Interaction between sodium dodecylsulfate (SDS) and pluronic L61 in aqueous medium: assessment of the nature and morphology of the formed mixed aggregates by NMR, EPR, SANS and FF-TEM measurements.

The interaction of copolymer L61 i.e., (EO)2(PO)32(EO)2 (where EO and PO are ethylene and propylene oxides, respectively) with surfactant SDS (sodium dodecylsulfate) in relation to their self-aggregation, dynamics and microstructures has been physicochemically studied in detail employing the Nuclear Magnetic Resonance (NMR), Electron Paramagnetic Resonance (EPR), Small-Angle Neutron Scattering (SANS), and Freeze-Fracture Transmission Electron Microscopy (FF-TEM) methods. The NMR self-diffusion study indicated a synergistic interaction between SDS and L61 forming L61-SDS mixed complex aggregates, and deuterium (2H) NMR pointed out the nonspherical nature of these aggregates with increasing [L61]. EPR spectral analysis of the motional parameters of 5-doxyl steraric acid (5-DSA) as a spin probe provided information on the microviscosity of the local environment of the L61-SDS complex aggregates. SANS probed the geometrical aspects of the SDS-L61 assemblies as a function of both [L61] and [SDS]. Progressive evolution of the mixed-aggregate geometries from globular to prolate ellipsoids with axial ratios ranging from 2 to 10 with increasing [L61] was found. Such morphological changes were further corroborated with the results of 2H NMR and FF-TEM measurements. The strategy of the measurements, and data analysis for a concerted conclusion have been presented.

Vesicle to micelle transition in the ternary mixture of L121/SDS/D2O: NMR, EPR and SANS studies.

Subtle changes in the microstructure and dynamics of the triblock copolymer L121, (ethylene oxide)5 (propylene oxide)68 (ethylene oxide)5i.e., E5P68E5, and sodium dodecylsulfate (SDS) system in aqueous medium were investigated using high-resolution nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) and small-angle neutron scattering (SANS) methods. NMR self-diffusion measurements helped us to understand the nature of binding of SDS with L121, and the formation of their mixed aggregates. These results showed that even at low [SDS] (∼2 mM), the addition of L121 stabilized the dynamics of SDS. Furthermore, the increase in [SDS] resulted in progressive changes in the diffusion behavior of both SDS and L121. 13C chemical shift analysis revealed that preferential binding of L121 occurred on the SDS micelle surface. Deuterium (2H) NMR spin-relaxation data evidenced that the formed mixed aggregates were non-spherical in terms of relaxation rate changes, and slowed the dynamics. The rotational correlation times of mixed aggregates were estimated from EPR analysis. A SANS study indicated the presence of uni- and multi-lamellar vesicles of L121 at low [SDS]. The vesicles transformed to mixed L121-SDS micelles in the presence of a higher [SDS]. This was supported by the measurements of 2H NMR spin-relaxation and EPR rotational correlation times.

Evaluation of the role of substrate and albumin on Pseudomonas aeruginosa biofilm morphology through FESEM and FTIR studies on polymeric biomaterials.

Bacterial biofilms pose the greatest challenge to implant surgeries leading to device-related infections and implant failure. Our present study aims at monitoring the variation in the biofilm architecture of a clinically isolated strain and ATCC 27853 strain of Pseudomonas aeruginosa on two polymeric biomaterials, used in implants. The perspective of our study is to recognize the potential of these two biomaterials to create biofilm infections and develop the understanding regarding their limitations of use and handle patients with this deeper insight. The final goal, however, is an accurate interpretation of substrate-microbe interactions in the two biomaterials, which will provide us the knowledge of possible surface modifications to develop of an efficacious anti-biofilm therapy for deterring implant infections. The reference strain ATCC 27853 and a clinical isolate of P. aeruginosa collected from urinary catheters of patients suffering from urinary tract infections, have been used as microbes while clinical grades of polypropylene and high density polyethylene, have been used as 'substrates' for biofilm growth. The variation in the nature of the 'substrate' and 'conditioning layer' of BSA have been found to affect the biofilm architecture as well as the physiology of the biofilm-forming bacteria, accompanied by an alteration in the nature and volume of EPS (extracellular polysaccharide) matrices.

