K. Srinivasa Rao

Aggregation behavior of amino acid ionic liquid surfactants in aqueous media.

Self-aggregation of amino acid ionic liquid surfactants (AAILSs) in aqueous solution has been investigated through surface tension, conductivity, steady-state fluorescence, dynamic light scattering (DLS), and transmission electron microscopy (TEM). The critical aggregation concentration (cac) of AAILSs obtained from different techniques showed fairly good agreement. Surface tension measurements have been used to derive surface adsorption properties such as adsorption efficiency (pC(20), effectiveness of surface tension reduction (Π(cac)), and minimum surface area per molecule (A(min)) at the air-water interface. Temperature-dependent conductivity measurements have been used to obtain the degree of counterion binding (β), and the thermodynamic parameters such as standard free energy (ΔG(agg)(0)), enthalpy (ΔH(agg)(0)), and entropy (ΔS(agg)(0)) of aggregation. The aggregation number (N(agg)) for various AAILSs has been derived by using the fluorescence quenching technique. Size of the aggregates has been obtained from DLS and TEM measurements. The aggregation properties of AAILSs have been analyzed as a function of structure of amino acids and compared with those of analogous ionic liquids (ILs) and conventional ionic surfactants. Surface activity of the AAILSs has been found superior to that of analogous ILs and conventional ionic surfactants of the same alkyl chain length.

Aqueous-biamphiphilic ionic liquid systems: self-assembly and synthesis of gold nanocrystals/microplates.

Biamphiphilic ionic liquids (BAILs) based on 1,3-dialkylimidazolium cation and alkyl sulfate anions ([C(n)H(2n+1)mim][C(m)H(2m+1)OSO(3)]; n = 4, 6, or 8; m = 8, 12) have been synthesized and characterized for their self-assembling behavior in the aqueous medium. Effects of alteration of alkyl chain length in cation and anion on surfactant properties of BAILs have been examined from surface tension measurements. The effectiveness of surface tension reduction for BAILs has been found to be exceptionally higher as compared to single chain surface active ILs/conventional surfactants. The thermodynamics of the aggregation process has been studied using isothermal titration calorimetry (ITC) and temperature dependent conductivity experiments. Dynamic light scattering (DLS), nuclear magnetic resonance (NMR), and transmission electron microscopy (TEM) studies showed that BAILs formed distinct aggregated structures depending upon the amphiphilic character present in the cation and anion. BAILs ([C(n)H(2n+1)mim][C(m)H(2m+1)OSO(3)]) form micelles when n = 4, 6; m = 8, intermicellar aggregates when n = 4, 6; m = 12, and vesicles when n = 8; m = 8, 12. Gold nanoparticles and microplates have been synthesized in micellar and vesicle solutions of BAILs using a simple photoreduction method. The studies show the potential of BAILs for constructing micelles and supramolecular assemblies, such as bilayer vesicles, which are effective in preparation of nanomaterials of controlled size and morphology.

Biamphiphilic Ionic Liquid Induced Folding Alterations in the Structure of Bovine Serum Albumin in Aqueous Medium

3-Methyl-1-octylimidazolium dodecylsulfate, [C8mim][C12OSO3], a vesicle forming biamphiphilic ionic liquid (BAIL) (J. Phys. Chem. B 2012, 116, 14363-14374), has been found to induce significant folding alterations in the structure of bovine serum albumin (BSA) in the aqueous medium at pH 7.0. Such alterations have been investigated in detail using various physicochemical and spectroscopic techniques. Different concentration regimes (monomeric, shared aggregation, and post-vesicular) of [C8mim][C12OSO3]-BSA interactions have been defined through adsorption and binding isotherms using tensiometry and isothermal titration calorimetry (ITC). Fluorimetry, circular dichroism (CD), and dynamic light scattering (DLS) measurements have shown that [C8mim][C12OSO3] induces a small unfolding of BSA in the monomeric regime at low concentration (designated as C(f)), which is followed by a refolding up to critical aggregation concentration (CAC) (designated as C1). Above C1, i.e., in the shared aggregation concentration regime, again a small unfolding of BSA was observed up to critical vesicular concentration (CVC) (designated as C2). In the vesicular and post-vesicular regimes, the BSA remained stable against folding alterations. The kinetic stability of BSA in the vesicular concentration regimes was studied for a month using turbidimetry. It has been found that [C8mim][C12OSO3] stabilizes BSA against the aggregation which is the major cause of protein destabilization. The present study gives insights for the design of surface active ILs for protein stabilization as a potential replacement for the mixed micelles of conventional surfactants used in detergent industries for enzyme stabilization and as an artificial chaperone.

