Determination of pKa Values for Acrylic, Methacrylic and Itaconic Acids by 1H and 13C NMR in Deuterated Water

Authors

  • Emma Lilia Ibarra-Montaño CIP, S.A. de C.V., Marcos Achar Lobaton No 2, Tepexpan Municipio Acolman de Nezahualcóyotl, CP 55885Estado de México
  • Norma Rodríguez-Laguna Universidad Autónoma Metropolitana-Iztapalapa, Depto. de Química, Área de Química Analítica, San Rafael Atlixco 186, Col. Vicentina, CP 09340 México
  • Aníbal Sánchez-Hernández Universidad Autónoma Metropolitana-Iztapalapa, Depto. de Química, Área de Química Analítica, San Rafael Atlixco 186, Col. Vicentina, CP 09340 México
  • Alberto Rojas-Hernández Universidad Autónoma Metropolitana-Iztapalapa, Depto. de Química, Área de Química Analítica, San Rafael Atlixco 186, Col. Vicentina, CP 09340 México

DOI:

https://doi.org/10.6000/1929-5030.2015.04.01.2

Keywords:

pKa values, acrylic acid derivatives, HYPNMR, 1H NMR, 13C NMR.

Abstract

Acrylic, methacrylic and itaconic acids have Brønsted acidity given by carboxylic groups, and they are extensively used in polymerization for modification of several soft-mater materials. By this reason it is important to propose better characterization studies and alternatives to obtain more of their physicochemical properties. In this work the pKa values of these acids are obtained by adjusting NMR chemical shifts for hydrogen and carbon nuclei as a function of pH with program HYPNMR, and compared with those obtained by potentiometric and conductometric titrations.

