Keywords
heavy trivalent lanthanides
thermoanalytical study
thermal decomposition
phase transition
How to Cite
Funding data
-
Fundação de Amparo à Pesquisa do Estado de São Paulo
Grant numbers 2023/06756-1 -
Conselho Nacional de Desenvolvimento Científico e Tecnológico
Grant numbers 317282/2021-2 -
Conselho Nacional de Desenvolvimento Científico e Tecnológico
Grant numbers 443152/2024-1
Abstract
Heavy trivalent lanthanide and yttrium complexes with p-aminobenzoate were synthesized and characterized using thermoanalytical, spectroscopic, and complementary techniques. The results provide in-depth knowledge, particularly regarding the thermal behavior of these complexes, which had not been previously reported. Analytical and thermoanalytical data showed that the complexes exhibit a 1:3 metal-to-p-ABA stoichiometry, and FTIR spectra indicated coordination through the carboxylate and amino groups for the Ho(III)-Yb(III), and Y(III) complexes, whereas the lutetium complex showed coordination only by carboxylate group. The complexes exhibited a crystalline structure and, except the lutetium complex, were monohydrated. Simultaneous Thermogravimetric and Differential Thermal Analysis (TG-DTA) and Evolved Gas Analysis (EGA) results allowed investigation of the thermal behavior of the complexes under pyrolytic and oxidative atmospheres. EGA identified CO₂, CO, and NH₃ as the main gaseous products released during thermal decomposition in an air atmosphere, while aniline, CO₂, CO, and NH₃ were identified under a nitrogen atmosphere. Differential Scanning Calorimetry (DSC) enabled the determination of dehydration enthalpies and the study of phase transitions for the Ho(III), Er(III), Y(III) complexes
References
Akberova, S. I. New Biological Properties of p-Aminobenzoic Acid. Biology Bulletin. 2002, 29 (4), 390–393. https://doi.org/10.1023/A:1016871219882
Aquaroni, N. A. S.; Nakahata, D. H.; Lazarini, S. C.; Resende, F. A.; Cândido, A. L. P.; da Silva Barud, H.; Claro, A. M.; de Carvalho, J. E.; Ribeiro, C. M.; Pavan, F. R.; Lustri, B. C.; Ribeiro, T. R. M.; Moreira, C. G.; Cândido, T. Z.; Lima, C. S. P.; Ruiz, A. L. T. G.; Corbi, P. P.; Lustri, W. R. Antibacterial Activities and Antiproliferative Assays over a Tumor Cells Panel of a Silver Complex with 4-Aminobenzoic Acid: Studies In Vitro of Sustained Release Using Bacterial Cellulose Membranes as Support. Journal of Inorganic Biochemistry. 2020, 212, 111247. https://doi.org/10.1016/j.jinorgbio.2020.111247
Caires, F. J.; Nunes, W. D. G.; Gaglieri, C.; Do Nascimento, A. L. C. S.; Teixeira, J. A.; Zangaro, G. A. C.; Treu-Filho, O.; Ionashiro, M. Thermoanalytical, Spectroscopic and DFT Studies of Heavy Trivalent Lanthanides and Yttrium(III) with Oxamate as Ligand. Materials Research. 2017, 20 (4), 937–944. https://doi.org/10.1590/1980-5373-mr-2016-0633
Deacon, G. B.; Phillips, R. J. Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination. Coordination Chemistry Reviews. 1980, 33, 227–250. https://doi.org/10.1023/A:1016871219882
Flaschka, H. A.; Naiman, B. EDTA Titrations: An Introduction to Theory and Practice. Journal of The Electrochemical Society. 1959, 106 (8), 226C. https://doi.org/10.1149/1.2427458
