Unveiling the pH dependent interaction between bolaamphiphiles (dicarboxylic acids) and C10TAB (decyltrimethylammonium bromide) in aqueous medium.

Development of stable self-assembled nanostructures (especially vesicles and liposomes), and understanding their physicochemical behaviors in aqueous solution is a long-standing topic of interest in chemical and biochemical research. In this progressive area, we report for the first-time formation of mixed micelles (at pH 12), and vesicles of anionic bolaamphiphiles (dicarboxylic acids viz. [Formula: see text] , with moderate values of n 10, 11, 12, and 14) in combination with a cationic surfactant decyltrimethylammonium bromide (C10TAB) in buffered aqueous medium at different pH (6.0, 6.5, 6.8, and 8.0 for bola 10, 11, 12, and 14, respectively). Three pH dependent states of the solutions are observed: clear (high pH > 8), turbid and translucent (mid pH ≈ 6-8), and viscous inhomogeneous oil-like state (low pH < 6). The micelle size varies from 6.24 to 7.43 nm at pH 12, for vesicles the values are large (220-296 nm), and small (∼30-70 nm) in the pH range of 6.0-8.0. The self-assembly formation properties of their mixtures are herein investigated using different techniques viz. UV-vis spectroscopy, fluorescence spectroscopy, dynamic light scattering, laser confocal scanning microscopy, and isothermal titration calorimetry. The formed vesicles are fairly polydisperse, and show overall spherical shape. Formation of the bilayer assemblies, and their conversion to mixed micelles by the temperature effect are observed from steady state fluorescence anisotropy measurements. Micellization of the mixed bola-C10TAB species is endothermic and fairly entropy controlled; their formation/deformation is pH sensitive. They have spherical morphologies, and once formed at the right pH they are found to be very stable in terms of time. Thus, these vesicles have prospects for encapsulation and delivery of materials like drugs, and other substrates by controling the acid-base conditions of the system environment. The formed mixed micelles, and vesicles are expected to be low toxic, and thus green materials in nature with wider application possibilites.

Enthalpy-Entropy Compensation (EEC) Effect: Decisive Role of Free Energy.

The "enthalpy-entropy compensation" (EEC) effect has been a long-standing fascinating yet unresolved phenomenon in chemical thermodynamics. The reasons for the observation of EEC are not clear. Various views such as empirical, extrathermodynamic, error-related, solvation, and so forth as reasons for the H/S linear correlation are floating. Statistical reasons and a hidden Carnot's cycle (involving microscopic "heating and cooling" machines) have also been proposed recently for the observation of EEC. In this work, we have attempted a different line of approach to understand and explain the phenomenon. In the EEC treatment, the enthalpy (ΔH) and entropy (ΔS) values of "similar processes" are considered keeping aside the role of the other important thermodynamic parameter, that is, the free energy (ΔG). Considering ΔG along with ΔH and ΔS, it is established that the conventional EEC plot is not appropriate and mathematically sound. Consideration of ΔG may account for correlations of different kinds, linear, nonlinear, and so forth. Reports of non- or anticompensation phenomenon also prevail in the literature. A realistic account of the role of ΔG along with ΔH and ΔS in the understanding of such EEC correlations using authentic literature data is presented and discussed herein. EEC has several facets. Planned studies on similar systems with a wide range of ΔG values are required for realistic evaluation of the EEC and antienthalpy entropy compensation manifestations.

Stability of curcumin in different solvent and solution media: UV-visible and steady-state fluorescence spectral study.

In aqueous solution, curcumin is photodegradable (light sensitive), it is also self-degradable in the dark. In basic medium, the second process is enhanced. The dark process has been studied in water and also in a number of protic and aprotic solvents, and aqueous solutions of ionic liquids, pluronics, reverse micelles and salt. The kinetics of the process followed the first order rate law; a comparative as well as individual assessment of which has been made. The kinetics of curcumin self-degradation has been found to be fairly dependent on salt (NaCl) concentration. Curcumin molecules in solution may remain in the enol or keto-enol form. From the visible spectral analysis, an estimate of the proportions of these forms in aqueous ethanol medium has been made. The temperature effect on the visible and fluorescence spectra of curcumin has been also studied. The steady state fluorescence anisotropy of the photoactive curcumin has been evaluated in different solvent and solution media. The reversibility of the steady state fluorescence anisotropy of curcumin on heating and cooling conditions has been examined. The results herein presented are new and ought to be useful as the study of physicochemistry of curcumin has been gaining importance in the light of its biological importance.

