Tailoring molecular recognition in predesigned multifunctional enzyme mimicking porphyrin imprinted interface for high affinity and differential selectivity; sensing etoposide in lung cancer patients

Aqsa Tariq; Amina Arif; Muhammad Akram; Usman Latif; Mian Hasnain Nawaz; Silvana Andreescu; Hongxia Zhang; Akhtar Hayat

doi:10.1016/j.bios.2023.115833

Tailoring molecular recognition in predesigned multifunctional enzyme mimicking porphyrin imprinted interface for high affinity and differential selectivity; sensing etoposide in lung cancer patients

Biosens Bioelectron. 2024 Feb 1:245:115833. doi: 10.1016/j.bios.2023.115833. Epub 2023 Nov 14.

Authors

Aqsa Tariq¹, Amina Arif², Muhammad Akram³, Usman Latif³, Mian Hasnain Nawaz³, Silvana Andreescu⁴, Hongxia Zhang⁵, Akhtar Hayat⁶

Affiliations

¹ State Key Laboratory of Biobased Material and Green Papermaking, College of Food Science and Engineering, Qilu University of Technology, Shandong Academy of Science, PO Box 250353, Jinan, Shandong, China; Interdisciplinary Research Center in Biomedical Materials (IRCBM), COMSATS University Islamabad (CUI), Lahore, 54000, Pakistan; Department of Basic and Applied Chemistry, Faculty of Science and Technology, University of Central Punjab, Lahore, Pakistan.
² Department of Basic and Applied Chemistry, Faculty of Science and Technology, University of Central Punjab, Lahore, Pakistan.
³ Interdisciplinary Research Center in Biomedical Materials (IRCBM), COMSATS University Islamabad (CUI), Lahore, 54000, Pakistan.
⁴ Department of Chemistry and Biomolecular Science, Clarkson University, Potsdam, NY, 13699-5810, USA.
⁵ State Key Laboratory of Biobased Material and Green Papermaking, College of Food Science and Engineering, Qilu University of Technology, Shandong Academy of Science, PO Box 250353, Jinan, Shandong, China. Electronic address: zhanghongxia326@hotmail.com.
⁶ State Key Laboratory of Biobased Material and Green Papermaking, College of Food Science and Engineering, Qilu University of Technology, Shandong Academy of Science, PO Box 250353, Jinan, Shandong, China; Interdisciplinary Research Center in Biomedical Materials (IRCBM), COMSATS University Islamabad (CUI), Lahore, 54000, Pakistan. Electronic address: akhtarhayat@cuilahore.edu.pk.

PMID: 37984317
DOI: 10.1016/j.bios.2023.115833

Abstract

Nanozymes are cost-effective and robust but they lack specificity and selectivity, limiting their potential practical applications. Herein, molecularly imprinted polymers (MIPs) were grown in combination with multifunctional 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphyrin (THPP) oxidase-like nanozyme to engineer THPP@MIP interface with high affinities and differential selectivity for structurally related target analytes. THPP nanozyme displayed a high level of predefined binding affinity for etoposide (ETO), and served as a predesigned functional monomer to rationally tailor the selectivity of THPP@MIP surface in the presence of different guest molecules. THPP nanozyme in combination with conventional monomers was imprinted on a portable and disposable cellulose paper matrix under UV light to create a UV-cured imprinted interface for optical detection of ETO. The THPP@MIP enzyme mimicking interface, having ETO specific and selective target recognition pockets, catalyzed the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to generate visible blue oxidized TMB (oxTMB) without exogenous hydrogen peroxide (H₂O₂). The ETO binding on the THPP@MIP surface blocked the channels for TMB access to THPP cavities. The THPP@MIP sensor permitted to detect ETO in the linear range of 0.005-10 μg mL^-1, with a limit of detection (LoD) of 0.002 μg mL^-1, and showed a remarkable specificity and selectivity against other drug molecules. Furthermore, the THPP@MIP sensor successfully differentiated the serum samples of lung cancer patients and healthy volunteers. The obtained results were validated with standard High performance liquid chromatography-mass spectrometry (HPLC/MS) analysis of the serum samples. Additionally, ETO injection/infusion solutions and ETO-free serum samples were used to perform the matrix effect and recovery studies. This work demonstrates that molecular imprinting with predesigned, enzyme mimicking, high-affinity functional monomer can serve as a highly selective and specific universal interface for broad spectrum sensing applications in various analytical domains.

Keywords: Cancer patients; Enzyme mimicking; Etoposide; Molecular imprinting; Porphyrin; Predesigned monomer.

MeSH terms

Biosensing Techniques* / methods
Etoposide
Humans
Hydrogen Peroxide
Lung Neoplasms* / drug therapy
Molecular Imprinting* / methods
Multifunctional Enzymes
Polymers / chemistry

Substances

Polymers
Etoposide
Multifunctional Enzymes
Hydrogen Peroxide
flopropione