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Selectivity through an asymmetric pathway in the degradation of non-steroidal anti-inflammatory drugs (NSAIDs) using mixed-ligand cobalt(II) complexes: experimental and theoretical insights

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Abstract

Understanding the asymmetric catalytic mechanism involving organometallic species provides exceptional insight into the strategies for the degradation of emerging organic contaminants. The present work demonstrates such insights on the oxidation of commonly used non-steroidal anti-inflammatory drugs (NSAIDs) such as diclofenac, paracetamol, ibuprofen, and aspirin using optically active novel Schiff base Co(II) complexes derived from salicylaldehyde containing five different amino acids (L-methionine, L-leucine, L-asparagine, L-tryptophan, and L-glutamic acid). Among the studied chiral catalysts, asymmetric degradation in the presence of a Co(II) complex containing glutamic acid mixed ligand showed an elevated rate of oxidation of non-amine NSAIDs such as ibuprofen (3.86 × 10–2 s−1) and aspirin (3.70 × 10–3 s−1) using H2O2 oxidant under visible light conditions at neutral pH. The formation of chiral intermediate species in both drugs has been detected and characterized by FTIR and Raman analysis. On the other hand, NSAIDs containing secondary amine groups (–NH–), such as diclofenac and paracetamol, generate effective coordination between the complex catalyst and the nitrogen atom. This explains the high activity of the Co(II) complex with glutamic acid mixed salicylaldehyde with 100% selectivity in the degradation of ibuprofen and aspirin. The thermodynamical feasibility of the proposed degradation route for ibuprofen and aspirin was analyzed with theoretically calculated total energy values of all the intermediates formed in each step of the proposed mechanism.

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Acknowledgements

Authors gratefully acknowledge COMECYT (Consejo Mexiquense de Ciencia y Tecnología, Folio: FICDTEM-2021-047), Estado de México, for the financial support through “Financiamiento para Investigación de Mujeres Científica EDOMEX-FICDTEM-2021-01”. Also, acknowledge DGTIC (Dirección General de Cómputo y de Tecnologías de Información y Comunicación) of Universidad Nacional Autónoma de México (UNAM) for the computational services.

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Authors and Affiliations

  1. División de Ingeniería en Nanotecnología, Universidad Politécnica del Valle de México, Av. Mexiquense S/N, 54910, Tultitlan, Estado de México, México

    Susana Dianey Gallegos Cerda, Miguel Morales Rodríguez, José Antonio Juanico Loran & Jayanthi Narayanan

  2. School of Engineering and Sciences, Tecnologico de Monterrey, 5718 Atlixcáyotl, 72453, Puebla, México

    Carlos Alberto Huerta Aguilar

  3. Department of Chemistry, School of Chemical Engineering and Physical Sciences, Lovely Professional University, Phagwara, 144411, India

    Jashanpreet Singh

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  1. Susana Dianey Gallegos Cerda
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Contributions

Susana Dianey Gallegos Cerda participated in methodology and data curation. Carlos Alberto Huerta Aguilar participated in software, data curation, and validation. Miguel Morales Rodríguez participated in the resources and formal analysis. Jose Antonio Juanico Loran participated in the XRD studies. Jayanthi Narayanan participated in conceptualization, validation, writing the original draft, writing the review, and editing. All authors reviewed the manuscript.

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Correspondence to Jayanthi Narayanan.

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Cerda, S.D.G., Aguilar, C.A.H., Singh, J. et al. Selectivity through an asymmetric pathway in the degradation of non-steroidal anti-inflammatory drugs (NSAIDs) using mixed-ligand cobalt(II) complexes: experimental and theoretical insights. Transit Met Chem 48, 401–414 (2023). https://doi.org/10.1007/s11243-023-00553-8

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