1. Two-dimensional surface properties of PEO-PPO-PEO triblock copolymer film at the air/water interface in the absence and presence of Tyr-Phe dipeptide, Val-Tyr-Val tripeptide, SDS and stearic acid
Jilly James, Chidambaram Ramalechume, Asit Baran Mandal Colloids Surf B Biointerfaces. 2011 Feb 1;82(2):345-53. doi: 10.1016/j.colsurfb.2010.09.007. Epub 2010 Sep 15.
Two-dimensional surface properties of PEO-PPO-PEO triblock copolymer film (Mol.Wt. 2800) in the absence and presence of Tyr-Phe dipeptide, Val-Tyr-Val tripeptide, sodium dodecylsulfate and stearic acid have been investigated for the first time at the air/water interface using Langmuir film balance technique. It is observed that the above polymer forms fairly stable film at the air/water interface. There are no significant changes observed in the surface pressure-area (π-A) isotherms of polymer in the presence of SDS. However, more expanded film was formed in presence of SDS since the solubility of the polymer is more in SDS and the polymer network is disturbed in presence of SDS, which results in the increase in surface area of the polymer films. In the presence of dipeptide and tripeptide, the surface area of the polymer film decreased with a slight increase in the surface pressure indicating the binding of these peptides to polymer, which enhances the stability of the polymer film. Thermodynamic studies on the change in surface area (ΔA) and excess free energy of mixing (ΔG(mix)(E)) associated with the formation of the mixed film suggest the occurrence of a thermodynamically unstable mixed film. The presence of SDS slightly decreases the formation of mixed film of stearic acid with triblock copolymer and peptides due to the solubilization of these compounds in SDS. However, the hydrophobicity of the polymer films increases in the presence of stearic acid, leading to the increase in surface pressure. The positive deviation of ΔA and the positive ΔG(mix)(E) values show the non-ideality and incompatibility of thermodynamically unstable mixed films. The thermodynamic results suggest that the stability and compatibility of the polymer, peptides and their mixed films with stearic acid in the presence of SDS are decreased, which is in good agreement with the results obtained for other polymeric systems.
2. Micelle formation of Tyr-Phe dipeptide and Val-Tyr-Val tripeptide in aqueous solution and their influence on the aggregation of SDS and PEO-PPO-PEO copolymer micelles
Jilly James, Asit Baran Mandal Colloids Surf B Biointerfaces. 2011 May 1;84(1):172-80. doi: 10.1016/j.colsurfb.2010.12.029. Epub 2011 Jan 7.
The aggregation properties of Tyr-Phe dipeptide and Val-Tyr-Val tripeptide were studied in aqueous solution and in the presence of SDS and SDS-polymer environments using UV-visible, surface tension, fluorescence and circular dichroism (CD) techniques. Both the peptides formed micelles. The cmc values obtained for dipeptide and tripeptide are 2×10(-5) and 4×10(-5) M, respectively in aqueous solution at 25°C. The presence of additives (SDS and polymer) hindered the micelle formation of peptides. The cmc values obtained by various methods are in good agreement with each other. Effect of peptides on the aggregation properties of SDS also was investigated. The cmc of SDS was decreased in presence of peptides and were reduced with increase in temperature. Using monophasic micellization concept, the association constant (K(A)) for the SDS-peptide mixed micellar systems was determined. Using biphasic model, the thermodynamic parameters viz; ΔG°(m), ΔH°(m) and ΔS°(m) for SDS-water and SDS-peptide-water mixed micellar systems, the standard free energy for transfer of SDS from aqueous to peptide additive environments were estimated at various temperatures. These results suggest that the SDS is more stable in micellized form in the SDS-water-peptide ternary systems compared to the situation in the corresponding SDS-water binary systems.
3. The aggregation of Tyr-Phe dipeptide and Val-Tyr-Val tripeptide in aqueous solution and in the presence of SDS and PEO-PPO-PEO triblock copolymer: fluorescence spectroscopic studies
Jilly James, Asit Baran Mandal J Colloid Interface Sci. 2011 Aug 15;360(2):600-5. doi: 10.1016/j.jcis.2011.04.058. Epub 2011 Apr 29.
The micelle formation of Tyr-Phe dipeptide and Val-Tyr-Val tripeptide has been studied for the first time. The aggregation numbers were determined for both the peptides in aqueous solution and in the presence of SDS and PEO-PPO-PEO triblock copolymer additive environments. The results obtained by steady state and time-resolved fluorescence spectroscopic techniques are in good agreement with each other. The higher value of aggregation number confirms the formation of mixed micelles. The fluorescence lifetime of tyrosine in various micellar and mixed micellar systems were also determined. The decreased lifetime values with the quencher suggested the dynamic nature of the quenching process. However, the possibility of static quenching cannot be ruled out. The accessibility of DPC quencher was found to be more in dipeptide than tripeptide.
