Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches
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 th...
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my.um.eprints.410722023-08-17T04:05:52Z http://eprints.um.edu.my/41072/ Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches Narimani, Leila Lee, Vannajan Sanghiran Alias, Yatimah Manan, Ninie Suhana Abdul Woi, Pei Meng QD Chemistry 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. MDPI 2022-10 Article PeerReviewed 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 <https://doi.org/10.3390/molecules27196248>. 10.3390/molecules27196248 |
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QD Chemistry Narimani, Leila Lee, Vannajan Sanghiran Alias, Yatimah Manan, Ninie Suhana Abdul Woi, Pei Meng Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches |
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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. |
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Article |
author |
Narimani, Leila Lee, Vannajan Sanghiran Alias, Yatimah Manan, Ninie Suhana Abdul Woi, Pei Meng |
author_facet |
Narimani, Leila Lee, Vannajan Sanghiran Alias, Yatimah Manan, Ninie Suhana Abdul Woi, Pei Meng |
author_sort |
Narimani, Leila |
title |
Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches |
title_short |
Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches |
title_full |
Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches |
title_fullStr |
Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches |
title_full_unstemmed |
Rational design of a fluorescent chromophore as a calcium receptor via DFT and multivariate approaches |
title_sort |
rational design of a fluorescent chromophore as a calcium receptor via dft and multivariate approaches |
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MDPI |
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2022 |
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http://eprints.um.edu.my/41072/ |
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