{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,23]],"date-time":"2026-01-23T21:09:17Z","timestamp":1769202557058,"version":"3.49.0"},"reference-count":37,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2026,1,22]],"date-time":"2026-01-22T00:00:00Z","timestamp":1769040000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"European Union\u2014NextGenerationEU under the National Recovery and Resilience Plan","award":["0001052"],"award-info":[{"award-number":["0001052"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The widespread occurrence of pharmaceutical residues in aquatic environments necessitates the development of advanced porous materials for efficient remediation. This study investigates the adsorption mechanisms of ibuprofen and atenolol within the high-silica zeolite Y. Batch adsorption experiments demonstrated significant uptake, with loading capacities of 191.6 mg\/g for ibuprofen and 273.0 mg\/g for atenolol, confirming the material\u2019s effectiveness. Using a combination of neutron and X-ray powder diffraction, complemented by Rietveld refinement and simulated annealing algorithms, we achieved the exact localization of the guest molecules. While the pristine zeolite maintains cubic symmetry Fd3\u00af, the incorporation of pharmaceutical molecules induces significant residual nuclear density and anisotropic lattice distortions. To accurately model these perturbations, a systematic symmetry reduction to the acentric triclinic space group F1 was implemented. This approach enabled an ab initio refinement of the structure, revealing that drug uptake of each guest is governed by distinct chemical drivers. Ibuprofen is stabilized via steric confinement and long-range dispersive interactions. In contrast, atenolol stability is governed by electrostatic charge compensation within the zeolitic voids. Our results suggest that the final adsorption geometry is dictated by the spatial orientation of functional groups and host\u2013guest proximity rather than molecular chirality. These results provide a microscopic model describing the fundamental host\u2013guest interactions in FAU zeolites. This structural understanding is an essential step towards the potential use of zeolitic materials in environmental remediation and complex guest sequestration.<\/jats:p>","DOI":"10.3390\/molecules31020384","type":"journal-article","created":{"date-parts":[[2026,1,23]],"date-time":"2026-01-23T17:52:38Z","timestamp":1769190758000},"page":"384","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Combined Neutron and X-Ray Diffraction Study of Ibuprofen and Atenolol Adsorption in Zeolite Y"],"prefix":"10.3390","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6467-881X","authenticated-orcid":false,"given":"Annalisa","family":"Martucci","sequence":"first","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1, I-44121 Ferrara, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1389-9292","authenticated-orcid":false,"given":"Maura","family":"Mancinelli","sequence":"additional","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1, I-44121 Ferrara, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3175-322X","authenticated-orcid":false,"given":"Tatiana","family":"Chenet","sequence":"additional","affiliation":[{"name":"Department of Environmental and Prevention Sciences, University of Ferrara, Via L. Borsari 46, I-44121 Ferrara, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-8530-3953","authenticated-orcid":false,"given":"Luca","family":"Adami","sequence":"additional","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1, I-44121 Ferrara, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Caterina","family":"D\u2019anna","sequence":"additional","affiliation":[{"name":"Department of Environmental and Prevention Sciences, University of Ferrara, Via L. Borsari 46, I-44121 Ferrara, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5966-5929","authenticated-orcid":false,"given":"Emmanuelle","family":"Suard","sequence":"additional","affiliation":[{"name":"Institute Max von Laue and Paul Langevin, D2B Beamline, BP156, 38042 Grenoble, France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2980-3654","authenticated-orcid":false,"given":"Luisa","family":"Pasti","sequence":"additional","affiliation":[{"name":"Department of Environmental and Prevention Sciences, University of Ferrara, Via L. Borsari 46, I-44121 Ferrara, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2026,1,22]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"140043","DOI":"10.1016\/j.scitotenv.2020.140043","article-title":"Toxicity of the Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) acetylsalicylic acid, paracetamol, diclofenac, ibuprofen and naproxen towards freshwater invertebrates: A review","volume":"740","author":"Parolini","year":"2020","journal-title":"Sci. Total Environ."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"122","DOI":"10.1016\/j.aquatox.2005.09.009","article-title":"Ecotoxicology of human pharmaceuticals","volume":"76","author":"Fent","year":"2006","journal-title":"Aquat. Toxicol."