of ReaxFF Branches and Experimental Results. J. Anal. Appl. Pyrolysis, 177.","DOI":"10.1016\/j.jaap.2023.106266"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"5357","DOI":"10.1021\/acs.jpcb.9b04298","article-title":"Atomistic Scale Analysis of the Carbonization Process for C\/H\/O\/N-Based Polymers with the ReaxFF Reactive Force Field","volume":"123","author":"Kowalik","year":"2019","journal-title":"J. Phys. Chem. B"},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Polruang, S., Asokbunyarat, V., Bouthong, P., Rizqa, F., and Somprasong, A. (2025). Simulated Environmental Weathering of Expanded Polystyrene Foam and Polypropylene under UV and Wave Agitation. Sci. Rep., 15.","DOI":"10.1038\/s41598-025-22367-7"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"3263","DOI":"10.1021\/acs.analchem.4c04281","article-title":"\u03bc-FTIR Reflectance Spectroscopy Coupled with Multivariate Analysis: A Rapid and Robust Method for Identifying the Extent of Photodegradation on Microplastics","volume":"97","author":"Conterosito","year":"2025","journal-title":"Anal. Chem."},{"key":"ref_29","doi-asserted-by":"crossref","unstructured":"Ravelo, R., Holian, B., Germann, T., and Lomdahl, P. (2004). Constant-Stress Hugoniostat Method for Following the Dynamical Evolution of Shocked Matter. Phys. Rev. B, 70.","DOI":"10.1103\/PhysRevB.70.014103"},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Daymon, S.P., Olson, B.G., Reynolds, K.J., Zagho, M.M., Rothberg, M., Pisani, W.A., Bowman, A.L., Thornell, T.L., Shukla, M.K., and Nazarenko, S. (2025). Molecular Dynamics Simulation of Shock Compression in Polyisobutylene: Effect of Chain Orientation. Phys. Rev. Mater., 9.","DOI":"10.1103\/d6gj-nhhr"},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Boronat, C., Correcher, V., Garc\u00eda-Guinea, J., and Bravo-Yag\u00fce, J.C. (2024). Effects of UVC Irradiation on Polystyrene for Healthcare Packaging: Study by FTIR and Raman Spectroscopy with Thermoluminescence. Polym. Degrad. Stab., 222.","DOI":"10.1016\/j.polymdegradstab.2024.110700"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"10411","DOI":"10.1021\/acs.est.0c03221","article-title":"Foamed Polystyrene in the Marine Environment: Sources, Additives, Transport, Behavior, and Impacts","volume":"54","author":"Turner","year":"2020","journal-title":"Environ. Sci. Technol."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"11191","DOI":"10.1021\/acs.est.0c02288","article-title":"Rapid Production of Micro- and Nanoplastics by Fragmentation of Expanded Polystyrene Exposed to Sunlight","volume":"54","author":"Song","year":"2020","journal-title":"Environ. Sci. Technol."},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Chelomin, V.P., Dovzhenko, N.V., Slobodskova, V.V., Mazur, A.A., Kukla, S.P., and Zhukovskaya, A.F. (2023). Expanded Polystyrene-Debris-Induced Genotoxic Effect in Littoral Organisms. Toxics, 11.","DOI":"10.3390\/toxics11090781"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"4119","DOI":"10.1021\/ma00042a012","article-title":"Polystyrene Photooxidation. 1. Identification of the IR-Absorbing Photoproducts Formed at Short and Long Wavelengths","volume":"25","author":"Mailhot","year":"1992","journal-title":"Macromolecules"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1312","DOI":"10.1021\/acs.est.3c06498","article-title":"Single-Particle Analysis of the Photodegradation of Submicron Polystyrene Particles Using Infrared Photothermal Heterodyne Imaging","volume":"58","author":"Nwachukwu","year":"2024","journal-title":"Environ. Sci. Technol."},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Rabek, J.F. (1995). Polymer Photodegradation, Springer.","DOI":"10.1007\/978-94-011-1274-1"},{"key":"ref_38","unstructured":"Socrates, G. (2010). Infrared and Raman Characteristic Group Frequencies: Tables and Charts, Wiley. [3rd ed.]. repr. as paperback."