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.

Interaction of normal and reverse pluronics (L44 and 10R5) and their mixtures with anionic surfactant sodium N-dodecanoylsarcosinate.

Interaction of monomeric normal L44 [(PEO)10(PPO)23(PEO)10]) and reverse 10R5 [(PPO)8(PEO)22(PPO)8] pluronics designated as L and R, respectively, and their mixtures with the anionic surfactant sodium N-dodecanoylsarcosinate (SDDS) in aqueous medium has been studied by tensiometry, conductometry, calorimetry and dynamic light scattering methods. The critical aggregation concentration (CAC), concentration of maximum binding (CS), and the extended critical micelle concentration (CMCe) of SDDS resulted from the interaction have been presented. L has shown the formation of CAC, CS and CMCe, whereas R has shown the absence of CAC but the presence of both CS and CMCe. Micellization of SDDS is an endothermic process whereas the formation of CAC and CMCe is exothermic events, the formation of CS is endothermic. The hydrodynamic diameter (Dh) and zeta potential of L and R, and their SDDS interacted species have been determined. Dh decreased with increasing SDDS concentration for L whereas it was invariant for R. Mixed L and R in varied proportions have been also examined in the solution state to probe into their mutual interaction, and interaction with SDDS. The formation of CAC of their mixtures was absent; CMCe formation was exothermic while that of CS was endothermic like their individuals.

Amphiphilic activities of anionic sodium cholate (NaC), zwitterionic 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (CHAPS) and their mixtures: a comparative study.

Anionic biological surfactant sodium cholate (NaC) and the zwitterionic nontoxic surfactant CHAPS (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) having common steroidal skeleton have not been studied in a comparative level to explore their amphiphilic behaviors separately and in mixed states. Their adsorption at the interface in relation to self-association in solution has been examined in both pure and mixed states with reference to detailed thermodynamic analysis of their surface chemical and solution behaviors. Their head group differences are responsible for the differences in their properties viz. critical micelle concentration (CMC), aggregation number (N), hydrodynamic diameter, Gibbs surface excess (Γmax), minimum head group area (Amin), mixed micelle composition and their mixing ideality/nonideality. Although the CMC values found from tensiometry and isothermal titration calorimetry (ITC) are in good agreement, the standard enthalpy of micellization (ΔHm(0)) found from ITC at different temperatures are different from that evaluated by the van't Hoff method. This is because van't Hoff rationale is a differential method which estimates the enthalpy of the monomer â†” micelle equilibrium process whereas calorimetry is an integral process that evaluates all probable/possible processes in addition to monomer to micelle conversion. Results are analyzed, compared and discussed in the light of physicochemical parameters of pure NaC and CHAPS and their mixtures. These fundamental findings are considered prospective in pharmaceutical, biochemical and biomedical applications of the studied bio-friendly amphiphiles.

Tensiometric determination of Gibbs surface excess and micelle point: a critical revisit.

Amphiphile adsorption at the air/water interface lowers the surface tension (γ) of the solution. After a critical surfactant concentration (C), γ becomes constant (with a break in the γ-logC plot), which is considered the critical micelle concentration (CMC). At very low amphiphile concentration, γ decreases slowly, forming a plateau, then decreases sharply and often nonlinearly by a co-operative adsorption process till the second plateau is reached at CMC. To get the Gibbs surface excess (Γ) of the amphiphile relative to water, a polynomial equation of appropriate degree needs to be used, since the drop in γ progresses with continuous changing slope, which maximizes at CMC and becomes zero afterward. Recent research has evidenced that a complete saturated Gibbs monolayer may not always form at CMC; there may be formation of multilayer of micelles below the Gibbs monolayer, which cannot be assessed by ST measurements. A method like neutron reflectometry (NR) can evaluate the Γ beyond CMC. A procedure for determining Γ(max) from tensiometric results is herein proposed. Amphiphiles do sometimes show a linear decline in γ with logC followed by a break with a plateau at CMC. There, a single slope leading to a single surface excess quantity is obtained for the Gibbs equation at all concentrations up to CMC. Possible reasons for such results are given. Current conflicting ideas and criticisms on the issue of Gibbs equation and determination of Γ and Γ(max) have been addressed.

Amphiphilic behavior of two phosphonium based ionic liquids.

