Langmuir 1991, 7, 23-29
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Articles Micellization Properties of Zwitterionic Surfactants Derived from Nicotinic Acid in Aqueous Solutions N. A. Wiederkehr,? K. Kalyanasundaram,*pt M. Gratzel,? G. Viscardi,j P. Savarino,t and E. Barnit Institut de Chimie Physique, Ecole Polytechnique F6dbrale de Lausanne, CH-1015 Lausanne, Switzerland, and Dipartmento di Chimica Generale ed Organica Applicata, Universith di Torino, I-10125 Torino, Italy Received February 14, 1990. In Final Form: June 7, 1990
Various properties of monomeric and micellar (aggregated)forms of a series of zwitterionic surfactants based on nicotinic acid (N-alkylnicotinicacids, R-NA (R = Cg,CIO, C12,(214,and C16)have been determined in aqueous solution by utilization of a number of physical methods (visible light absorption, fluorescence probe analysis, surfactant tension measurements, and low-angle light scattering): protonation equilibria, extent of counterion adsorption, critical micellar temperature, critical micellar concentration, and micellar aggregation number.
Introduction Surfactant derivatives that carry functional groups (socalled "functional surfactants")allow chemical reactions (thermal or photochemical) to be carried out under controlled microheterogenenus conditions.lv2 Typical examples of functional surfactants with demonstrated applications are the long-chain derivatives with chromophores such as Ru(bpy)32+,3electron acceptors such as ~ i o l o g e n ,a~n d electron d o n o r s such a s 1,4dihydr~nicotinamide.~ Surfactants with pendant fluorescent groups such as pyrenes are yet another case of functional surfactants of great utility in studies of microheterogeneous media. For several years, we and several other groups have been interested in the development of such functional surfactants. Recently we described the properties and applications of nicotinamide-based surfactant^.^ In this work, we continue this theme and + Ecole
Polytechnique FBdhrale de Lausanne, Switzerland. Universite di Torino, Italy. (1) Thomas, J. K. Chemistry of Excitation at Interfaces;American Chemical Society: Washington, QC, 1984. (2) Kalyanasundaram, K. Photochemistry in Microheterogeneous Systems; Academic Press: London, 1987. (3) For some early applications, see: (a) Gaines, G. L. Inorg. Chem. 1980, 19, 1710. (b) Schmehl, R. H.; Whitesell, L. G.; Whitten, D. G. J. Am. Chem. SOC.1981,103,3761. (c) Foreman, T. K.; Sobol, W. M.; Whitten, D. G. J.A m . Chem. SOC.1981,103,5339. (d) Brugger, P.-A.; Gritzel, M.; Gaurr, T.; McLendon, G. J. Phys. Chem 1982,86,944. (e) Ford, W. E.; Otvos, J. W.; Calvin, M. Proc. Natl. Acad. Sci. U.S.A. 1979, 76,3590. (0 Tunuli, M. S.; Fendler, J. H. J. Am. Chem. SOC.1981,103, 2507. (4) For some early applications, see: (a) Krieg, M.; Pileni, M.-P.; Braun, A. M.; Gritzel, M. J. Colloid Interface Sci 1981,83, 209. (b) Brugger, P.-A.; Infelta, P. P.; Braun, A. M.; Gritzel, M. J. Am. Chem. SOC.1981, 103, 320. (c) Laane, C.; Ford, W. E.; Calvin, M. Proc. Natl. Acad. Sci. U.S.A. 1981, 78, 2017. (d) Kurihara, K.; Tundo, P.; Fendler, J. H. J. Phys. Chem. 1983,87,3777.