Physicochemical perspectives (aggregation, structure and dynamics) of interaction between pluronic (L31) and surfactant (SDS).

The influence of the water soluble non-ionic tri-block copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E2P16E2 (L31) on the microstructure and self-aggregation dynamics of the anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution was investigated using cloud point (CP), isothermal titration calorimetry (ITC), high resolution nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and small-angle neutron scattering (SANS) measurements. CP provided the thermodynamic information on the Gibbs free energy, enthalpy, entropy and heat capacity changes pertaining to the phase separation of the system at elevated temperature. The ITC and NMR self-diffusion measurements helped to understand the nature of the binding isotherms of SDS in the presence of L31 in terms of the formation of mixed aggregates and free SDS micelles in solution. EPR analysis provided the micro-viscosity of the spin probe 5-DSA in terms of rotational correlation time. The SANS study indicated the presence of prolate ellipsoidal mixed aggregates, whose size increased with the increasing addition of L31. At a large [L31], SANS also revealed the progressive decreasing size of the ellipsoidal mixed aggregates of SDS-L31 into nearly globular forms with the increasing SDS addition. Wrapping of the spherical SDS micelles by L31 was also corroborated from (13)C NMR and SANS measurements.

Micellization and related behavior of sodium dodecylsulfate in mixed binary solvent media of tetrahydrofuran (Tf) and formamide (Fa) with water: a detailed physicochemical investigation.

The detailed aggregation behavior of sodiumdodecyl sulfate (SDS) in tetrahydrofuran (Tf)-water (W) and formamide (Fa)-water (W) media at varied volume percent compositions has been investigated. Surface tension (ST), conductance (Cond), viscosity (Visc), isothermal titration calorimetry (ITC), nuclear magnetic resonance (NMR) and small angle neutron scattering (SANS) were used in this study. The presence of nonaqueous solvents affected the critical micelle concentration (CMC) of SDS, the counter-ion binding of the micelle, the energetics of the air/water interfacial adsorption and micellization of the amphiphiles in the bulk, the ion-association (ion-pair, triple-ion, quadruple, etc. between Na(+) and DS(-) ions) as well as the weakly soluble (aggregation less) amphiphile solution. Tf has been observed to produce a "dead zone" or "non-micelle formation zone" in the mixed Tf-W domain of 10-40 vol%. Fa influenced the SDS aggregation up to 70 vol%, at higher proportions (below the Krafft temperature (K(T))), instead of the micelle, "randomly arranged globular assembly" (RAGA) was formed. The correlation of the standard free energy of micellization (ΔG(m)(0)) with different solvent parameters (1) dielectric constant (ε), (2) viscosity (η0), (3) Reichardt parameter (E(T)(30)), (4) Gordon parameter (G), and (5) Hansen-Hildebrand hydrogen bonding parameter (δ(h)) has been attempted. It has been found that δ(h) produced a master correlation between ΔG(m)(0) and δ(h) for different binary mixtures such as Tf-W, Fa-W, Ml-W and Dn-W.

Amphiphile behavior in mixed solvent media I: self-aggregation and ion association of sodium dodecylsulfate in 1,4-dioxane-water and methanol-water media.

Mixed aquo-organic solvents are used in chemical, industrial, and pharmaceutical processes along with amphiphilic materials. Their fundamental studies with reference to bulk and interfacial phenomena are thus considered to be important, but such detailed studies are limited. In this work, the interfacial adsorption of sodium dodecylsulfate (SDS, C12H25SO4(-)Na(+)) in dioxane-water (Dn-W) and methanol-water (Ml-W) media in extensive mixing ratios along with its bulk behavior have been investigated. The solvent-composition-dependent properties have been identified, and their quantifications have been attempted. The SDS micellization has been assessed in terms of different solvent parameters, and the possible formation of an ion pair and triple ion of the colloidal electrolyte, C12H25SO4(-)Na(+) in the Dn-W medium has been correlated and quantified. In the Ml-W medium at a high volume percent of Ml, the SDS amphiphile formed special associated species instead of ion association. The formation of self-assembly and the energetics of SDS in the mixed solvent media have been determined and assessed using conductometry, calorimetry, tensiometry, viscometry, NMR, and DLS methods. The detailed study undertaken herein with respect to the behavior of SDS in the mixed aquo-organic solvent media (Dn-W and Ml-W) is a new kind of endeavor.

