Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis

Overview

Journal Int J Mol Sci

Publisher MDPI

Specialties Biochemistry
Chemistry
Molecular Biology

Date 2023 May 27

PMID 37240293

Authors

Nikita E Safronov

Irena P Kostova

Mauricio Alcolea Palafox

Nataliya P Belskaya

Affiliations

Soon will be listed here.

Abstract

The peculiarities of the optical properties of 2-aryl-1,2,3-triazole acids and their sodium salts were investigated in different solvents (1,4-dioxane, dimethyl sulfoxide DMSO, methanol MeOH) and in mixtures with water. The results were discussed in terms of the molecular structure formed by inter- and intramolecular noncovalent interactions (NCIs) and their ability to ionize in anions. Theoretical calculations using the Time-Dependent Density Functional Theory (TDDFT) were carried out in different solvents to support the results. In polar and nonpolar solvents (DMSO, 1,4-dioxane), fluorescence was provided by strong neutral associates. Protic MeOH can weaken the acid molecules' association, forming other fluorescent species. The fluorescent species in water exhibited similar optical characteristics to those of triazole salts; therefore, their anionic character can be assumed. Experimental H and C-NMR spectra were compared to their corresponding calculated spectra using the Gauge-Independent Atomic Orbital (GIAO) method and several relationships were established. All these findings showed that the obtained photophysical properties of the 2-aryl-1,2,3-triazole acids noticeably depend on the environment and, therefore, are good candidates as sensors for the identification of analytes with labile protons.

Citing Articles

Molecular properties of a triazole-Ce(III) complex with antioxidant activity: structure, spectroscopy, and relationships with related derivatives. Influence of the ligands in the complex.

Palafox M, Belskaya N, Todorov L, Hristova-Avakumova N, Kostova I Front Chem. 2024; 12:1450106.

PMID: 39569014 PMC: 11576285. DOI: 10.3389/fchem.2024.1450106.

Special Issue: "Rational Design and Synthesis of Bioactive Molecules".

Kostova I Int J Mol Sci. 2024; 25(18).

PMID: 39337415 PMC: 11432531. DOI: 10.3390/ijms25189927.

Effect of Lanthanide Ions and Triazole Ligands on the Molecular Properties, Spectroscopy and Pharmacological Activity.

Palafox M, Belskaya N, Todorov L, Hristova-Avakoumova N, Kostova I Int J Mol Sci. 2024; 25(14).

PMID: 39063204 PMC: 11276792. DOI: 10.3390/ijms25147964.

Study of the Molecular Architectures of 2-(4-Chlorophenyl)-5-(pyrrolidin-1-yl)-2-1,2,3-triazole-4-carboxylic Acid Using Their Vibrational Spectra, Quantum Chemical Calculations and Molecular Docking with MMP-2 Receptor.

Palafox M, Belskaya N, Kostova I Pharmaceutics. 2023; 15(12).

PMID: 38140027 PMC: 10747663. DOI: 10.3390/pharmaceutics15122686.

Structural Study of a La(III) Complex of a 1,2,3-Triazole Ligand with Antioxidant Activity.

Palafox M, Belskaya N, Todorov L, Kostova I Antioxidants (Basel). 2023; 12(10).

PMID: 37891952 PMC: 10604163. DOI: 10.3390/antiox12101872.

References

Lodewyk M, Soldi C, Jones P, Olmstead M, Rita J, Shaw J . The correct structure of aquatolide-experimental validation of a theoretically-predicted structural revision. J Am Chem Soc. 2012; 134(45):18550-3. DOI: 10.1021/ja3089394. View

Migda W, Rys B . GIAO/DFT evaluation of 13C NMR chemical shifts of selected acetals based on DFT optimized geometries. Magn Reson Chem. 2004; 42(5):459-66. DOI: 10.1002/mrc.1366. View

Sarotti A, Pellegrinet S . A multi-standard approach for GIAO (13)C NMR calculations. J Org Chem. 2009; 74(19):7254-60. DOI: 10.1021/jo901234h. View

Zhao S, Liu J, Lv Z, Zhang G, Xu Z . Recent updates on 1,2,3-triazole-containing hybrids with in vivo therapeutic potential against cancers: A mini-review. Eur J Med Chem. 2023; 251:115254. DOI: 10.1016/j.ejmech.2023.115254. View