Solution and surface chemical behavior of two phosphonium based ionic liquids triisobutyl (methyl) phosphonium tosylate (IL-1) and trihexyl (tetradecyl) phosphonium bis 2,4,4-(trimethylpentyl)phosphinate (IL-2) have been studied. The polar IL-1 is surface active and water soluble, whereas the weakly polar IL-2 is more surface active with very low aqueous solubility. IL-1 does not form micelles but affects the micellization properties of ionic, nonionic, and zwitterionic surfactants more strongly than conventional electrolytes. IL-2 itself forms micelles and mixed micelles with Triton X-100 (TX-100) in aqueous solution. It also forms Langmuir monolayers of liquid expanded type, at the air/water interface. IL-1 can replace water in forming microemulsions with the oil isopropylmyristate (IPM), stabilized by IL-2 (surfactant)+isopropanol (IP as a co-surfactant) like the IL-1/IPM/(IL-2+IP) system. It produces a large monophasic zone in the pseudoternary phase diagram. The thermodynamics of formation of the microemulsions of IL-1 in oil (IPM) have been examined. The dimensions and the polydispersity of the dispersed nano-droplets in the microemulsions have been determined by DLS. The thermal stability of the microemulsion forming systems has also been studied. ILs studied against Sarcoma-180 cell lines have evidenced proficient anti-cancer activity of IL-1 and moderate activity of IL-2.

Effect of bovine serum albumin on the functionality and structure of catanionic surfactant at air-buffer interface.

Interaction of bovine serum albumin (BSA) with the solvent spread monolayer of a catanionic surfactant, octadecyltrimethylammonium dodecylsulfate, (C18TA(+)DS(-)) at the air-buffer interface was investigated by measuring the surface pressure with time and change in surface area. Dipalmitoylphosphatidylcholine (DPPC) was used as reference. Kinetics of BSA desorption from the interface to the buffer subphase, that of C18TA(+)DS(-) and DPPC through their interaction with BSA, were also studied at different BSA concentrations (in the subphase) and surface pressures. Surface pressure (π)-area (A) isotherms (at pH = 5.4, µ = 0.01, T = 298 K) revealed that the coacervate/DPPC monolayer becomes expanded in the presence of BSA at low π while their protein bound species are released into the subphase at high π. Film morphology, studied by epifluorescence microscopy (EFM) and atomic force microscopy (AFM), reveals that the sizes of the domains of both DPPC and coacervate decrease in the presence of BSA. Presence of BSA in the coacervate and DPPC monolayer was supported from AFM data analysis.

Solution behavior of normal and reverse triblock copolymers (pluronic L44 and 10R5) individually and in binary mixture.

Solution properties of pluronics L44 or L [(PEO)(10)(PPO)(23)(PEO)(10)] and 10R5 or R [(PPO)(8)(PEO)(22)(PPO)(8)] were studied individually as well in their binary mixtures in aqueous medium. The critical micelle concentration (CMC), critical micelle temperature, and cloud point (CP) were determined. Ideal and nonideal behaviors of their mixtures in the formation of CMC and CP were observed; the energetics of the studied processes were determined. Spectrophotometry, isothermal titration calorimetry and dynamic light scattering (DLS) methods were used for evaluations. Morphologies of the dispersed L, R, and their mixtures along with their polydispersities were determined from DLS measurements. Atomic force microscopy was also employed. The interfacial properties of L and R were investigated forming Langmuir monolayers in a surface balance. The surface pressures (π) generated by the compounds were moderate, the area per molecule was higher for R than L. R has shown antibacterial activity against both gram positive and gram negative bacteria whereas L was inactive in this respect.

Behavior of the amphiphile CHAPS alone and in combination with the biopolymer inulin in water and isopropanol-water media.

Self-aggregation of the zwitterionic surfactant 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (CHAPS) in water and isopropanol-water media, and interaction of the amphiphile with the biopolymer inulin in these media were investigated. The micellar properties of the zwitterionic surfactant and its associated interfacial and bulk properties along with the related energetic, and aggregation number were determined. The different stages of interaction of the CHAPS-inulin combines were identified and assessed. The complexes were formed and aggregated in solution at different stages of their molecular compositions. The aggregated sizes were determined by dynamic light scattering study and the morphology in the solvent removed states were examined using scanning electron microscope and transmission electron microscope techniques. The results witnessed formation of ensembles of varied and striking patterns.