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"321","DOI":"10.1016\/S0141-3910(00)00016-1","article-title":"Comparative Analysis of the Photo-Oxidation of Polystyrene and Poly(\u03b1-Methylstyrene)","volume":"68","author":"Mailhot","year":"2000","journal-title":"Polym. Degrad. Stab."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Campanale, C., Savino, I., Massarelli, C., and Uricchio, V.F. (2023). Fourier Transform Infrared Spectroscopy to Assess the Degree of Alteration of Artificially Aged and Environmentally Weathered Microplastics. Polymers, 15.","DOI":"10.3390\/polym15040911"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"6183","DOI":"10.1021\/acs.jcim.3c01153","article-title":"AmberTools","volume":"63","author":"Case","year":"2023","journal-title":"J. Chem. Inf. Model."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"W511","DOI":"10.1093\/nar\/gkr288","article-title":"R.E.D. Server: A Web Service for Deriving RESP and ESP Charges and Building Force Field Libraries for New Molecules and Molecular Fragments","volume":"39","author":"Vanquelef","year":"2011","journal-title":"Nucleic Acids Res."},{"key":"ref_43","doi-asserted-by":"crossref","unstructured":"Dupradeau, F.-Y., Pigache, A., Zaffran, T., Savineau, C., Lelong, R., Grivel, N., Lelong, D., Rosanski, W., and Cieplak, P. (2010). The R.E.D. Tools: Advances in RESP and ESP Charge Derivation and Force Field Library Building. Phys. Chem. Chem. Phys., 12.","DOI":"10.1039\/c0cp00111b"},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Thompson, A.P., Aktulga, H.M., Berger, R., Bolintineanu, D.S., Brown, W.M., Crozier, P.S., In \u2019T Veld, P.J., Kohlmeyer, A., Moore, S.G., and Nguyen, T.D. (2022). LAMMPS\u2014A Flexible Simulation Tool for Particle-Based Materials Modeling at the Atomic, Meso, and Continuum Scales. Comput. Phys. Commun., 271.","DOI":"10.1016\/j.cpc.2021.108171"},{"key":"ref_45","doi-asserted-by":"crossref","unstructured":"Nakatani, H., Ohshima, Y., Uchiyama, T., and Motokucho, S. (2022). Degradation and Fragmentation Behavior of Polypropylene and Polystyrene in Water. Sci. Rep., 12.","DOI":"10.1038\/s41598-022-23435-y"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"37590","DOI":"10.1039\/C8RA06448B","article-title":"Biofilm Formation by Exiguobacterium Sp. DR11 and DR14 Alter Polystyrene Surface Properties and Initiate Biodegradation","volume":"8","author":"Chauhan","year":"2018","journal-title":"RSC Adv."},{"key":"ref_47","doi-asserted-by":"crossref","unstructured":"Achhammer, B.G., Reiney, M.J., and Reinhart, F.W. (1951). Study of Degradation of Polystyrene, Using Infrared Spectrophotometry. J. Res. Natl. Bur. Stand., 47.","DOI":"10.6028\/jres.047.016"},{"key":"ref_48","unstructured":"Dole, M. (1973). The Radiation Chemistry of Macromolecules, Volume II, Academic Press."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1006\/jcph.1995.1039","article-title":"Fast Parallel Algorithms for Short-Range Molecular Dynamics","volume":"117","author":"Plimpton","year":"1995","journal-title":"J. Comput. Phys."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"245","DOI":"10.1016\/j.parco.2011.08.005","article-title":"Parallel Reactive Molecular Dynamics: Numerical Methods and Algorithmic Techniques","volume":"38","author":"Aktulga","year":"2012","journal-title":"Parallel Comput."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"3358","DOI":"10.1021\/j100161a070","article-title":"Charge Equilibration for Molecular Dynamics Simulations","volume":"95","author":"Rappe","year":"1991","journal-title":"J. Phys. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/31\/10\/1730\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,5,23]],"date-time":"2026-05-23T04:11:49Z","timestamp":1779509509000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/31\/10\/1730"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,5,19]]},"references-count":51,"journal-issue":{"issue":"10","published-online":{"date-parts":[[2026,5]]}},"alternative-id":["molecules31101730"],"URL":"https:\/\/doi.org\/10.3390\/molecules31101730","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,5,19]]}}}