Circular Dichroism and Derivative Spectra Study of the Excitonic Aggregation of Pinacyanol by Aerosol-OT


Different structures are proposed for the complexes formed from the interaction between the cationic cyanine dye 1, 1’-diethyl-2, 2’-carbocyanine chloride (Pinacyanol chloride) and the anionic surfactant sodium bis (2-ethylhexyl) sul- fosuccinate (Aerosol-OT) in ethanol-water solutions. UV/vis and electronic circular dichroism (CD) spectra provide tools to study the concentration and solvent dependence of this interaction. The aggregation spectra of the dye are dominated by a strongly blue-shifted, sharp and single visible band, which appears at concentrations much below the critical micelle concentration (cmc) of Aerosol-OT. Above the cmc, the spectra in pure aqueous solution indicate disso- ciation into monomer and dimer species, and the system becomes completely empty of chirality. Two different CD spectra with a distinct isosbestic point are observed for complexes with different surfactant to dye ratios. Both the addi- tion of ethanol (more than 7.5%) and increasing the temperature retards the metachromatic process between the dye and Aerosol-OT. By using the peakFit program, the two overlapping excitonic absorption bands together with the optically inactive absorption band for one spectrum (the most optimal one) at a specific Aerosol-OT concentration were sepa- rated.

Share and Cite:

