Derivados de tiourea como receptores en sensores de Pb(II): descripción teórica y experimental
Palavras-chave:
1-aroiltioureas-3,3-disustituidas; electrodos selectivos a iones Pb(II); cálculos de TFD; OMF; parámetros de reactividad global.Resumo
Los derivados de tiourea han sido empleados como receptores en el desarrollo de electrodos selectivos a iones metálicos (ESIs). Entre los receptores utilizados para la construcción de ESIs a iones Pb(II) se encuentran: 1-benzoil-3,3-dimetiltiourea (1), 1-(2-furoil)-3,3-dimetiltiourea (2) y 1-(2-tiofenil)-3,3-dimetiltiourea (3). Aunque existen varios estudios analíticos sobre el comportamiento de estos sensores, es importante el desarrollo de modelos teóricos que permitan esclarecer las diferencias observadas en su respuesta. En este trabajo se emplea el funcional B3LYP y la base 6-311G(d,p) para calcular la geometría, la estructura electrónica, los espectros IR, las energías de los orbitales HOMO-LUMO y los parámetros de reactividad global de estas moléculas. Se relacionaron los parámetros calculados con los de respuesta analítica que muestran los sensores construidos. Se encontró una buena correspondencia entre los parámetros teóricos y experimentales y se pudo establecer el orden de reactividad: (3) > (1) ≈ (2) para los receptores estudiados.
Referências
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24. SAEED, A.; FLÖRKE, U.; ERBEN, M. F. “A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas”, Journal of Sulfur Chemistry. 2014, 35 (3), 318-355. ISSN: 1741-5993
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26. ESTÉVEZ-HERNÁNDEZ, O.; et al. “A Raman and infrared study of 1-furoyl-3monosubstituted and 3, 3-disubstituted thioureas”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2005, 62 (4-5), 964-971. ISSN: 1386-1425
27. NATARAJ, A.; BALACHANDRAN, V.; KARTHICK, T. “Molecular structure, vibrational spectra, first hyperpolarizability and HOMO–LUMO analysis of p-acetylbenzonitrile using quantum chemical calculation”, Journal of Molecular Structure. 2013, 1038, 134-144. ISSN: 0022-2860
28. RUIZ-MORALES, Y. “HOMO− LUMO gap as an index of molecular size and structure for polycyclic aromatic hydrocarbons (PAHs) and asphaltenes: A theoretical study. I”, The Journal of Physical Chemistry A. 2002, 106 (46), 11283-11308. ISSN: 1089-5639
29. ARMSTRONG, R. D.; HORVAI, G. “Properties of PVC based membranes used in ionselective electrodes”, Electrochimica Acta. 1990, 35 (1), 1-7. ISSN: 1873-3859
2. FRAGA, A. R. L.; et al. “Could N-(diethylcarbamothioyl)benzamide be a good ionophore for sensor membranes?”, Journal of Molecular Structure. 2010, 981 (1-3), 86-92. ISSN: 0022-2860
3. VILTRES-PORTALES, M. Nuevos electrodos selectivos a iones Pb(II) basados en aroiltioureas 3,3-dimetilsustituidas. Tesis de Maestría, IMRE-Universidad de La Habana, Cuba, 2019. Disponible en: www.uh.cu. (consultado: 28-8-2020)
4. PÉREZ, H.; et al. “N-Benzoyl-N′,N′-dimethylthiourea”, Acta Crystallographica Section E: Structure Reports Online. 2011, 67 (3), o647-o647. ISSN: 1600-5368
5. CAIRO, R. R.; et al. “Understanding the conformational changes and molecular structure of furoyl thioureas upon substitution”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2017, 176, 8-17. ISSN: 1386-1425
6. SAEED, S.; et al. “Synthesis, spectroscopic characterization, crystal structure and pharmacological properties of some novel thiophene‐ thiourea core derivatives”, European Journal of Chemistry. 2010, 1 (3), 221-227. ISSN: 2153-2257
7. GEERLINGS, P.; DE PROFT, F.; LANGENAEKER, W. “Conceptual density functional theory”, Chemical reviews. 2003, 103 (5), 1793-1874. ISSN: 0009-2665
8. CASTRO, M.; et al. “Theoretical study of the Hg2+ recognition by 1,3-diphenyl-thiourea”, The Journal of Physical Chemistry A. 2003, 107 (42), 9000-9007. ISSN: 1089-5639
9. GIL, D. M.; et al. “Quantum chemical studies on molecular structure, spectroscopic (IR, Raman, UV–Vis), NBO and Homo–Lumo analysis of 1-benzyl-3-(2-furoyl) thiourea”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2015, 145, 553-562. ISSN: 1386-1425
10. LESTARD, M. E. D.; et al. “Structural, vibrational and electronic characterization of 1benzyl-3-furoyl-1-phenylthiourea: an experimental and theoretical study”, New Journal of Chemistry. 2015, 39 (9), 7459-7471. ISSN: 1369-9261