Physicochemical studies on goat pulmonary surfactant.

The large aggregate (LA) fraction of goat pulmonary surfactant (GPS) was isolated and characterized. Goat lung surfactant extract (GLSE) was obtained by chloroform-methanol extraction of the saline suspended LA fraction. Total phospholipid (PL), cholesterol (CHOL), and protein were biochemically estimated. It was composed of approximately 83% (w/w) PL, approximately 0.6% (w/w) CHOL and approximately 16% (w/w) protein. CHOL content was found to be lower while the protein content was found to be higher than other mammalian pulmonary surfactants. Electrospray Ionization Mass Spectrometry (ESIMS) of GLSE confirmed dipalmitoylphosphatidylcholine (DPPC) as the major phospholipid species, with significant amounts of palmitoyl-oleoyl phosphatidylcholine (POPC), palmitoyl-myristoyl phosphatidylcholine (PMPC) and dioleoylphosphatidylcholine (DOPC). Functionality of the solvent spread GLSE film was carried out in a Langmuir surface balance by way of surface pressure (pi)-area (A) measurements. A high value of pi (approximately 65 mN m(-1)) could be attained with a lift-off area of approximately 1.2 nm(2) molecule(-1). A relatively large hysteresis was observed during compression-expansion cycles. Monolayer deposits at different pi, transferred onto freshly cleaved mica by Langmuir-Blodgett (LB) technique, were imaged by atomic force microscopy. DPPC-enriched domains (evident from height analyses) showed dimensions of 2.5 microm and underwent changes in shapes after 30 mN m(-1). Functionality and structure of the surfactant films were proposed to be controlled by the relative abundances of protein and cholesterol.

Biocompatible microemulsions and their prospective uses in drug delivery.

Efficacy of lipophilic drugs is often hindered due to their poor aqueous solubility leading to low absorption after in vivo administration. A part of the administered dose is absorbed and reaches the pharmacological site of action and the remainder causes toxicity and undesirable side effects due to unwanted biodistribution. Enhancement in drug efficacy and lowering of drug toxicity could be achieved through encapsulation and delivery of the lipophilic drugs in aqueous based delivery systems. Microemulsions are macroscopically homogeneous pseudoternary and ternary colloidal assemblies having polar and nonpolar micro domains. Their dispersed phases in nanodimension have good shelf-life (due to thermodynamic stability), large surface area, low viscosity (in some compositions), and ultraslow surface tension. These properties qualify them to be prospective drug delivery systems provided they are composed of biocompatible excipients. Due to the existence of polar, nonpolar, and interfacial microdomains, encapsulation of different kinds of drugs is possible. The review entails reports on development and characterization of biocompatible microemulsion systems and their evaluation as probable vehicles for encapsulation, stabilization, and delivery of bioactive natural products and prescription drugs.

Preparation of prospective plant oil derived micro-emulsion vehicles for drug delivery.