S. Khouri and V. Buss, "Circular Dichroism and Derivative Spectra Study of the Excitonic Aggregation of Pinacyanol by Aerosol-OT," Open Journal of Physical Chemistry, Vol. 2 No. 1, 2012, pp. 34-40. doi: 10.4236/ojpc.2012.21005.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] A. N. Maitra and H. F. Eicke, “Effect of Rotational Isom- erism on the Water-Solubilizing Properties of Aerosol OT as Studied by Hydrogen-1 NMR Spectroscopy,” Journal of Physical Chemistry, Vol. 85, No. 18, 1981, pp. 2687- 2691. doi:10.1021/j150618a024
[2] E. Pramauro and E. Pelizzetti, “Surfactants in Analytical Chemistry: Applications of organized amphiphilic media,” Elsevier, Amsterdam, 1996.
[3] F. Candau, Y. S. Leong, G. Pouyet and S. Candau, “In- verse Microemulsion Polymerization of Acrylamide: Cha- racterization of the Water-in-Oil Microemulsions and the Final Microlatexes,” Journal of Colloid and Interface Science, Vol. 101, No. 1, 1984, pp. 167-183. doi:10.1016/0021-9797(84)90017-1
[4] J. Eastoe, B. H. Robinson, A. J. W. G. Visser and D. C. Steytler, “Rotational Dynamics of AOT Reversed Micelles in Near-Critical and Supercritical Alkanes,” Journal of the Chemical Society, Faraday Transactions, Vol. 87, No. 12, 1991, pp. 1899-1903. doi:10.1039/ft9918701899
[5] G. Calvaruso, A. Minore and V. Turco Liveri, “FT-IR Investigation of the Urea State in AOT Reversed Mi- celles,” Journal of Colloid and Interface Science, Vol. 243, No. 1, 2001, pp. 227-232. doi:10.1006/jcis.2001.7878
[6] L. M. Nikolenko, A. V. Ivanchihina, S. B. Brichkin and V. F. Razumov, “Ternary AOT/Water/Hexane Systems as ‘Micellar Sieves’ for Cyanine Dye J-Aggregates,” Journal of Colloid and Interface Science, Vol. 332, No. 2, 2009, pp. 366-372. doi:10.1016/j.jcis.2008.12.022
[7] A. Jada, J. Lang and R. Zana, “Relation between Electrical Percolation and Rate Constant for Exchange of Material between Droplets in Water in Oil Microemulsions,” Journal of Physical Chemistry, Vol. 93, No. 1, 1989, pp. 10-12. doi:10.1021/j100338a004
[8] S. Bisal, P. K. Bhattacharya and S. P. Moulik, “Conductivity Study of Microemulsions: Dependence of Structural Behavior of Water/Oil Systems on Surfactant, Cosurfactant, Oil, and Temperature,” Journal of Physical Chemistry, Vol. 94, No. 1, 1990, pp. 350-355. doi:10.1021/j100364a060
[9] W. West and S. Pearce, “The Dimeric State of Cyanine Dyes,” Journal of Physical Chemistry, Vol. 69, No. 6, 1965, pp. 1894-1903. doi:10.1021/j100890a019
[10] D. L. Akins and J. W. Macklin, “Dependence of Raman Scattering by Aggregated 2,2-Cyanine on pH and Excitation Wavelength,” Journal of Physical Chemistry, Vol. 93, No. 16, 1989, pp. 5999-6007. doi:10.1021/j100353a014
[11] P. Bilski, R. N. Holt and C. F. Chignell, “Premicellar Aggregates of Rose Bengal with Cationic and Zwitterionic Surfactants,” Journal of Photochemistry and Photobiology A, Vol. 110, No. 1, 1997, pp. 67-74. doi:10.1016/S1010-6030(97)00166-4
[12] M. Sarkar and S. Poddar, “Studies on the Interaction of Surfactants with Cationic Dye by Absorption Spectros- copy,” Journal of Colloid and Interface Science, Vol. 221, No. 2, 2000, pp. 181-185. doi:10.1006/jcis.1999.6573
[13] H. Von Berlepsch and C. B?ttcher, “Network Superstructure of Pseudoisocyanine J-Aggregates in Aqueous Sodium Chloride Solution Revealed by Cryo-Transmission Elec- tron Microscopy,” Journal of physical chemistry B, Vol. 106, No. 12, 2002, pp. 3146-3150. doi:10.1021/jp0143701
[14] P. Mukerjee and K. J. Mysels, “A Re-Evaluation of the Spectral Change Method of Determining Critical Micelle Concentration,” Journal of the American Chemical Society, Vol. 77, No. 11, 1955, pp. 2937-2943. doi:10.1021/ja01616a003
[15] M. K. Pal and P. K. Pal, “Dichroic Probe of Different Modes of Aggregation of Pinacyanol by Bis(2-ethylhe- xyl)sulfosuccinate below and above Its Critical Micelle Concentration,” Journal of Physical Chemistry, Vol. 94, No. 6, 1990, pp. 2557-2559. doi:10.1021/j100369a062
[16] R. Sabaté and J. Estelrich, “Determination of Micellar Microenvironment of Pinacyanol by Visible Spectros- copy,” Journal of physical chemistry B, Vol. 107, No. 17, 2003, pp. 4137-4142. doi:10.1021/jp027409q
[17] L. Antonov and D. Nedeltchera, “Resolution of Overlapping UV-Vis Absorption Bands and Quantitative Analysis,” Chemical Society Reviews, Vol. 29, No. 3, 2000, pp. 217-227. doi:10.1039/a900007k
[18] H. Min, J. Park, J. Yu and D. Kim, “The Spectroscopic Studies on the Aggregation Behavior of Cyanine Dyes,” Bulletin of the Korean Chemical Society, Vol. 19, No. 6, 1998, pp. 650-654.
[19] S. J. Khouri, and V. Buss, “UV/Vis Spectral Study of the Self-Aggregation of Pinacyanol Chloride in Ethanol- Water Solution,” Journal of Solution Chemistry, Vol. 39, No. 1, 2010, pp. 121-130. doi:10.1007/s10953-009-9476-2
[20] E. F. Williams, N. T. Woodberry and J. K. Dixon, “Purification and Surface Tension Properties of Alkyl Sodium Sulfosuccinates,” Journal of Colloid and Interface Science, Vol. 12, No. 4, 1957, pp. 452-459.
[21] W. C. Presto and W. Preston, “Some Correlating Principles of Detergent Action,” Journal of Physical and Colloid Chemistry, Vol. 52, No. 1, 1948, pp. 84-97. doi:10.1021/j150457a010
[22] C. Burda, X. Chen, R. Narayanan and M. A. El-Sayed, “Chemistry and Properties of Nanocrystals of Different Shapes,” Chemical Reviews, Vol. 105, No. 4, 2005, pp. 1025-1102. doi:10.1021/cr030063a
[23] N. Berova and K. Nakanishi, “Exciton Chirality Method: Principles and Applications,” In: N. Berova, K. Nakanishi and R. Woody, Eds., Circular Dichroism: Principles and Applications, Wiley-VCH, New York, 2000, p. 337.
[24] J. L. Lynn and B. H. Bory, “Surfactants,” In: R. Kirk, Ed., Concise Encyclopaedia of Chemical Technology, Wiley, New York, 1999, p. 1949.

Copyright © 2023 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.