Physicochemistry of interaction between the cationic polymer poly(diallyldimethylammonium chloride) and the anionic surfactants sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium N-dodecanoylsarcosinate in water and isopropyl alcohol-water media.

The physicochemistry of interaction of the cationic polymer poly(diallyldimethylammonium chloride) (PDADMAC) with the anionic surfactants sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium N-dodecanoylsarcosinate was studied in detail using tensiometry, turbidimetry, calorimetry, viscometry, dynamic light scattering (DLS), and scanning electron microscopy (SEM). Fair interaction initially formed induced small micelles of the surfactants and later on produced free normal micelles in solution. The interaction process yielded coacervates that initially grew by aggregation in the aqueous medium and disintegrated into smaller species at higher surfactant concentration. The phenomena observed were affected by the presence of isopropyl alcohol (IP) in the medium. The hydrodynamic sizes of the dispersed polymer and its surfactant-interacted species were determined by DLS measurements. The surface morphologies of the solvent-removed PDADMAC and its surfactant-interacted complexes from water and IP-water media were examined by the SEM technique. The morphologies witnessed different patterns depending on the composition and the solvent environment. The head groups of the dodecyl chain containing surfactants made differences in the interaction process.

Interaction of gums (guar, carboxymethylhydroxypropyl guar, diutan, and xanthan) with surfactants (DTAB, CTAB, and TX-100) in aqueous medium.

The interaction of surfactants dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB), and p-tert-octylphenoxypolyoxyethylene (9.5) ether (TX-100) with guar (Gr), carboxymethylhydroxypropyl guar (CMHPG), diutan (Dn), and xanthan (Xn) gums has been studied employing conductometry, tensiometry, microcalorimetry, viscometry, and atomic force microscopy (AFM) techniques. Both weak and strong interactions were observed. CTAB interacted stronger than DTAB with the gums. The surfactant-gum interaction process was enhanced by the presence of borate ions in the solution; the borate ion itself also manifested interaction with the surfactants comparable with that of water-soluble polymers polyvinyl alcohol, polyoxyethylene, and so forth. Viscometric results supported configurational changes of the gum molecules by interaction with surfactants. The geometry of the pure gums and their CTAB interacted products in the dried states was ascertained from AFM measurements; spherical and prolate shapes were observed for pure gums, and distorted states were observed for their surfactant complexed species. Detailed topological features of these entities were ascertained.

Self-aggregation of synthesized novel bolaforms and their mixtures with sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) in aqueous medium.

Bolaforms B(1), B(2), and B(3) of the formulas, Br(-)Me(3)N(+)(CH(2))(10)N(+)Me(3)Br(-), Br(-)Me(3)N(+)(CH(2))(10)OH, and Br(-)Me(3)N(+)(CH(2))(10)COO(-)Na(+), respectively, were synthesized, and their properties in the bulk as well as at the air/aqueous NaBr (10 mM) solution interface have been studied. Their interactions with sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) also have been investigated. Tensiometry, conductometry, spectrophotometry, and microcalorimetry techniques were used for characterization and estimation. Both pure bolaforms and their mixtures with SDS and CTAB have been found to self-aggregate, forming micelles in solution. The mixed systems of bolaform and SDS have been observed to form both micelles and vesicles. Their mutual interactions were synergistic, which at the interface was more spontaneous than in the bulk. The interfacial and bulk compositions of the mixed binary systems (bolaform and SDS or CTAB) with their associated interaction parameters have been estimated from the Rosen interaction model and the regular solution theory of Rubingh, respectively. The formed vesicles have been found to entrap the water-soluble dye, bromophenol blue, and the dye solubilized vesicles of B(1)-SDS and B(2)-SDS completely eluted out of the sephadex column proving their formation. A rough estimation of the size and polydispersity index of the formed micelles and vesicles has been made from DLS measurements.

Sorption of water vapor, hydration, and viscosity of carboxymethylhydroxypropyl guar, diutan, and xanthan gums, and their molecular association with and without salts (NaCl, CaCl2, HCOOK, CH3COONa, (NH4)2SO4 and MgSO4) in aqueous solution.