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1016\/j.jhazmat.2009.10.100","article-title":"Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment","volume":"175","author":"Santos","year":"2010","journal-title":"J. Hazard. Mater."},{"key":"ref_4","first-page":"823","article-title":"Pharmaceuticals in the environment\u2014Global occurrences and perspectives","volume":"35","author":"Weber","year":"2016","journal-title":"Environ. Toxicol. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"112777","DOI":"10.1016\/j.envres.2022.112777","article-title":"Ibuprofen exposure in Europe; ePiE as an alternative to costly environmental monitoring","volume":"209","author":"Austin","year":"2022","journal-title":"Environ. Res."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1007\/s10311-020-01065-y","article-title":"Analysis, fate and toxicity of chiral non-steroidal anti-inflammatory drugs in wastewaters and the environment: A review","volume":"19","author":"Petrie","year":"2021","journal-title":"Environ. Chem. Lett."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1831","DOI":"10.1080\/10934520600779000","article-title":"Biodegradability and toxicity of pharmaceuticals in biological wastewater treatment plants","volume":"41","author":"Carucci","year":"2006","journal-title":"J. Environ. Sci. Health A"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"514","DOI":"10.1897\/IEAM_2009-050.1","article-title":"Environmental risk assessment of human pharmaceuticals in the European Union: A case study with the beta-blocker atenolol","volume":"6","author":"Alder","year":"2010","journal-title":"Integr. Environ. Assess. Manag."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Mancinelli, M., and Martucci, A. (2025). Exploring the Potential of Zeolites for Sustainable Environmental Applications. Sustain. Chem., 6.","DOI":"10.20944\/preprints202501.0157.v1"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"133166","DOI":"10.1016\/j.cej.2021.133166","article-title":"Lanthanum carbonate grafted ZSM-5 for superior phosphate uptake: Investigation of the growth and adsorption mechanism","volume":"430","author":"Yang","year":"2022","journal-title":"Chem. Eng. J."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"58","DOI":"10.1016\/j.micromeso.2015.10.034","article-title":"Natural zeolites for pharmaceutical formulations: Preparation and evaluation of a clinoptilolite-based material","volume":"223","author":"Cerri","year":"2016","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"137","DOI":"10.1016\/j.chemosphere.2018.04.085","article-title":"Equilibrium and kinetic studies of the adsorption of antibiotics from aqueous solutions onto powdered zeolites","volume":"205","author":"Insa","year":"2018","journal-title":"Chemosphere"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"345","DOI":"10.1016\/j.apcatb.2018.08.015","article-title":"An advanced oxidation process by photoexcited heterogeneous sodium decatungstate for the degradation of drugs present in aqueous environment","volume":"239","author":"Pasti","year":"2018","journal-title":"Appl. Catal. B Environ."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Belviso, C., Guerra, G., Abdolrahimi, M., Peddis, D., Maraschi, F., Cavalcante, F., Ferretti, M., Martucci, A., and Sturini, M. (2021). Efficiency in ofloxacin antibiotic water remediation by magnetic zeolites formed combining pure sources and wa1stes. Processes, 9.","DOI":"10.3390\/pr9122137"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"978","DOI":"10.1002\/open.202000183","article-title":"L-lysine amino acid adsorption on zeolite L: A combined synchrotron, X-ray and neutron diffraction study","volume":"9","author":"Beltrami","year":"2020","journal-title":"ChemistryOpen"},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Altomare, A., Capitelli, F., Corriero, N., Cuocci, C., Falcicchio, A., Moliterni, A., and Rizzi, R. (2018). The Rietveld refinement in the EXPO software: A powerful tool at the end of the elaborate crystal structure solution pathway. Crystals, 8.","DOI":"10.3390\/cryst8050203"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"111465","DOI":"10.1016\/j.commatsci.2022.111465","article-title":"Direct space approach in action: Challenging structure solution of microcrystalline materials using the EXPO software","volume":"210","author":"Cuocci","year":"2022","journal-title":"Comput. Mater. Sci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"184312","DOI":"10.1063\/1.4874258","article-title":"A combined experimental and computational study of the molecular interactions between anionic ibuprofen and water","volume":"140","author":"Guerra","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1378","DOI":"10.1107\/S0108270193000629","article-title":"Structure of (S)-(+)-ibuprofen","volume":"49","author":"Freer","year":"1993","journal-title":"Acta Crystallogr. Sect. C Cryst. Struct. Commun."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/j.ijpharm.2007.04.023","article-title":"The molecular conformation of Ibuprofen, C13H18O2, through X-ray diffuse scattering","volume":"343","author":"Goossens","year":"2007","journal-title":"Int. J. Pharm."