Animesh Pan

Enthalpy-Entropy Compensation (EEC) Effect: A Revisit.

A short account of the developments and perspectives of IKR (iso-kinetic relation) and EEC (enthalpy (H) - entropy (S) compensation) has been presented. The IKR and EEC are known to be extra thermodynamic or empirical correlations though linear H-S correlation can be thermodynamically deduced. Attempt has also been made to explain the phenomena in terms of statistical thermodynamics. In this study, we have briefly revisited the fundamentals of both IKR and EEC from kinetic and thermodynamic grounds. A detailed revisit of the EEC phenomenon on varied kinetic and equilibrium processes has been also presented. Possible correlations among the free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes of different similar and nonsimilar chemical processes under varied conditions have been discussed with possible future projections.

Amphiphile behavior in mixed solvent media I: self-aggregation and ion association of sodium dodecylsulfate in 1,4-dioxane-water and methanol-water media.

Mixed aquo-organic solvents are used in chemical, industrial, and pharmaceutical processes along with amphiphilic materials. Their fundamental studies with reference to bulk and interfacial phenomena are thus considered to be important, but such detailed studies are limited. In this work, the interfacial adsorption of sodium dodecylsulfate (SDS, C12H25SO4(-)Na(+)) in dioxane-water (Dn-W) and methanol-water (Ml-W) media in extensive mixing ratios along with its bulk behavior have been investigated. The solvent-composition-dependent properties have been identified, and their quantifications have been attempted. The SDS micellization has been assessed in terms of different solvent parameters, and the possible formation of an ion pair and triple ion of the colloidal electrolyte, C12H25SO4(-)Na(+) in the Dn-W medium has been correlated and quantified. In the Ml-W medium at a high volume percent of Ml, the SDS amphiphile formed special associated species instead of ion association. The formation of self-assembly and the energetics of SDS in the mixed solvent media have been determined and assessed using conductometry, calorimetry, tensiometry, viscometry, NMR, and DLS methods. The detailed study undertaken herein with respect to the behavior of SDS in the mixed aquo-organic solvent media (Dn-W and Ml-W) is a new kind of endeavor.

Self-aggregation of MEGA-9 (N-nonanoyl-N-methyl-D-glucamine) in aqueous medium: physicochemistry of interfacial and solution behaviors with special reference to formation energetics and micelle microenvironment.

Self-aggregation of MEGA-9 (N-nonanoyl-N-methyl-D-glucamine), a nonionic sugar-based surfactant, was studied with respect to the effect of salt (NaCl) and ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) on its critical micelle concentration (cmc), aggregation number, hydrodynamic dimensions, energetics of micellization, and micellar microenvironment. Fluorimetry (both steady state and time resolved) was used to understand the microenvironments under the influence of additives. NaCl was found to decrease cmc, increase aggregation number (N), increase micellar size, and decrease enthalpy of micelle formation; the IL effect on the parameters was mostly opposite. The microscopic properties of micelles were probed using two fluorophores: one nonpolar C-153 (2,3,5,6-1H,4H-tetrahydro-8-trifluormethylquinolizino-(9,9a,1-gh)coumarin) and the other fairly polar ANS (8-anilinonaphthalene-1-sulfonate); they delivered information on the palisade layer and the peripheral region of the micelle interface, respectively. Energy of activation and entropy of activation of the dynamics of the probes were evaluated from their decay time, lifetime, and rotational movements in the regions of residency in the micelles. Density functional theory (DFT) calculations showed that the ternary combination MEGA-9/IL/H2O had the maximum interaction energy compared to any of the binary combinations. Thus, the ionic liquid reduced MEGA-9 self-association to a large extent.

The cholesterol aided micelle to vesicle transition of a cationic gemini surfactant (14-4-14) in aqueous medium

The cholesterol (Chol) aided micelle to vesicle transition of the cationic (14-4-14) gemini surfactant (GS) (tetramethylene-1,4-bis(dimethyltetradecylammonium bromide)) has been investigated employing spectrophotometry (visible and fluorescence), dynamic light scattering (DLS) and high resolution transmission electron microscopy (HRTEM) at different R (R = [Chol]/[GS]) values. Turbidity of the mixed solutions gradually increased with increasing R, and was highest at R = 1. There were hypsochromic spectral shifts with varied R, supporting transformation of micelles to vesicles, corroborated by DLS measurements. The vesicle sizes ranged between ∼160–240 nm. The steady state fluorescence anisotropy measurements suggested Chol induced anisotropy to the formed vesicles; they were structurally incongruent. The vesicle phase was found to be stable in the studied temperature range of 15–60 °C. The increased rotational relaxation time of the probe molecule C-153 (coumarin 153) supported enhanced rigidity of the local environment of the vesicles with an increasing proportion of Chol in the mixture.

A Rational Study of the Origin and Generality of Anti-Enthalpy–Entropy Compensation (AEEC) Phenomenon

Abstract In addition to enthalpy–entropy compensation (EEC), anti-enthalpy–entropy compensation (AEEC) phenomenon is also found in literature. The reports on the latter are limited, and analyses and justifications are so far unclear. Herein we present demonstration on the nature and possibility of the AEEC phenomenon. Although literature reports so far have mostly shown linear AEEC, we have found both linear and non-linear dependences. The non-linearity we consider arises from large “free energy window” (FEW) like EEC, recently presented and discussed. Attempts have been made to rationalize the observations in terms of solvation–desolvation phenomenon of the involved processes anticipated in previous studies. We have found that enthalpy and entropy of formation of gaseous and solid materials may also exhibit AEEC, it can be thus classified as a global phenomenon. In addition to AEEC, the phenomenon of no-enthalpy–entropy compensation (NEEC) is also reported. Thus, the phenomena EEC, AEEC and NEEC are thermodynamic puzzles that require close attention and analysis. With the help of wide range of physical chemical processes, an elaborate general understanding of the linear and non-linear AEEC phenomena has been attempted. The experimental data herein used are collected from literature reports, new measurements were not done. A variety of examples have supported possible generality of AEEC.