Galbinur, T.; Obolensky, A.; Berenshtein, E.; Vinokur, V.; Chowers, I.; Chevion, M.; Banin, E. Effect of para-aminobenzoic acid on the course of retinal degeneration in the rd10 mouse. Journal of Ocular Pharmacology and Therapeutics. 2009, 25 (6), 475–482. https://doi.org/10.1089/jop.2009.0020
Ghosh, D.; Luwang, M. N. p-Aminobenzoic acid (pABA) sensitization of LaF3 :Tb3+ nanoparticles and its applications in the detection of explosive materials. RSC Advances. 2015, 5, 10468–10478. https://doi.org/10.1039/C4RA15304A
Gómez, N. A. G.; Silva, G. M.; Wilhelm, H. M.; Wypych, F. Zn2Al Layered Double Hydroxides Intercalated with Nitrate and p-Aminobenzoate as Ultraviolet Protective Agents in Low-Density Polyethylene Nanocomposites and Natural Insulating Oils. Journal of the Brazilian Chemical Society. 2020 31 (5), 971–981. https://doi.org/10.21577/0103-5053.20190262
Horozić, E.; Ademović, Z.; Suljagić, J.; Cipurković, A.; Rosa, E.; Sejfić, A.; Husejnagić, D.; Hodzić, S. Synthesis, spectral characterization, antibacterial and antifungal activity of copper (II)-pABA complex. Technologia Acta. 2019, 12 (1), 27–30. https://doi.org/10.5281/zenodo.3268784
Jesty, T.; Ambili, K. S.; Baby, A. M.; Sonyamol, S. Characterization and optical studies of hybrid materials synthesized by covalently linking Eu3+ ions, para-aminobenzoic acid, and titania. Journal of Applied Spectroscopy. 2017, 84 (1), 156-161. https://doi.org/10.1007/s10812-017-0444-0
Kalembkiewicz, J.; Kosińska, M.; Zapała, L. Complexes of aminobenzoic acids: A comprehensive review concerning synthesis, physical chemistry, structure and application. Coordination Chemistry Reviews. 2017, 348, 25–53. https://doi.org/10.1016/j.ccr.2017.07.004
Koma, D.; Yamanaka, H.; Moriyoshi, K.; Sakai, K.; Masuda, T.; Sato, Y.; Toida, K.; Ohmoto, T. Production of p-Aminobenzoic acid by metabolically engineered Escherichia coli. Bioscience, Biotechnology, and Biochemistry. 2014, 78 (2), 350-357. https://doi.org/10.1080/09168451.2014.878222
LeBlanc, J. G.; Milani, C.; de Giori, G. S.; Sesma, F.; van Sinderen, D.; Ventura, M. Bacteria as vitamin suppliers to their host: A gut microbiota perspective. Current Opinion in Biotechnology. 2013, 24 (2), 160–168. https://doi.org/10.1016/j.copbio.2012.08.005
Murugavel, R.; Karambelkar, V. V.; Anantharaman, G. Synthetic, spectroscopic and structural studies on 4-aminobenzoate complexes of divalent alkaline earth metals: X-ray crystal structures of [{Mg(H2O)6}(4-aba)2]·2H2O and [Ca(H2O)2(4-aba)2] (4-aba=4-aminobenzoate). Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical, and Analytical Chemistry. 2000, 39 (8), 843–850. https://doi.org/10.1021/ic990895k
Nunes, W. D. G.; Teixeira, J. A.; do Nascimento, A. L. C. S.; Caires, F. J.; Ionashiro, E. Y.; Ionashiro, M. A comparative study on thermal behavior of solid-state light trivalent lanthanide isonicotinates in dynamic dry air and nitrogen atmospheres. Journal of Thermal Analysis and Calorimetry. 2016, 125 (1), 397–405. https://doi.org/10.1007/s10973-016-5339-4
Olanrewaju, A. A.; Ibeji, C. U.; Fabiyi, F.; Ibeji, C. U.; Fabiyi, F. S. Synthesis, Characterization, and Computational Studies of Metal(II) Complexes Derived from β-diketone and Para-aminobenzoic Acid Corrosion inhibition View project Mechanistic chemistry View project Synthesis, Characterization, and Computational Studies of Metal(II) Complexes Derived from β-diketone and Para-aminobenzoic Acid. Indian Journal of Heterocyclic Chemistry. 2018, 28 (3), 351–361.
