Surajit Ghosh

Picosecond solvation dynamics--a potential viewer of DMSO-water binary mixtures.

In this work, we have investigated the composition dependent anomalous behavior of dimethyl sulfoxide (DMSO)-water binary mixture by collecting the ultrafast solvent relaxation response around a well known solvation probe Coumarin 480 (C480) by using a femtosecond fluorescence up-conversion spectrometer. Recent molecular dynamics simulations have predicted two anomalous regions of DMSO-water binary mixture. Particularly, these studies encourage us to investigate the anomalies from experimental background. DMSO-water binary mixture has repeatedly given evidences of its dual anomalous nature in front of our systematic investigation through steady-state and time-resolved measurements. We have calculated average solvation times of C480 by two individual well-known methods, among them first one is spectral-reconstruction method and another one is single-wavelength measurement method. The results of both the methods roughly indicate that solvation time of C480 reaches maxima in the mole fraction of DMSO XD = 0.12-0.17 and XD = 0.27-0.35, respectively. Among them, the second region (XD = 0.27-0.35) is very common as most of the thermodynamic properties exhibit deviation in this range. Most probably, the anomalous solvation trend in this region is fully guided by the shear viscosity of the medium. However, the first region is the most interesting one. In this region due to formation of strongly hydrogen bonded 1DMSO:2H2O complexes, hydration around the probe C480 decreases, as a result of which solvation time increases.

Ultrafast FRET to Study Spontaneous Micelle-to-Vesicle Transitions in an Aqueous Mixed Surface-Active Ionic-Liquid System†

The spontaneous micelle-to-vesicle transition in an aqueous mixture of two surface-active ionic liquids (SAILs), namely, 1-butyl-3-methylimidazolium n-octylsulfate ([C4mim][C8SO4]) and 1-dodecyl-3-methylimidazoium chloride ([C12mim]Cl) is described. In addition to detailed structural characterization obtained by using dynamic light scattering, transmission electron microscopy (TEM), and cryogenic TEM techniques, ultrafast fluorescence resonance energy transfer (FRET) from coumarin 153 (C153) as a donor (D) to rhodamine 6G (R6G) as an acceptor (A) is also used to study micelle-vesicle transitions in the present system. Structural transitions of SAIL micelles ([C4mim][C8SO4] or [C12mim]Cl micelles) to mixed SAIL vesicles resulted in significantly increased D-A distances, and therefore, increased timescale of FRET. In [C4mim][C8SO4] micelles, FRET between C153 and R6G occurs on an ultrafast timescale of 3.3 ps, which corresponds to a D-A distance of about 15 Å. As [C4mim][C8SO4] micelles are transformed into mixed micelles upon the addition of a 0.25 molar fraction of [C12mim]Cl, the timescale of FRET increases to 300 ps, which suggests an increase in the D-A distance to 31 Å. At a 0.5 molar fraction of [C12mim]Cl, unilamellar vesicles are formed in which FRET occurs on multiple timescales of about 250 and 2100 ps, which correspond to D-A distances of 33 and 47 Å. Although in micelles and mixed micelles the obtained D-A distances are well correlated with their radius, in vesicles the obtained D-A distance is within the range of the bilayer thickness.

The Chameleon‐Like Nature of Zwitterionic Micelles: The Effect of Ionic Liquid Addition on the Properties of Aqueous Sulfobetaine Micelles

We used fluorescence probing, ζ potentials, and dynamic light scattering measurements to study the interactions between the zwitterionic surfactant N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB-16) and three ionic liquids (ILs), 1-ethyl-3-methylimidazolium ethylsulfate ([C(2)mim][C(2)SO(4)]), 1-ethyl-3-methylimidazolium n-butylsulfate ([C(2)mim][C(4)SO(4)]), and 1-ethyl-3-methylimidazolium n-hexylsulfate ([C(2)mim][C(6)SO(4)]). The three ILs have the same cationic part and their anionic parts differ only in the length of the alkyl chain. The aim of our work is to offer a comparative study and establish the role of the alkyl chain length of the anion of ILs on 1) the incorporation of these anions in the zwitterionic micelles of SB-16 (selectivity of anions) and 2) the physicochemical properties of aqueous solutions of SB-16. Results show that, at lower concentrations (i.e. ≤20 mM), the different ILs modify the properties of the aqueous SB-16 solution in similar manner. All of them bring about a decrease in the critical micelle concentration (CMC) and also in size, and increase the aggregation number of the SB-16 micelles; these effects are more dramatic when [C(2)mim][C(6)SO(4)] is used as the additive rather than [C(2)mim][C(4)SO(4)] and [C(2)mim][C(2)SO(4)]. It is proposed that, in case of [C(2)mim][C(6)SO(4)], the presence of a hexyl chain on the hexylsulfate ion allows the ion to align itself with the tail part of SB-16, whereas, in the case of [C(2)mim][C(2)SO(4)], the presence of ethyl chain in the ethylsulfate ion is not sufficient to bring about a similar alignment of the ethylsulfate anion with the tail part of SB-16. This difference in the location of the anions of the ILs is responsible for the different behavior of the ILs.

