Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite consistent with that of 1H NMR and fluorescence spectroscopy at cac from the concentration dependence of refractive index measurements. Standard free energies of aggregation DeltaGom of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.

Measurements of the static dielectric constant (epsilon) of ionic liquids (ILs) are very difficult because of the decay of field by the ionic conductivity of ILs. Herein, we describe an easy method for the prediction of epsilon of various imidazolium-based ILs [C_n mim] from n, i.e. the ratio of internal pressure (P_i) and cohesive energy density (ced). A calibration curve of n vs epsilon for conventional organic solvents (mainly the linear alcohols) has been used to estimate the epsilon of the ILs. Estimated epsilon values for ILs having the anions [Cl]-, [BF 4]-, [PF 6]-, [TfO]-, and [Tf 2N]- showed a very good comparison with the literature results, whereas ILs having the anions [C_n OSO3]- tend to deviate from such correlation. Also, for a series of ILs having a common anion, the epsilon is shown to follow a very good correlation with the molecular volumes. Predicted values show that both the nature of the anion and alkyl chain length of the cation contribute significantly to the epsilon of the ILs. The method developed makes use of properties which can be either experimentally determined or estimated with good accuracy and can be extended to the other categories of ILs with ease and reasonable accuracy.

Structural changes of a globular protein, bovine serum albumin (BSA), as a consequence of interaction with the surface active ionic liquids (ILs)-3-methyl-1-octylimidazolium chloride, [C(8)mim][Cl], and 1-butyl-3-methylimidazolium octylsulfate, [C(4)mim][C(8)OSO(3)]-have been investigated using various physicochemical and spectroscopic techniques such as tensiometry, conductometry, steady-state fluorescence, far-UV circular dichroism spectroscopy (CD), and dynamic light scattering (DLS). The interactional behavior of ILs (monomers and self-assembled structures) toward BSA in different IL concentration regimes at the air/solution interface as well as in the bulk is investigated and discussed depending upon the nature of ions of ILs. CD combined with the steady state fluorescence spectroscopy provided valuable insights into the unfolding of BSA as a consequence of IL binding. The complementary results obtained from the multitechnique approach proved very useful in drawing out the mechanism of interaction between ILs and BSA in different IL concentration regimes.

VersatAAIL Surfactants: Biodegradable, chiral amino acid ionic liquid surfactants (AAILSs) with a very high surface activity are synthesized and characterized. The AAILS can be applied as task‐specific ionic liquids; two examples given are the mitigation of harmful algal blooms from sea water and the shape‐ and size‐specific synthesis of nanomaterials.

No abstract