(5) (a) Kalyanasundaram, K.;Colassis, T.; Humphry-Baker, R.; Savarino, p.; Barni, E.; Pellizzetti, E.; Graetzel, M. J.Am. chem. SOC.1989, 111,3300. (b) Kalyanasundaram, K.; Colassis, T.; Humphry-Baker, R.; Savarino, P.; Barni, E.; Pellizzetti, E.; Graetzel, M. J. Colloid Interface
Sci. 1989, 132, 469. (6) For some early applications, see: (a) Katusin-Razem, B.; Wong, M.; Thomas, J. K. J. A m . Chem. SOC.1981, 100, 2507. (b) Sengupta, P.; Sackmann, E.; Kiihnle, W.; Scholtz, H. P. Biochem. Biophys. Acta 1976, 436, 869. (c) Galla, H.-J.; Hartmann, W.; Thiele, U.; Sackmann, E. J. Membr. Biol. 1979, 48, 216. (d) Kano, K.; Kawazumi, H.; Ogawa, T.; Sunamoto, J. J. Phys. Chem. 1981,85,2204. (e) Hunter, T. F.; Younis, A. I. J. Chem. Soc., Faraday Trans 1, 1981, 75, 550.
describe the basic properties of surfactants based on nicotinic acid chromophore. Nicotinic acid derivatives are an important class of biological molecules closely related to their carboxamide. Nicotinic acid (known as niacin) itself is widely used as vitamin B3. N-methylnicotinic acid, commonly known as "trigoneline" is considered to play an important biological role in controling (Gzfactor) mechanisms.' It is the first mitotic cycle hormone shown to regulate cell division and was synthesized for the first time by Spath in 1944. Trigacid form) and its oneline (1-methyl-3-carboxypyridinium isomer homarine (l-methyl-2-carboxypyridinium,acid form) have a wide distribution in the plant and animal kingdoms. Despite their importance and wide occurrence, there has not been any systematic study on these compounds. References 8-13 list some of the few publications available on these compounds. Recently, we have initiated a systematic study of this class of compounds using several physical techniques. This report summarizes results of our observations on the characterization and aggregation properties in aqueous solution.
Trigoneline
Homarine
N-alkylnicotinic acid (R-NA)
An interesting aspect of the nicotinic acid surfactants (7) (a)Pimental, G. Ed. Opportunities in Chemistry;National Academy of Sciences Report: Washington, 1987. (b) Dictionary of Organic Compounds; Chapman and Hall: London, 1982; Vol. 4, edition V. (8)Gama, Y.; Suzuki, H.; Narasaki, H. J. J p n . Oil Chcm. SOC.1981, 31, 11. (9) Kourai, H.;Takechi, H.; Horie,T.;Takuichi,K.; Shibasaki, LBokin Bobai 1985,136, 245. (10) Hakala, M. T.; Schwert, G. W. Biochim. Biophys. Acta 1985,16, 489. (11) Ghosal, S.; Srivastava, R. S.; Bhattacharya, S. K.; Debnath, P. K. J. Plant. Med. 1973, 23, 321. (12) (a) Rusling, J. F. J.Electroanal. Chem. 1981,125,447. (b) Carter, M. T.; Geoffrey, N. K.; Rusling, J. R. J. Electroanal. Chem. 1984,170,
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(13) Wang, S. Y. Biochemistry 1968, 7, 10.
0743-7463/91/2~01-0023$02.50/00 1991 American Chemical Society
24 Langmuir, Vol. 7,No. 1, 1991
Wiederkehr e t al.
Table I. Data on Elemental Analysis and Melting Point for Various N-Alkulnicotinic Acid Derivatives ~~
elemental analysis: % C H N Br 46.17 5.38 5.30 30.61 (46.17) (5.43) (5.39) (30.72) CaNA-Br(A) 53.10 7.05 4.28 25.13 (53.17) (7.01) (4.43) (25.27) 7.53 4.34 23.56 CloNA-Br(A) 55.50 (55.82) (7.61) (4.07) (23.21) Cr*NA-Br(A) 57.98 8.17 3.96 21.47 . . (58.06) (8.12) (3.76) (21.46) 9.32 4.11 10.79 CiZNA-Cl(A) 65.88 (63.91) (8.88) (4.14) (10.50) 19.51 CldNA-Br(A) 60.03 8.53 3.60 (60.00) (8.56) (3.50) (19.96) CIGNA-Br(A) 61.70 18.19 9.11 3.32 (61.67) (8.94) (3.27) (18.65) 10.14 4.41