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"6484","DOI":"10.1021\/acs.jctc.8b00702","article-title":"Dynamics and thermodynamics of ibuprofen conformational isomerism at the crystal-solution interface","volume":"14","author":"Marinova","year":"2018","journal-title":"J. Chem. Theory Comput."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"999","DOI":"10.1007\/s11224-016-0893-8","article-title":"Structural stability of diclofenac vs. inhibition activity from ab initio molecular dynamics simulations. Comparative study with ibuprofen and ketoprofen","volume":"28","author":"Kozlowska","year":"2017","journal-title":"Struct. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"118","DOI":"10.1080\/0889311X.2016.1251909","article-title":"The way from isostructurality to polymorphism. Where are the borders? The role of supramolecular interactions and crystal symmetries","volume":"23","author":"Bombicz","year":"2017","journal-title":"Crystallogr. Rev."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Gackowski, M., and Paczwa, M. (2021). The impact of hydration and dehydration on the mobility and location of ibuprofen molecules in the voids of ultra-stable zeolite Y. Materials, 14.","DOI":"10.3390\/ma14247823"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"496","DOI":"10.1021\/cg0601857","article-title":"Conformational isomorphism of organic crystals: Racemic and homochiral atenolol","volume":"7","author":"Canotilho","year":"2007","journal-title":"Cryst. Growth Des."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Altomare, A., Corriero, N., Cuocci, C., Falcicchio, A., and Rizzi, R. (2019). Solving a structure in the reciprocal space, real space and both by using the EXPO software. Crystals, 10.","DOI":"10.3390\/cryst10010016"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1589","DOI":"10.1007\/s11224-024-02306-4","article-title":"Elucidation of the enantiomer migration order of atenolol by theoretical calculations","volume":"35","author":"Maia","year":"2024","journal-title":"Struct. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"113741","DOI":"10.1016\/j.comptc.2022.113741","article-title":"Chiral separation study of atenolol and carvedilol beta-blocker drugs by DFT calculations","volume":"1213","author":"Maia","year":"2022","journal-title":"Comput. Theor. Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"357","DOI":"10.1016\/j.molstruc.2010.12.014","article-title":"Spectroscopic and DFT study of atenolol and metoprolol and their copper complexes","volume":"993","author":"Cozar","year":"2011","journal-title":"J. Mol. Struct."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1194","DOI":"10.1016\/j.saa.2006.10.007","article-title":"Infrared spectroscopy of racemic and enantiomeric forms of atenolol","volume":"67","author":"Canotilho","year":"2007","journal-title":"Spectrochim. Acta A Mol. Biomol. Spectrosc."},{"key":"ref_31","unstructured":"Larson, A.C., and Von Dreele, R.B. (2004). General Structure Analysis System (GSAS)."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"210","DOI":"10.1107\/S0021889801002242","article-title":"EXPGUI, a graphical user interface for GSAS","volume":"34","author":"Toby","year":"2001","journal-title":"J. Appl. Crystallogr."},{"key":"ref_33","first-page":"28284","article-title":"Removing pharmaceuticals from water with natural and modified zeolites: Kinetics, thermodynamics, and competitive adsorption in a multi-drug system","volume":"41","author":"Demiti","year":"2025","journal-title":"Langmuir"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"308","DOI":"10.1021\/cm0011559","article-title":"A new property of MCM-41: Drug delivery system","volume":"13","year":"2001","journal-title":"Chem. Mater."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1459","DOI":"10.1016\/j.solidstatesciences.2006.07.016","article-title":"Controlled release of Ibuprofen from dealuminated faujasites","volume":"8","author":"Horcajada","year":"2006","journal-title":"Solid State Sci."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"11","DOI":"10.1180\/claymin.2015.050.1.02","article-title":"Ibuprofen sorption and release by modified natural zeolites as prospective drug carriers","volume":"50","year":"2015","journal-title":"Clay Miner."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"111260","DOI":"10.1016\/j.envres.2021.111260","article-title":"Ibuprofen elimination from water and wastewater using sonication\/ultraviolet\/hydrogen peroxide\/zeolite-titanate photocatalyst system","volume":"198","author":"Farhadi","year":"2021","journal-title":"Environ. Res."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/31\/2\/384\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,1,23]],"date-time":"2026-01-23T17:53:09Z","timestamp":1769190789000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/31\/2\/384"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,1,22]]},"references-count":37,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2026,1]]}},"alternative-id":["molecules31020384"],"URL":"https:\/\/doi.org\/10.3390\/molecules31020384","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,1,22]]}}}