Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches

Narimani, Leila and Lee, Vannajan Sanghiran and Alias, Yatimah and Manan, Ninie Suhana Abdul and Woi, Pei Meng (2022) Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches. Molecules, 27 (19). ISSN 1420-3049, DOI https://doi.org/10.3390/molecules27196248.

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Computational and experimental approaches were adopted to utilize a chromophore diglycolic functionalized fluorescein derivative as a Ca2+ receptor. Fluorescein diglycolic acid (Fl-DGA, 1) was synthesized and used in multivariate determination of Ca2+ and K+. Full-structure computation shows that the complexes of 1 and Ca2+ have comparable energies regardless of additional interaction with lactone moiety. The initial formation of diglycolic-Ca2+ complex followed by macrocyclization is thermodynamically disfavored. A U-shaped pre-organized 1 allows Ca2+ to interact simultaneously with diglycolic and lactone motifs. Both motifs actively participate in Ca2+ recognition and the eleven methylene units in the undecyl arm provides excellent flexibility for reorganization and optimum interaction. Principal component analysis (PCA) of computational molecular properties reveals a simple method in evaluating motifs for cation recognition. Fragment models support full-structure results that negative charge causes significant structural changes, but do not reproduce the full extent of C-O bond breaking observed in the latter. Experimental optical responses show that 1 is selective towards Ca2+ and discriminates against K+ and Mg2+. PCA of emission intensities affords distinct clusters of 0.01, 0.1 and 1 mM Ca2+ and K+, and suggests applicability of this technique for simultaneous determination of cationic plant macronutrients in precision agriculture and a wide variety of other applications.

Item Type: Article
Funders: Universiti Malaya (UM) International Collaboration Grant (ST005-2022), UM KW IPPP-Research Maintenance Fee (RMF) (RMF1433-2021)
Uncontrolled Keywords: Fluorescein diglycolic acid; Calcium; Multivariate; DFT; Principal component analysis
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science > Department of Chemistry
Depositing User: Ms. Juhaida Abd Rahim
Date Deposited: 17 Aug 2023 04:05
Last Modified: 17 Aug 2023 04:05
URI: http://eprints.um.edu.my/id/eprint/41072

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