Parmar, B.; Bisht, K. K.; Maiti, P.; Paul, P.; Suresh, E. Syntheses, characterization and crystal structures of potassium and barium complexes of a Schiff base ligand with different anions. Journal of Chemical Sciences. 2014, 126 (5), 1373–1384. https://doi.org/10.1007/s12039-014-0701-1
Pavia, D. L.; Lampman, G. M.; Kriz, G. S.; Vyvyan, J. R. Introdução à Espectroscopia, Tradução da 4ª Edição norte-americana; Cengage Learning, 2010.
Peters, J. A.; Djanashvili, K.; Geraldes, C. F. G. C.; Platas-iglesias, C. The chemical consequences of the gradual decrease of the ionic radius along the Ln-series. Coordination Chemistry Reviews. 2020, 406, 213146. https://doi.org/10.1016/j.ccr.2019.213146
Rodrigues, E. C.; Siqueira, A. B.; Ionashiro, E. Y.; Bannach, G.; Ionashiro, M. Synthesis, characterization, and thermal behaviour of solid 4-methoxybenzoates of heavier trivalent lanthanides. Thermochimica Acta. 2006, 451 (1–2), 149–155. https://doi.org/10.1016/j.tca.2006.09.014
Rosbottom, I.; Ma, C. Y.; Turner, T. D.; O’Connell, R. A.; Loughrey, J.; Sadiq, G.; Davey, R. J.; Roberts, K. J. Influence of Solvent Composition on the Crystal Morphology and Structure of p-Aminobenzoic Acid Crystallized from Mixed Ethanol and Nitromethane Solutions. Crystal Growth and Design. 2017, 17 (8), 4151–4161. https://doi.org/10.1021/acs.cgd.7b00425
Samsonowicz, M.; Hrynaszkiewicz, T.; Świsłocka, R.; Regulska, E.; Lewandowski, W. Experimental and theoretical IR, Raman, NMR spectra of 2-, 3- and 4-aminobenzoic acids. Journal of Molecular Structure. 2005, 744–747, 345–352. https://doi.org/10.1016/j.molstruc.2004.11.063
Sapijanskaitė-Banevič, B.; Palskys, V.; Vaickelionienė, R.; Šiugždaitė, J.; Kavaliauskas, P.; Grybaitė, B.; Mickevičius, V. Synthesis and antibacterial activity of new azole, diazole and triazole derivatives based on p-aminobenzoic acid. Molecules. 2021, 26 (9), 2597. https://doi.org/10.3390/molecules26092597
Silva, R. C.; Caires, F. J.; Gomes, D. J. C.; Colman, T. A. D.; Ionashiro, M. Synthesis, characterization, and thermal study of solid-state alkaline earth metal mandelates, except beryllium and radium. Journal of Thermal Analysis and Calorimetry. 2014, 117, 217–221. https://doi.org/10.1007/s10973-014-3694-6
Silverstein, R. M.; Webster, F. X.; Kiemle, D. Spectrometric Identification of Organic Compounds, 7th Edition; Wiley, 2005. https://books.google.com/books?id=mQ8cAAAAQBAJ&pgis=1
Sowinska, M.; Morawiak, M.; Bochyńska-Czyż, M.; Lipkowski, A. W.; Ńska, E. Z.; Zabłocka, B.; Urbanczyk-Lipkowska, Z. Molecular antioxidant properties and in vitro cell toxicity of the p-aminobenzoic acid (PABA) functionalized peptide dendrimers. Biomolecules. 2019, 9 (3), 89. https://doi.org/10.3390/biom9030089
Sun, H. L.; Ye, C. H.; Wang, X. Y.; Li, J. R.; Gao, S.; Yu, K. B. Lanthanide contraction and pH value controlled structural change in a series of rare earth complexes with p-aminobenzoic acid. Journal of Molecular Structure. 2004, 702 (1–3), 77–83. https://doi.org/10.1016/j.molstruc.2004.06.013
Susanthy, D.; Santosa, S. J.; Kunarti, E. S. Antibacterial activity of silver nanoparticles capped by p-aminobenzoic acid on Escherichia coli and Staphylococcus aureus. Indonesian Journal of Chemistry. 2020, 20 (1), 182–189. https://doi.org/10.22146/ijc.44652
