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Synthesis, CMC determination and influence of the micelles, β-cyclodextrin, ionic liquids and liposome(dipalmitoylphosphatidylcholine) vesicles on the kinetics of an outer-sphere electron transfer reaction

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Abstract

The surfactant–cobalt(III) complex, cis-[Co(trien)(4AMP)(DA)](ClO4)3, trien = triethylenetetramine, 4AMP = 4-aminopyridine, DA = dodecylamine was synthesized and characterized by various spectroscopic and physico-chemical techniques. The critical micelle concentration (CMC) value of this surfactant–cobalt(III) complex in aqueous solution was found out from conductance measurements. The conductivity data (at 303, 308, 313, 318 and 323 K) were used for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG °m , ΔHm and ΔS °m ). Also the kinetics of reduction of this surfactant–cobalt(III) complex by hexacyanoferrate(II) ion in micelles, β-cyclodextrin, ionic liquids (ILs) and in liposome vesicles (DPPC) media were studied at different temperature. The rate constant for the electron transfer reaction in micelles was found to increase with increase in the initial concentration of the surfactant–cobalt(III) complex. This peculiar behaviour of dependence of second-order rate constant on the initial concentration of one of the reactants has been attributed to the presence of various concentration of micelles under different initial concentration of the surfactant–cobalt(III) complex in the reaction medium. Inclusion of the long aliphatic chain of the surfactant complex ion into β-cyclodextrin leads to decrease in the rate constant. Below the phase transition temperature of DPPC, the rate decreased with increasing concentration of DPPC, while above the phase transition temperature the rate increased with increasing concentration of DPPC. It is concluded that below the phase transition temperature, there is an accumulation of surfactant–cobalt(III) complex at the interior of the vesicle membrane through hydrophobic effects, and above the phase transition temperature the surfactant–cobalt(III) complex is released from the interior to the exterior surface of the vesicle. In the presence of ionic liquid medium the second order rate constant for this electron transfer reaction for the same complex was found to increase with increasing concentration of ILs has also been studied. An outer-sphere mechanism is proposed for all these reactions and the results have been explained based on the hydrophobicity of the ligand and the reactants with opposite charges.

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Acknowledgments

We are grateful to the UGC–COSIST and DST–FIST programmes of the Department of Chemistry, Bharathidasan University, and UGC–RFSMS fellowship to one of the authors, K. Nagaraj, by Bharathidasan University. Financial assistance from the CSIR (Grant No. 01(2461)/11/EMR-II), DST (Grant No. SR/S1/IC-13/2009) and UGC (Grant No. 41-223/2012(SR) sanctioned to S. Arunachalam are also gratefully acknowledged.

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  1. School of Chemistry, Bharathidasan University, Trichirappalli, 620024, Tamilnadu, India

    Karuppiah Nagaraj & Sankaralingam Arunachalam

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  1. Karuppiah Nagaraj
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Correspondence to Sankaralingam Arunachalam.

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Nagaraj, K., Arunachalam, S. Synthesis, CMC determination and influence of the micelles, β-cyclodextrin, ionic liquids and liposome(dipalmitoylphosphatidylcholine) vesicles on the kinetics of an outer-sphere electron transfer reaction. J Incl Phenom Macrocycl Chem 79, 425–435 (2014). https://doi.org/10.1007/s10847-013-0365-3

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