References


[1] Teramoto N, Shigehiro O, Ogawa Y, Maruyama Y, Shimasaki T, Shibata M. Polymer foam-reinforced hydrogels inspired by plant body frameworks as high-performance soft matter. Polymer J 2014; 46: 592-7. http://dx.doi.org/10.1038/pj.2014.41
[2] Kru I MK, Filipovi J. Copolymer hydrogels based on Nisopropylacrylamide and itaconic acid. Polymer 2006; 47: 148-55. http://dx.doi.org/10.1016/j.polymer.2005.11.002
[3] Dvo áková K, Dole el P, Ma ková E, Muselík J, Kejdu ová M, Vetch D. The effect of acid pH modifiers on the release characteristics of weakly basic drug from hydrophlilic– lipophilic matrices. AAPS PharmSciTech 2013; 14: 1341-8. http://dx.doi.org/10.1208/s12249-013-0019-1
[4] Koo H-J, So J-H, Dickey MD, Velev OD. Towards all-soft matter circuits: Prototypes of quasi-liquid devices with memristor characteristics. Adv Mater 2011; 23:3559-64. http://dx.doi.org/10.1002/adma.201101257
[5] Zohra R, Malana MA, Iqbal Z. Formulation, characterization, study of swelling kinetics and network parameters of Poly (MA-co-VA-co-AA) terpolymeric hydrogels with various concentrations of acrylic acid. J Res Updates Pol Sci 2013; 2: 142-52.
[6] Kim S, Kim JY, Huh KM, Acharya G, Park K. Hydrotropic polymer micelles containing acrylic acid moieties for oral delivery of paclitaxel. J Control Rel 2008; 132: 222-9. http://dx.doi.org/10.1016/j.jconrel.2008.07.004
[7] Bezençon J, Wittwer MB, Cutting B, Smie ko M, Wagner B, Kansy M, Ernst B. pKa determination by 1 H NMR spectroscopy – An old methodology revisited. J Pharm Biomed Anal 2014, 93: 147-55. http://dx.doi.org/10.1016/j.jpba.2013.12.014
[8] Rodríguez-Barrientos D, Rojas-Hernández A, Gutiérrez A, Moya-Hernández R, Gómez-Balderas R, Ramírez-Silva MT. Determination of pKa values of tenoxicam from 1 H NMR chemical shifts and of oxicams from electrophoretic mobilities (CZE) with the aid of programs SQUAD and HYPNMR. Talanta 2009; 80: 754-76. http://dx.doi.org/10.1016/j.talanta.2009.07.058
[9] De Robertis A, De Stefano C, Rigano C, Sammartano S. Thermodynamic parameters for the protonation of carboxylic acids in aqueous tetraethylammoniun iodide solutions. J Solution Chem 1990; 19: 569-87. http://dx.doi.org/10.1007/BF00647030
[10] Frassineti Ch, Ghelli S, Gans P, Sabatini A, Moruzzi MS, Vacca A. Nuclear Magnetic Resonance as a tool for determining protonation constants of natural polyprotic bases in solution. Anal Biochem 1995; 231: 374-82.
[11] FrassinetiCh, Alderighi L, Gans P, Sabatini A, Vacca A, Ghelli S. Determination of protonation constants of some fluorinated polyamines by means of 13C data processed by the new computer program HypNMR2000. Protonation sequence of polyamines. Anal Bioanal Chem 2003; 376: 1041-52. http://dx.doi.org/10.1006/abio.1995.9984
[12] Asuero A, Micha owski T. Comprehensive formulation of titration curves for complex acid-base systems and its analytical implications. Crit Rev Anal Chem 2011; 41: 151- 87. http://dx.doi.org/10.1007/s00216-003-2020-0
[13] Rojas-Hernández A, Rodríguez-Laguna N, Ramírez-Silva MT, Moya-Hernández R. Distribution diagrams and graphical methods to determine or to use the stoichiometric coefficients of acid-base and complexation reactions. In: Innocenti A, editor. Stoichiometry and research. The importance of quantity in biomedicine. Rijeka: InTech, 2011; p. 287-310. Available from: http://cdn.intechopen.com/pdfs-wm/30991.pdf
[14] Gans P, Sabatini A, Vacca A. SUPERQUAD: an improved general program for computation of formation constants from potentiometric data. J Chem Soc Dalton Trans 1985; 1195- 200. http://dx.doi.org/10.1039/dt9850001195
[15] Hoye TR, Zhao H. A Method for easily determining coupling constant values. J Org Chem 2002; 67: 4014-6. http://dx.doi.org/10.1021/jo001139v
[16] De Stefano C, Gianguzza A, Piazzese D, Sammartano S. Polyacrylite protonation in various aqueous ionic media at different temperatures and ionic strengths. J Chem Eng Data 2000; 45: 876-81. http://dx.doi.org/10.1021/je0000219
[17] Organization for Economic Co-operation and Development. Screening Information Data Sets. Methacrylic Acid Initial Assessment Profile. United Nations Environment Program Publications 2006. Available from: http://www.chem.unep.ch/irptc/sids/OECDSIDS/79414.pdf
[18] Bard AJ, Faulkner LR. Electrochemical methods. Fundamentals and applications. New York: Wiley 1980; (p 66.)
[19] Islas-Martínez JM, Rodríguez-Barrientos D, Galano A, et al. Deprotonation mechanism of new antihypertensive piperidinyl methylphenols: a combined experimental and theoretical study J Phys Chem B 2009; 113: 11765-74. http://dx.doi.org/10.1021/jp904474m
[20] Sanpedro-Montoya K, Martínez-Pérez B, Galano A, et al. Deprotonation mechanism and logP values of new antihypertensive thiomorpholinyl methylphenols: a combined experimental and theoretical study. J Chem Eng Data 2010; 55: 4323-31. http://dx.doi.org/10.1021/je100470g

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Published

2015-02-25

How to Cite

Ibarra-Montaño, E. L., Rodríguez-Laguna, N., Sánchez-Hernández, A. ., & Rojas-Hernández, A. (2015). Determination of pKa Values for Acrylic, Methacrylic and Itaconic Acids by 1H and 13C NMR in Deuterated Water. Journal of Applied Solution Chemistry and Modeling, 4(1), 7–18. https://doi.org/10.6000/1929-5030.2015.04.01.2

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General Articles