Teixeira, J. A.; Siqueira, A. B. Thermal and spectroscopic characterization, antioxidant evaluation and pyrolysis of losartan with some bivalent metals. Journal of Analytical and Applied Pyrolysis. 2016, 117, 17–24. https://doi.org/10.1016/j.jaap.2015.12.023
Teixeira, J. A.; Nunes, W. D. G.; Colman, T. A. D.; Do Nascimento, A. L. C. S.; Caires, F. J.; Campos, F. X.; Gálico, D. A.; Ionashiro, M. Thermal and spectroscopic study to investigate p-aminobenzoic acid, sodium p-aminobenzoate and its compounds with some lighter trivalent lanthanides. Thermochimica Acta. 2016a, 624, 59–68. https://doi.org/10.1016/j.tca.2015.11.023
Teixeira, J. A.; Nunes, W. D. G.; do Nascimento, A. L. C. S.; Colman, T. A. D.; Caires, F. J.; Gálico, D. A.; Ionashiro, M. Synthesis, thermoanalytical, spectroscopic study and pyrolysis of solid rare earth complexes (Eu, Gd, Tb and Dy) with p-aminobenzoic acid. Journal of Analytical and Applied Pyrolysis. 2016b, 121, 267–274. https://doi.org/10.1016/j.jaap.2016.08.006
Teixeira, J. A.; Nunes, W. D. G.; Fernandes, R. P.; do Nascimento, A. L. C. S.; Caires, F. J.; Ionashiro, M. Thermal behavior in oxidative and pyrolysis conditions and characterization of some metal p-aminobenzoate compounds using TG–DTA, EGA and DSC-photovisual system. Journal of Analytical and Applied Pyrolysis. 2017, 128, 261–267. https://doi.org/10.1016/j.jaap.2017.10.002
Teixeira, J. A.; Fernandes, R. P.; Isquibola, G.; Gaspari, A. P. S.; Machado, A. E. H.; Caires, F. J.; Ionashiro, M. Synthesis, thermal behavior in oxidative and pyrolysis conditions, spectroscopic and DFT studies of some alkaline earth metals p-aminobenzoate complexes using TG-DTA, DSC, PXRD and EGA (TG-FTIR) techniques. Thermochimica Acta. 2022, 711, 179184. https://doi.org/10.1016/j.tca.2022.179184
Tsaryuk, V.; Vologzhanina, A.; Zhuravlev, K.; Kudryashova, V.; Szostak, R.; Zolin, V. Structures and manifestation of ortho-, meta-, and para-NH2-substitution in the optical spectra of europium and terbium aminobenzoates. Journal of Photochemistry and Photobiology A: Chemistry. 2014, 285, 52–61. https://doi.org/10.1016/j.jphotochem.2014.04.014
Xie, W.; Pan, W. P. Thermal characterization of materials using evolved gas analysis. Journal of Thermal Analysis and Calorimetry. 2001, 65 (3), 669–685. https://doi.org/10.1023/A:1011946707342
Ye, C. H.; Sun, H. L.; Wang, X. Y.; Li, J. R.; Nie, D. B.; Fu, W. F; Gao, S. Preparation of three terbium complexes with p-aminobenzoic acid and investigation of crystal structure influence on luminescence property. Journal of Solid State Chemistry. 2004, 177 (10), 3735–3742. https://doi.org/10.1016/j.jssc.2004.06.038
Zeleňák, V.; Vargová, Z.; Györyová, K. Correlation of infrared spectra of zinc(II) carboxylates with their structures. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy. 2007, 66 (2), 262–272. https://doi.org/10.1016/j.saa.2006.02.050
Zhai, L.; Zhang, W.-W.; Ren, X.-M.; Zuo, J.-L. Luminescent lanthanide MOFs based on conjugated 1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate ligand: syntheses, structures and photoluminescent properties. Dalton Trans. 2015, 44, 5746-5754. https://doi.org/10.1039/C4DT03794D
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