11. PLUTÍN, A. M.; et al. “Alkylation of benzoyl and furoylthioureas as polydentate systems”, Tetrahedron. 2000, 56 (11), 1533-1539. ISSN: 0040-4020
12. LIMA, J. L. F. C.; MACHADO, A. A. S. C. “Procedure for the construction of all-solid-state PVC membrane electrodes”, Analyst. 1986, 111 (7), 799-802.ISSN: 1364-5528
13. LAZO-FRAGA, A. R.; et al. “Evaluación de diferentes aroiltioureas como ionóforos en sensores de plomo (II)”, Revista Cubana de Química. 2015, 27 (3), 262-274. ISSN: 2224-5421
14. BUCK, R. P.; LINDNER, E. “Recommendations for nomenclature of ion selective electrodes (IUPAC Recommendations 1994)”, Pure and Applied Chemistry. 1994, 66 (12), 2527-2536. ISSN: 1365-3075
15. UMEZAWA, Y.; UMEZAWA, K.; SATO, H. “Selectivity coefficients for ion-elective
electrodes: Recommended methods for reporting values (Technical Report) ”, Pure and
Applied Chemistry. 1995, 67 (3), 507-518. ISSN: 1365-3075
16. BECKE, A. D. “Density‐ functional thermochemistry. I. The effect of the exchange‐ only gradient correction”, The Journal of Chemical Physics. 1992, 96 (3), 2155-2160. ISSN: 00219606
17. LEE, C.; YANG, W.; PARR, R. G. “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density”, Physical review B. 1988, 37 (2), 785.ISSN: 1098-0121
18. WOLDU, M. G.; DILLEN, J., “A quantum mechanical study of the stability and structural properties of substituted acylthiourea compounds”, Theoretical Chemistry Accounts, 2008, 121 (1-2), 71–82. ISSN: 1432-2232
19. FRISCH, M. J. et al. Gaussian 09, D.01, Gaussian, Inc., Wallingford CT (2013).
20. EL-AZHARY, A. A.; SUTER, H. U. “Comparison between optimized geometries and vibrational frequencies calculated by the DFT methods”, The Journal of Physical Chemistry. 1996, 100 (37), 15056-15063. ISSN: 0022-3654
21. FRAGA, A. R. L.; et al. “Structures and properties in different media of N,N(diethylcarbamothioyl)furan-2-carboxamide: A ionophore for sensor membranes”, Journal of Molecular Structure. 2009, 929 (1-3), 174-181. ISSN: 0022-2860
22. SUNDARAGANESAN, N.; et al. “Comparison of experimental and ab initio HF and DFT vibrational spectra of benzimidazole”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2007, 67, 628-635. ISSN: 1386-1425
23. YOSHIDA, H.; et al. “A new approach to vibrational analysis of large molecules by density functional theory: wavenumber-linear scaling method”, The Journal of Physical Chemistry A. 2002, 106 (14), 3580-3586. ISSN: 1089-5639
24. SAEED, A.; FLÖRKE, U.; ERBEN, M. F. “A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas”, Journal of Sulfur Chemistry. 2014, 35 (3), 318-355. ISSN: 1741-5993
25. LIN-VIEN, D.; et al. The handbook of infrared and Raman characteristic frequencies of organic molecules. Edición Reino Unido, Londres: Academic Press, 1991. ISBN: 0080571166
26. ESTÉVEZ-HERNÁNDEZ, O.; et al. “A Raman and infrared study of 1-furoyl-3monosubstituted and 3, 3-disubstituted thioureas”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2005, 62 (4-5), 964-971. ISSN: 1386-1425
27. NATARAJ, A.; BALACHANDRAN, V.; KARTHICK, T. “Molecular structure, vibrational spectra, first hyperpolarizability and HOMO–LUMO analysis of p-acetylbenzonitrile using quantum chemical calculation”, Journal of Molecular Structure. 2013, 1038, 134-144. ISSN: 0022-2860
28. RUIZ-MORALES, Y. “HOMO− LUMO gap as an index of molecular size and structure for polycyclic aromatic hydrocarbons (PAHs) and asphaltenes: A theoretical study. I”, The Journal of Physical Chemistry A. 2002, 106 (46), 11283-11308. ISSN: 1089-5639
29. ARMSTRONG, R. D.; HORVAI, G. “Properties of PVC based membranes used in ionselective electrodes”, Electrochimica Acta. 1990, 35 (1), 1-7. ISSN: 1873-3859
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2021-04-26
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Bustamante-Sánchez, M., Lazo-Fraga, A. R., Viltres-Portales, M., González-Quintela, M., Sánchez-Díaz, G., Díaz-García, A., & Estévez-Hernández, O. (2021). Derivados de tiourea como receptores en sensores de Pb(II): descripción teórica y experimental. Revista Cubana De Química, 33(2), 91–112. Recuperado de https://cubanaquimica.uo.edu.cu/index.php/cq/article/view/5178
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