Biocompatible oil-in-water (o/w) micro-emulsions can be prospective drug delivery vehicles for their capability to solubilize lipophilic (oil soluble) drugs in the dispersed oil. Plant oils are considered suitable for such a purpose. In this study, we have attempted to examine the dispersion of corn, cottonseed, clove, orange and peppermint oils, as well as isopropyl myristate (IPM) in water continuum in presence of surfactants Tween-20, Brij-30 and Brij-92 and co-surfactants ethanol (EtOH) and isopropyl alcohol (iPrOH). Both ternary (oil/surfactant/water) and psedoternary (oil/surfactant + co-surfactant/water) phase diagrams were constructed. The ternary systems produced larger micro-emulsion forming zones than the psedo-ternary systems. The combinations peppermint oil/iPrOH/water, IPM/iPrOH/water and 1:1 (v/v) peppermint oil + IPM/iPrOH/water were found to form fair proportion of single-phase surfactant-less micro-emulsion. The surfactant-aided ternary systems produced larger clear microemulsion zones, compared to pseudo-ternary systems, while the behaviour of surfactant-less systems was intermediate. The prepared systems had shelf life of 1 year and they withstood temperature variations in the range of 4-40 degrees C.

New pharmaceutical microemulsion system for encapsulation and delivery of diospyrin, a plant-derived bioactive quinonoid compound.

A new vegetable oil based oil-in-water microemulsion is developed and characterized as a prospective delivery system for in vivo application A particular weight percent composition 5/30/65 (clove oil/Tween-20/water) was selected (V1) from the clear oil-in-water zone of the pseudoternary phase diagram comprising clove oil, polyoxyethylene sorbitan monolaurate (Tween-20), and water. Two modifications of V1, (V2 and V3) were prepared by addition of dipalmitoyl phosphatidyl choline (DPPC), and a mixture of DPPC and cholesterol, respectively. A model drug diospyrin (a plantderived quinonoid compound) was encapsulated in the dispersed clove oil droplets of the three systems and designated as DV1, DV2, and DV3, respectively. The size of the dispersed clove oil droplets ranged between 9-20 nm as determined by dynamic light scattering. The stability of the vehicles, before and after encapsulation, was assessed under varying conditions of time and temperature and was found to be stable for 1 year and over a temperature range of 4-40 degrees C. The ultraviolet-visible spectrum of diospyrin after encapsulation in the compartmentalized medium remained almost identical to that dissolved in chloroform. The single-dose acute toxicity of V1 and DV1 was assessed in vivo by carrying out survival study and enzyme assay in Swiss Albino mice. The vehicle was safe at a volume of 0.05 ml when injected intraperitoneally into the mice.

Self-aggregation of alkyltrimethylammonium bromides (C10-, C12-, C14-, and C16TAB) and their binary mixtures in aqueous medium: a critical and comprehensive assessment of interfacial behavior and bulk properties with reference to two types of micelle formation.

The detailed interfacial adsorption and micellization behavior of pure and mixed alkyltrimethylammonium bromides (ATABs: C10-, C12-, C14-, and C16TAB) were studied using tensiometric, conductometric, fluorimetric, viscometric, and calorimetric methods. The critical micellar concentration (CMC), thermodynamics of adsorption and micellization, counterion binding, aggregation number, and micellar polarity were determined. It was observed that the studied 1:1 molar mixtures of C10-C12TAB, C10-C14TAB, and C10-C16TAB, and the mixtures C12-C14TAB and C12-C16TAB at different mole ratios produced two CMCs that were supported by the conductometric, calorimetric and viscometric methods. Compared to the first micelle, the second micelle condensed more counterions and produced a higher aggregation number, but their interior polarity states were the same. The surface excess, area minimum of the ATABs at the CMC and Gibbs free energy of adsorption were evaluated and compared. The ideality/nonideality states of the mixed micelles formed in solution were tested in the light of Clint and Rubingh's formalisms; the mixed systems were found to undergo moderate to weak synergistic interaction. The contributions of the terminal methyl group, the intermediate methylene groups, and the hydrophilic tetramethylammonium group toward the standard Gibbs free energy, enthalpy, and entropy of the micellization processes were deciphered and discussed.

Designing and testing of an effective oil-in-water microemulsion drug delivery system for in vivo application.