Bagno A, Rastrelli F, Saielli G . Toward the complete prediction of the 1H and 13C NMR spectra of complex organic molecules by DFT methods: application to natural substances. Chemistry. 2006; 12(21):5514-25. DOI: 10.1002/chem.200501583. View

Bozorov K, Zhao J, Aisa H . 1,2,3-Triazole-containing hybrids as leads in medicinal chemistry: A recent overview. Bioorg Med Chem. 2019; 27(16):3511-3531. PMC: 7185471. DOI: 10.1016/j.bmc.2019.07.005. View

Keri R, Patil S, Budagumpi S, Nagaraja B . Triazole: A Promising Antitubercular Agent. Chem Biol Drug Des. 2015; 86(4):410-23. DOI: 10.1111/cbdd.12527. View

Bally T, Rablen P . Quantum-chemical simulation of 1H NMR spectra. 2. Comparison of DFT-based procedures for computing proton-proton coupling constants in organic molecules. J Org Chem. 2011; 76(12):4818-30. DOI: 10.1021/jo200513q. View

Benassi E . Benchmarking of density functionals for a soft but accurate prediction and assignment of (1) H and (13)C NMR chemical shifts in organic and biological molecules. J Comput Chem. 2016; 38(2):87-92. DOI: 10.1002/jcc.24521. View

10.

DAscenzo L, Auffinger P . A comprehensive classification and nomenclature of carboxyl-carboxyl(ate) supramolecular motifs and related catemers: implications for biomolecular systems. Acta Crystallogr B Struct Sci Cryst Eng Mater. 2015; 71(Pt 2):164-75. PMC: 4383392. DOI: 10.1107/S205252061500270X. View

11.

Reijenga J, van Hoof A, van Loon A, Teunissen B . Development of Methods for the Determination of pKa Values. Anal Chem Insights. 2013; 8:53-71. PMC: 3747999. DOI: 10.4137/ACI.S12304. View

12.

Zhang H, Ryono D, Devasthale P, Wang W, OMalley K, Farrelly D . Design, synthesis and structure-activity relationships of azole acids as novel, potent dual PPAR alpha/gamma agonists. Bioorg Med Chem Lett. 2009; 19(5):1451-6. DOI: 10.1016/j.bmcl.2009.01.030. View

13.

Britz D, Khlobystov A . Noncovalent interactions of molecules with single walled carbon nanotubes. Chem Soc Rev. 2006; 35(7):637-59. DOI: 10.1039/b507451g. View

14.

Santibanez-Moran M, Medina-Franco J . The Acid/Base Characterization of Molecules with Epigenetic Activity. ChemMedChem. 2021; 16(11):1744-1753. DOI: 10.1002/cmdc.202001009. View

15.

Yan W, Wang Q, Lin Q, Li M, Petersen J, Shi X . N-2-aryl-1,2,3-triazoles: a novel class of UV/blue-light-emitting fluorophores with tunable optical properties. Chemistry. 2011; 17(18):5011-8. DOI: 10.1002/chem.201002937. View

16.

Agalave S, Maujan S, Pore V . Click chemistry: 1,2,3-triazoles as pharmacophores. Chem Asian J. 2011; 6(10):2696-718. DOI: 10.1002/asia.201100432. View

17.

Soldatov D, Moudrakovski I, Grachev E, Ripmeester J . Micropores in crystalline dipeptides as seen from the crystal structure, He pycnometry, and 129Xe NMR spectroscopy. J Am Chem Soc. 2006; 128(20):6737-44. DOI: 10.1021/ja060474j. View

18.

Ferreira de Albuquerque A, Ribeiro D, de Amorim M . Structural determination of complex natural products by quantum mechanical calculations of (13)C NMR chemical shifts: development of a parameterized protocol for terpenes. J Mol Model. 2016; 22(8):183. DOI: 10.1007/s00894-016-3045-6. View

19.

Chai J, Head-Gordon M . Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. Phys Chem Chem Phys. 2008; 10(44):6615-20. DOI: 10.1039/b810189b. View

20.

Lai Q, Liu Q, Zhao K, Shan C, Wojtas L, Zheng Q . Rational design and synthesis of yellow-light emitting triazole fluorophores with AIE and mechanochromic properties. Chem Commun (Camb). 2019; 55(32):4603-4606. PMC: 6519987. DOI: 10.1039/c9cc00262f. View