Effect of confinement on excited-state proton transfer of Firefly's chromophore d-luciferin in AOT reverse micelles

Excited-state intermolecular proton transfer of D-luciferin in reverse micelles has been investigated using steady-state and time-resolved fluorescence spectroscopy measurement. The different polar cores have been chosen for the study of proton transfer dynamics in aerosol-OT (AOT) reverse micelles. It is shown that aqueous reverse micelle is the suitable environment for the photoprotolytic reaction of D-luciferin. The neutral form of the chromophore is present both in ground and excited state at W0 = 0. The proton transfer in nanometer size water pool of water/AOT/n-heptane begins at W0 = 8 and increases with increasing W0 values. However, the intermolecular excited-state proton transfer (ESPT) of D-luciferin is inhibited in nonaquous reverse micelles with DMF and DMSO as a polar core. Thus, the requirement of ESPT of D-luciferin to take place in reverse micelles consists of polar protic solvent like water as a polar core.

Solvent and rotational relaxation of coumarin-153 and coumarin-480 in ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) modified sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (NaAOT) micelle

Understanding ion transport dynamics, structure of surfactant aggregates in ionic liquids or ionic liquid/water solutions are quite interesting and potentially important due to widespread applications of surfactant-based systems. In this manuscript we have investigated the effect of 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)) addition on solvent and rotational relaxation of coumarin-153 (C-153) and coumarin-480 (C-480) in aqueous solution of sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (NaAOT) using steady state and picosecond time resolved fluorescence spectroscopy. The strong adsorption of the bmim(+) at the interface and the role of the ionic liquid particularly the cation bmim(+) in the modification of the interfacial geometry were probed by the analysis of decay parameters and the rotational relaxation parameters. Since the addition of the NaAOT in water-bmimBF(4) mixture above critical micellar concentration (48 mM, obtained from observing pyrene fluorescence) causes strong adsorption of the ionic liquid particularly the cation bmim(+), the average solvation time, particularly the slow component increases significantly. More importantly we have found the probe dependent solvation dynamics due to the different location of the probe molecules, C-153 and C-480. C-153 being hydrophobic in nature resides in the stern layer and the adsorption of the bmim(+) at the interface modifies stern layer more effectively. So we have observed more pronounced change in solvation dynamics in case of C-153 compared to that in case of C-480. The fluorescence anisotropy decays of the probe molecules were found to be biexponential in nature. The anisotropy decay was interpreted by using a model which consists of the wobbling (rotational) and translational diffusion of the dye coupled with the rotational motion of the micelle as a whole.

Micelle-vesicle-micelle transition in aqueous solution of anionic surfactant and cationic imidazolium surfactants: Alteration of the location of different fluorophores

The presence of different surfactants can alter the physicochemical behaviors of aqueous organized assemblies. In this article, we have investigated the location of hydrophobic molecule (Coumarin 153, C153) and hydrophilic molecule (Rhodamine 6G perchlorate, R6G) during micelle-vesicle-micelle transition in aqueous medium in presence of anionic surfactant, sodium dodecylbenzenesulfonate (SDBS) and cationic imidazolium-based surfactant, 1-alkyl-3-methylimidazolium chloride (CnmimCl; n=12, 16). Initially, the physicochemical properties of anionic micellar solution of SDBS has been investigated in presence of imidazolium-based surfactant, CnmimCl (n=12, 16) in aqueous medium by visual observation, turbidity measurement, zeta potential (ζ), dynamics light scattering (DLS), and transmission electron microscopy (TEM). Zeta potential (ζ) measurement clearly indicates that the incorporation efficiency of C16mimCl in SDBS micelle is better than the other one due to the involvement of strong hydrophobic as well as electrostatic interaction between the two associated molecules. Turbidity and DLS measurements clearly suggest the formation of vesicles over a wide range of concentration. Finally, the rotational motion of C153 and R6G has also been monitored at different mole fractions of CnmimCl in SDBS-CnmimCl (n=12, 16) solution mixtures. The hydrophobic C153 molecules preferentially located in the bilayer region of vesicle, whereas hydrophilic R6G can be solubilized at surface of the bilayer, inner water pool or outer surface of vesicles. It is observed that rotational motion of R6G is altered significantly in SDBS-CnmimCl solution mixtures in presence of different mole fractions of CnmimCl. Additionally, the translational diffusion motion of R6G is monitored using fluorescence correlation spectroscopy (FCS) techniques to get a complete scenario about the location and translational diffusion of R6G.

Zwitterionic micelles as a soft template for the extremely rapid synthesis of small hollow gold nanocontainers

Hollow gold nanoparticles (HGNs) are unique materials having properties which can be beneficial in controlled and traceable drug delivery and molecular imaging. In the recent past various methods have been developed for the synthesis of these HGNs, the most widely used method employed the galvanic replacement reaction of silver for gold. In this manuscript we have developed a simple approach for the formation of hollow gold nanoparticles (HGNs) using an aqueous solution of a zwitterionic surfactant, N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate SB-16, as a soft template and different ILs, N,N-dimethylethanolammonium formate/hexanoate (DAF/DAH), as reducing agents. The size distribution and morphology of these HGNs were determined by dynamic light scattering (DLS) measurement, and transmission electron microscopy (TEM). UV-vis spectroscopy was used to assess their optical properties. This soft template approach requires less than 1 min at 338 K for the production of HGNs of size less than 20 nm.