Gums are routinely used in food industry, pharmacy and oil recovery process. In these uses, the hydrocolloids very often encounter interactions with salts at moderate to high temperature. Since they are normally employed in the form of solution and gel, their viscous or fluidity properties need detailed investigation. In the present work, properties such as water vapor adsorption of finely powdered carboxymethylhydroxypropyl derivatized guar (CMHPG) as well as xanthan (Xn) and diutan (Dn) gums, their hydration in solution, their viscosity behaviors, and salt effects on fluidity have been studied. The concentration domains for the existence of free and associated molecules in the studied solutions have been assessed from the viscosity results. The gums have been found to bind a fair amount of water from the vapor phase with them. In solution, they can interact and arrest a large amount of water in their folded configuration. Intrinsic viscosities of the gums in aqueous medium declined in the presence of salts. The activation energies for their viscous flow were moderate and comparable, and were dependent on their concentrations. From the power law relation and viscosity master curve behavior mostly two critical association states of the macromolecular dispersions were envisaged.

Amphiphile self-aggregation: an attempt to reconcile the agreement-disagreement between the enthalpies of micellization determined by the van't Hoff and Calorimetry methods.

In this article, discrepancies between the enthalpies of micellization of amphiphiles in aqueous solution determined by the methods of van't Hoff (VH) and calorimetry have been addressed. The contributions of the hydrophobic interaction, electrostatic interaction and the micellar size effect have been considered to assess the total picture of the amphiphile self-association process and related energetic parameters, especially the enthalpy and the specific heat capacity. Literature results on 23 amphiphile systems (six nonionics, five anionics, and twelve cationics) have been analyzed, and the assessed enthalpies by VH method and direct calorimetry have been presented and compared. VH results considering participation of 5% of total amphiphile monomer to form micelle at cmc have been also compared. In addition to this, the changes in the standard specific heat of micellization for all the amphiphile aggregation processes evaluated by the VH and calorimetry procedures have been presented. The differences between the standard enthalpy of micellization DeltaH(m)(o) by the methods of VH and calorimetry are minor for nonionic surfactants but major for ionics, whereas the standard specific heat capacities of micellization (DeltaC(Pm)(o)) by both the procedures fairly agree for all types of surfactants. Like DeltaH(m)(o)-DeltaS(m)(o) compensation observed in kinetic and equilibrium processes, a linear correlation between Lt(T-->0)DeltaH(m)(o) and DeltaC(Pm)(o) has been observed with no distinction between the VH and calorimetry derived results for all the surfactant systems herein dealt with.

Physicochemistry of the interaction between inulin and alkyltrimethylammonium bromides in aqueous medium and the formed coacervates.

Inulin, a polydisperse reserve polysaccharide, has prospective uses in food, pharmacy, and industry. Its uses and applications often encounter interactions with lipids and amphiphiles. Reports on such interactions are scarcely found in literature. In the present study, we have examined the nature of interactions between inulin and cationic amphiphiles, alkyltrimethylammonium bromides (CnTAB: n=12, 14, 16, 18), over a fair range of concentrations for both the polymer and the amphiphile. At low concentration, small induced amphiphile aggregates form complexes with inulin; at moderate concentration, the complexed inulin self-aggregates leading to coacervate formation, and at higher concentration, the amphiphile forms free micelles in solution. Tensiometric, conductometric, viscometric, and turbidimetric methods have been employed to study the above phenomena. The isolated coacervates of inulin with C18TAB were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC), thermogravimetry (TG), and differential thermal analysis (DTA) to ascertain their morphology, structure, and thermal stability.

Physicochemical and conformational studies on BSA-surfactant interaction in aqueous medium.

