In this contribution we have tried to investigate whether the mechanical properties of the reverse micellar (RM) interface dictate the physical properties of entrapped water molecules in the RM waterpool. We choose AOT/Igepal-520/cyclohexane (Cy) mixed RM as a model system which exhibits synergistic water solubilization behavior as a function of interfacial stoichiometry. Such a phenomenon associates systematic modification of the interface curvature. Dynamic light scattering (DLS) studies reveal linear increase in the droplet size and aggregation number of the RMs with increasing XIgepal (mole fraction of Igepal in the surfactant mixture). FTIR study in the 3000-3800 cm(-1) region identifies that the relative population of the surface-bound water molecules is higher in AOT RM compared to that in Igepal RM, and in mixed systems it also follows a linear trend with XIgepal. Water relaxation dynamics as probed by time-resolved fluorescence spectroscopy using Coumarin-500 also reveals an overall linear trend with no characteristic feature around the solubilization inflation point. Our study clearly identifies that the physical properties of water in RM are mostly governed by the interfacial stoichiometry and water content, and merely bares any dependence on the mechanical properties of the interface.

Micelle-assisted "deintercalation" of intercalated drug/mutagen molecules from DNA is a well-established phenomenon; however, the driving energy cost for such a process is still not properly understood. In the present contribution, we have estimated the various energetic parameters for the SDS micelle-assisted deintercalation of a model DNA intercalator phenosafranine (PSF) using isothermal titration calorimetry (ITC) measurement. Both steady-state and picosecond-resolved fluorescence measurements provide strong evidence for the relocation of PSF molecules from the DNA interior to the micellar interface at an SDS concentration above cmc. The overall deintercalation process has been found to be enthalpy-wise forbidden (endothermic); however, it is strongly favored by a high positive entropy change, which can be correlated with the change in the associated hydration structure at the macromolecular interface.

Hydrogen-bonded structure and relaxation dynamics of water entrapped inside reverse micelles (RMs) composed of surfactants with different charged head groups: sodium bis(2-ethylhexyl) sulfosuccinate (AOT) (anionic), didodecyldimethylammonium bromide (DDAB) (cationic) and Igepal CO-520 (Igepal) (nonionic) in cyclohexane (Cy) have been studied as a function of hydration (defined by ). Sub-diffusive slow (sub-ns) relaxation dynamics of water has been measured by the time resolved fluorescence spectroscopy (TRFS) technique using two fluorophores, namely 8-anilino-1-naphthalenesulfonic acid (ANS) and coumarin-343 (C-343). The hydrogen bonded connectivity network of water confined in these RMs has been investigated by monitoring the hydrogen bond stretching and libration bands of water using far-infrared FTIR spectroscopy. In addition, the ultrafast collective relaxation dynamics of water inside these RMs has been determined by dielectric relaxation in the THz region (0.2-2.0 THz) using THz time domain spectroscopy (THz-TDS). While TRFS measurements establish the retardation of water dynamics for all the RM systems, FTIR and THz-TDS measurements provide with signature of charge specificity.

The photo physical properties of two mononuclear pentacoordinated copper(II) complexes formulated as [Cu(L)(Cl)(H2O)] (1) and [Cu(L)(Br)(H2O)] (2) HL = (1-[(3-methyl-pyridine-2-ylimino)-methyl]-naphthalen-2-ol) were synthesized and characterized by elemental, physicochemical, and spectroscopic methods. The density function theory calculations are used to investigate the electronic structures and the electronic properties of ligand and complex. The interactions of copper(II) complexes towards calf thymus DNA were examined with the help of absorption, viscosity, and fluorescence spectroscopic techniques at pH 7.40. All spectroscopy's result indicates that complexes show good binding activity to calf thymus DNA through groove binding. The optical absorption and fluorescence emission properties of microwires were characterized by fluorescence microscope. From a spectroscopic viewpoint, all compounds strongly emit green light in the solid state. The microscopy investigation suggested that microwires exhibited optical waveguide behaviour which are applicable as fluorescent nanomaterials and can be used as building blocks for miniaturized photonic devices. Antibacterial study reveals that complexes are better antimicrobial agents than free Schiff base due to bacterial cell penetration by chelation. Moreover, the antioxidant study of the ligand and complexes is evaluated by using 1,1-diphenyl-2-picrylhydrazyl (DPPH) free-radical assays, which demonstrate that the complexes are of higher antioxidant activity than free ligand.

In this contribution, we have examined a composition dependent self aggregated structural modification of a catanionic mixture of the surface active ionic liquid (IL) 1-butyl-3-methylimidazolium octyl sulphate and a cationic gemini surfactant (14-5-14) in aqueous medium. We have observed that the hydrodynamic diameter of the aggregates increases with increasing IL concentration and microscopic evidence (HRTEM, FESEM, and LCSM) shows the formation of vesicle like aggregates (Dh ≈ 200 nm) at XIL = 0.5. The steady state fluorescence anisotropy of the membrane binding probe DPH shows a micelle to vesicle transition at this composition. The viscosity of the solution shows a peak at XIL = 0.3, indicating the formation of a worm like micelle as an intermediate of the micelle to vesicle transition. The rotational dynamics shows a stiffer surfactant packing in the vesicles compared to the micelles, whereas, the solvation dynamics measurements indicate a higher abundance of bound type water in the vascular medium compared to that for the micelle. The formed vesicles also show stability towards temperature and biomolecules, which can be used for respective applications.

In this study, we have explored the slow (of the order of several hundreds of picoseconds) relaxation dynamics of water associated with the hydration shell of a biocompatible polymer, hydroxypropyl cellulose (HPC)-water mixture as a function of HPC concentration using time-resolved fluorescence spectroscopy. The relaxation dynamics slows down with a progressive increase in HPC content indicating restriction of the relaxation pathway of water molecules specially beyond a cellulose concentration of 20% wherein an isotropic to liquid crystalline cholesteric microscopic phase separation sets in. The activation energy calculated from the temperature dependent solvation dynamics studies also shows a similar trend. The nucleophilic activity of water molecules in these mixtures is determined by measuring the reaction kinetics of solvolysis of benzoyl chloride, and the reaction rate exhibits a marked decrease as the phase separation sets in. The observed results are correlated with a transition between the 'bulk' and 'bound' type of water molecules present in the system.

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Hydration of metal ions is critical to their adsorption, complexation, and discharge but remained elusive due to counterion interference. We introduce Raman difference spectroscopy with simultaneous curve fitting (RD-SCF) analysis to quantitatively retrieve the counterion-free OH stretch spectra of water in the hydration shell of various metal ions such as