Tackling antibiotic contaminations in wastewater with novel Modified-MOF nanostructures: A study of molecular simulations and DFT calculations

Iman Salahshoori; Majid Namayandeh Jorabchi; Afsaneh Mazaheri; Seyedeh Masoomeh Sadat Mirnezami; Mahdis Afshar; Mahdi Golriz; Marcos A L Nobre

doi:10.1016/j.envres.2024.118856

Tackling antibiotic contaminations in wastewater with novel Modified-MOF nanostructures: A study of molecular simulations and DFT calculations

Environ Res. 2024 Apr 8;252(Pt 2):118856. doi: 10.1016/j.envres.2024.118856. Online ahead of print.

Authors

Iman Salahshoori¹, Majid Namayandeh Jorabchi², Afsaneh Mazaheri³, Seyedeh Masoomeh Sadat Mirnezami⁴, Mahdis Afshar⁴, Mahdi Golriz⁵, Marcos A L Nobre⁶

Affiliations

¹ Department of Polymer Processing, Iran Polymer and Petrochemical Institute, Tehran, Iran; Department of Chemical Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran. Electronic address: i.salahshoori@ippi.ac.ir.
² Leibniz Institute for Catalysis, Albert-Einstein-Straße 29a, D-18059 Rostock, Germany; Department of Chemical Engineering, Quchan University of Technology, Quchan, Iran. Electronic address: majid.jorabchi@catalysis.de.
³ Department of Civil and Environmental Engineering, Faculty of Engineering, University of Birjand, Birjand, Iran.
⁴ Department of Chemical Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran.
⁵ Department of Polymer Processing, Iran Polymer and Petrochemical Institute, Tehran, Iran; Department of Energy Storage, Institute of Mechanics, Shiraz, Iran.
⁶ São Paulo State University (Unesp), School of Technology and Sciences, Presidente Prudente, SP, 19060-900, Brazil.

PMID: 38599447
DOI: 10.1016/j.envres.2024.118856

Abstract

The contamination of wastewater with antibiotics has emerged as a critical global challenge, with profound implications for environmental integrity and human well-being. Adsorption techniques have been meticulously investigated and developed to mitigate and alleviate their effects. In this study, we have investigated the adsorption behaviour of Erythromycin (ERY), Gentamicin (GEN), Levofloxacin (LEVO), and Metronidazole (MET) antibiotics as pharmaceutical contaminants (PHCs) on amide-functionalized (RC (=O)NH₂)/MIL-53 (Al) (AMD/ML53A), using molecular simulations and density functional theory (DFT) calculations. Based on our DFT calculations, it becomes apparent that the adsorption tendencies of antibiotics are predominantly governed by the presence of AMD functional groups on the adsorbent surface. Specifically, hydrogen bonding (HB) and van der Waals (vdW) interactions between antibiotics and AMD groups serve as the primary mechanisms facilitating adsorption. Furthermore, we have observed that the adsorption behaviors of these antibiotics are influenced by their respective functional groups, molecular shapes, and sizes. Our molecular simulations delved into how the AMD/ML53A surfaces interact with antibiotics as PHCs. Moreover, various chemical quantum descriptors based on Frontier Molecular Orbitals (FMO) were explored to elucidate the extent of AMD/ML53A adsorption and to assess potential alterations in their electronic properties throughout the adsorption process. Monte Carlo simulation showed that ERY molecules adsorb stronger to the adsorbent in acidic and basic conditions than other contaminants, with high energies: -404.47 kcal/mol in acidic and -6375.26 kcal/mol in basic environments. Molecular dynamics (MD) simulations revealed parallel orientation for the ERY molecule's adsorption on AMD/ML53A with 80% rejection rate. In conclusion, our study highlighted the importance of modeling in developing practical solutions for removing antibiotics as PHCs from wastewater. The insights gained from our calculations can facilitate the design of more effective adsorption materials, ultimately leading to a more hygienic and sustainable ecosystem.

Keywords: Computational analysis; Functionalized-MOF nanostructures; MIL-53 (Al); Molecular simulations; Pharmaceutical contaminants adsorption; Wastewater treatment.