Aqueous-Mixed Ionic Liquid System: Phase Transitions and Synthesis of Gold Nanocrystals

Micelle-vesicle-micelle (MVM) transitions are observed in the aqueous-mixed ionic liquid (1-butyl-3-methylimidazolium octyl sulfate and 3-methyl-1-octylimidazolium chloride) system. The surface activity of mixed ILs, phase behavior, and solution structures in the system have been thoroughly characterized using conductometry, tensiometry, fluorimetry, dynamic light scattering (DLS), viscometry, turbidity, atomic force microscopy (AFM), transmission electron microscopy (TEM), and (1)H NMR techniques. Synergetic interactions between the two ILs in monolayers at the air/water interface and in micelles/vesicles have been determined using the regular solution approach, and the origins of spontaneous vesicle formation in this novel system are discussed. Using a photoreduction method, the formation of stable gold nanoparticles (GNPs) and microscale nanosheets of different shapes and sizes in the micellar and vesicle solutions has been reported. The studies show the potential of a mixed IL system in constructing stable micelles/supramolecular assemblies, such as bilayer vesicles, which are effective in the preparation of the desired nanomaterials.

Effect of ethylene glycol and its derivatives on the aggregation behavior of an ionic liquid 1-butyl-3-methyl imidazolium octylsulfate in aqueous medium.

The effect of ethylene glycol (EG) and its derivatives, ethylene glycol monomethyl ether (EGMME), or ethylene glycol dimethyl ether (EGDME), on the aggregation behavior of a surfactant-like ionic liquid (IL), 1-butyl-3-methyl imidazolium octylsulfate, [C(4)mim][C(8)OSO(3)], in aqueous solutions is investigated using conductivity, surface tension, fluorescence, (1)H NMR, and dynamic light scattering (DLS) measurements. Thermodynamic parameters such as Gibbs free energy (ΔG(m)°), standard enthalpy (ΔH(m)°), and standard entropy (ΔS(m)°) of aggregation are determined from the temperature dependence of conductivity. The interfacial properties of IL at the air/water interface in various mixed solvents are evaluated from surface tension measurements. Information about the local microenvironment and size of the aggregates is obtained from steady-state fluorescence using pyrene as a polarity probe and DLS measurements, respectively. (1)H NMR data has been employed to get detailed insight into the effect of organic additives on the IL aggregate structure and aggregation number. It has been observed that the addition of organic additives to water decreases the spontaneity of aggregation of IL.

Sodium Bromide Induced Micelle to Vesicle Transitions of Newly Synthesized Anionic Surface Active Ionic Liquids Based on Dodecylbenzenesulfonate

Dodecylbenezenesulfonate-based anionic surface active ionic liquids (DBS-ILs) paired with onium cations, n-butyltrimethylammonium ([N1114]), 1-butyl-3-methylimidazolium ([C4mim]), and N-butylpyridinium ([C4Py]) have been synthesized. DBS-ILs were found to be highly surface active having critical micelle concentration (CMC) lower than that of their conventional analogue sodium dodecylbenezenesulfonate ([Na][DBS]). The CMC values of DBS-ILs were determined from surface tension (ST) and isothermal titration calorimetry (ITC). DBS-ILs formed micelles predominantly in the aqueous medium, and unlike [Na]DBS, the micelles of DBS-ILs could be transformed into vesicles with the addition of sodium bromide (NaBr). Micelle to vesicle transitions (MVTs) were evidenced from dynamic light scattering (DLS), turbidity, proton nuclear magnetic resonance ((1)H NMR), and cryo-TEM techniques. Thermodynamics of aggregation was investigated from ITC which indicated that the aggregation process is primarily driven by the entropy factor. The formation of a vesicle upon addition of NaBr has been accounted to the increased electrostatic interactions between the less hydrated sulfonate headgroup and the more populated bigger sized counterions along with the favored cation-π or π-π interactions between them as evidenced from 2D-NOESY NMR experiments. The stimuli-responsive morphological transitions in the self-assembly of the reported anionic surface active ionic liquids (SAILs) will be useful for encapsulation and delivery of active (bio)molecules in the targeted biomedical applications.

Spontaneous Formation of Multiarchitecture Vesicles of [C8mim]Br + [Na]DBS in Aqueous Medium: Synergic Interplay of Electrostatic, Hydrophobic, and π–π Stacking Interactions

A mixture of a cationic surface active ionic liquid, [C8mim]Br and anionic surfactant, [Na]DBS has been shown to form unilamellar vesicles in water over an exceptionally wide mole fraction range of [C8mim]Br (x1 = 0.2 to 0.8). Formation of vesicles has been evidenced from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) imaging. Cryo-TEM imaging of an equimolar mixture showed multiarchitectural unilamellar vesicles (spherical, tubular, and ribbon). Such complex architectures were earlier reported for Janus dendrimers of different structures (Science, 2010, 328, 1014). The synergism between oppositely charged single chain surfactants to form bilayer structures has been explained based on the evidence of π-π stacking interaction from 2D NOESY measurements, Coulombic interactions from zeta potential measurements and magnitude of interaction parameter from the critical aggregation concentration. The aggregation concentrations were measured from tensiometry and fluorescence using pyrene as a polarity probe. The phase behavior at different mixture compositions has been revealed from turbidity measurements and visual inspection. Hydrodynamic radii of self-assembled structures in the bulk solution phase were measured from dynamic light scattering. Vesicles formed have been explored as delivery vehicles for proteins using bovine serum albumin (BSA) as model.