In this paper, results of physicochemical studies on the interaction of bovine serum albumin (BSA) with alkyltrimethylammonium bromide (ATAB), pentaethylene glycol mono-n-dodecyl ether (C12E5), and sodium dodecyl sulfate (SDS) under the experimental conditions of phosphate buffer at pH 7 in the presence of 10 mM sodium bromide (NaBr), maintaining the ionic strength of the overall solution at micro = 0.015 M, have been presented and discussed. Here, BSA-ATAB corresponds to a polyion-surfactant system bearing opposite charges. BSA precipitated out of the solution on addition of ATAB solution over a certain range of ATAB concentration, the concentration range being dependent on the particular member of the ATAB family. In our earlier reports on the precipitation of oppositely charged polymer-surfactant, the tensiometric profile for surfactant addition in polymer solution differed significantly from that expected from addition of surfactant in the dispersion medium. In the present study, the precipitation process could hardly affect the smoothness of the tensiometric profile. This indicates the interaction process is operative in bulk solution. Microcalorimetric profiles also evidenced an extra hump in the interaction profile at lower surfactant concentrations, without much affecting the dilution enthalpograms beyond micellization. This interaction appeared unimodal and the extent of interaction increased with increasing tail length of ATAB, evidencing the hydrophobic effect to be an important factor. Addition of salt (NaBr) also affected the nature of interaction: at lower concentration of NaBr, the interaction was mildly assisted, whereas 50 mM NaBr fairly assisted the interaction. The nonionic surfactant C12E5 modestly interacted with BSA. The anionic amphiphile SDS, on the other hand, interacted with BSA in two distinctly different stages, as evidenced from the tensiometric profile. The complexity of the BSA-SDS tensiometric isotherm compared to that of BSA-ATAB arose from the presence of cationic binding sites adjacent to hydrophobic patches of BSA in its native state, so that electrostatic and hydrophobic interactions can cooperatively operate side by side. The interfacial saturation occurred at a lower concentration in the presence of BSA compared to the normal cmc of SDS under identical solution conditions in the absence of BSA, which was slightly delayed for nonionic C12E5. The multitechnique approach evidenced that different experimental techniques probe different physicochemical phenomena and an attempt to show the concurrence of the break points in different techniques is only diluting the essence of this area.

Physicochemical studies on the biopolymer inulin: a critical evaluation of its self-aggregation, aggregate-morphology, interaction with water, and thermal stability.

Physicochemical properties viz., aggregation, molar mass, shape, and size of chicory inulin in solution were determined by fluorimetry, DLS, SLS, TEM, and viscometry methods. The thermal stability of the biopolymer was examined by TGA, DTA, and DSC measurements. The water vapor adsorption of desiccated inulin was also studied by the isopiestic method, and the data were analyzed in the light of the BET equation. On the basis of the obstruction to ion conductance by the inulin aggregates in solution and analysis of the data, the extent of hydration of inulin in solution was estimated. The result was coupled with the intrinsic viscosity, [eta], of inulin to ascertain the shape of the biopolymer aggregates in aqueous solution. The critical aggregation concentration (cac) of inulin in aqueous as well as in salt solution was assessed by fluorimetry. The weight average molar mass, Mw , of inulin monomer and its aggregate was found to be 4468 and 1.03 x 10(6) g/mol, respectively, in aqueous solution. This aggregated mass was 2.4 x 10(6) g/mol in 0.5M NH(4)SCN solution. The [eta] values of the soft supramolecular aggregates in solution (without and with salt) were small and comparable with globular proteins evidencing spherical geometry of the biopolymer aggregates as supported by the TEM results. In DMSO, rod-like aggregates of inulin was found by the TEM study. The [eta] of the biopolymer in the DMSO medium was therefore, higher than that in the aqueous medium. Unlike aqueous medium, the aggregation in DMSO was not associated with a cac.

A LB film morphological study with reference to biopolymer-surfactant interaction taking gelatin-CTAB system as a model.

The interaction of gelatin with cetyltrimethylammonium bromide (CTAB) studied at pH 9 and an ionic strength of 0.005, produces an interfacial surface active gelatin-CTAB (monomer) complex (GS(n)(I)), a surface inactive gelatin-CTAB (micelle) complex in bulk (GS(m)(B)), followed by coacervation, and its solubilization in micellar solution of CTAB. We have herein attempted to probe the interfacial morphological changes of gelatin and its CTAB complexes, and not the bulk properties like coacervation and/or micellar solubilization. The morphologies of pure gelatin and CTAB films and that of gelatin-CTAB interacted complex at the interface have been investigated using LB, SEM, AFM and ellipsometric techniques. The stability of the gelatin monolayer at varied concentrations with and without CTAB has been examined. The SEM images of stabilized films of gelatin and gelatin-CTAB complex have witnessed compact smooth as well as rough surfaces with formation of distinct domains. Drastic morphological change in the film before the critical aggregational concentration of CTAB (T(2)) has been in line with an initial abrupt decrease in surface tension. This has been corroborated by AFM measurements, which along with morphology demonstration has provided information on the diameter of the ensembles formed and roughness of the LB films constituted of pure components and their complexes. Thickness of the film was at its maximum in the domain region, as corroborated by ellipsometric technique. Such an elaborate interfacial monolayer and film morphology study of biopolymer-amphiphile system has been rarely documented in literature.