The phase behavior of a new psedoternary system of clove oil/Tween 20 has been studied. Several compositions from the single-phase region were selected and their stability toward time, temperature, and electrolytes has been examined. A particular composition(clove oil/Tween 20/water as 5/30/65) was chosen as the drug delivery system from the clear oil-in-water zone of the pseudoternary system. The droplet dimension and the polydispersity state of the particular composition was determined by dynamic light scattering. A bioactive compound quarcetin was encapsulated in the vehicle. The efficacy of the drug in the vehicle was examined against leishmaniasis in hamster models. The hepatotoxicity of the vehicle (o/w microemulsion) with and without the drug quarcetin was examined by estimating serum alkaline phosphatase, glutamate pyruvate transaminase, urea, and creatinine.

Enhanced in vitro percutaneous absorption and in vivo anti-inflammatory effect of a selective cyclooxygenase inhibitor using microemulsion.

Celecoxib, a specific COX-2 inhibitor, was recently approved for the treatment of rheumatoid and osteoarthritis, acute pain, familial adenomatous polyposis and primary dysmenorrhea. Oral administration of celecoxib is effective against ultraviolet B radiation (UVB)-induced skin carcinogenesis; however, its clinical use is restricted because of its failure to block the characteristic cutaneous inflammatory response and lower availability at the site of inflammation. Topical application of celecoxib has been effective compared with oral in certain clinical conditions. The present study was undertaken to develop and investigate the development of microemulsion system (isopropyl myristate/medium-chain glyceride/polysorbate 80/water) for topical delivery of celecoxib. The pseudoternary phase diagram was constructed with constant surfactant concentration, and several compositions were identified and characterized by using dynamic light scattering. The in vitro permeation rate of celecoxib through rat skin was determined for microemulsions, microemulsion gel, and cream by using the modified Franz-type diffusion cell. In all formulations tested, celecoxib permeated more quickly, and the microemulsions increased the permeation rate of celecoxib up to 5 and 11 times compared with those of microemulsion gel and cream, respectively. Increasing the concentration of medium-chain mono-/di-glyceride in microemulsion imparted increased droplet size and viscosity and decreased diffusion coefficient. In vivo anti-inflammatory study suggested that the developed microemulsion formulations might serve as potential drug vehicle for the prevention of UVB-induced skin cancer.

Self-aggregation of binary mixtures of alkyltriphenylphosphonium bromides: a critical assessment in favor of more than one kind of micelle formation.

The micellization behavior of binary combinations of alkyltriphenylphosphonium bromides (ATPBs) with alkyl chain carbons 10, 12, 14, and 16 has been studied by conductometry and calorimetry. The combinations C(10)-C(12), C(10)-C(14), C(10)-C(16), C(12)-C(14), C(12)-C(16), and C(14)-C(16) were found to form two cmc's by both the methods, with good agreement, except C(14)-C(16)TPB, which has evidenced only a single cmc by calorimetry for all combinations. The combinations C(10)-C(12) (for both cmc(1) and cmc(2)) and C(10)-C(14)TPB (for cmc(2)) formed ideal mixtures, whereas the rest were nonideal. In the nonideal binary mixtures, the ATPB components showed antagonistic interaction with each other. The cmc, interaction parameter (beta), mixed micellar composition, extent of counterion binding, and thermodynamic parameters for the micellization process have been reported and discussed. The enthalpy of mixed micelle formation has been found to have a fair correlation with a Clint-type relation applicable to ideal binary mixtures of surfactants.

Kinetics in microemulsion V. Glucose oxidase catalyzed oxidation of beta-D-glucose in aqueous, micellar and water-in-oil microemulsion media.

The oxidation of beta-D-glucose by the enzyme glucose oxidase was studied in aqueous medium, in solutions of surfactants AOT (2-ethylhexylsulfosuccinate, sodium salt) TX-100 (polyethylene glycol p-tert octyl phenyl ether) and in w/o microemulsion medium (water/AOT/decane) at different water/AOT mole ratio (omega), pH, temperature and in presence of additives. The time-dependent activities of the enzyme in aqueous and microemulsion media were determined. The catalytic process was retarded in the presence of TX-100 and AOT. In microemulsion medium, kcat values exhibited a deformed W-shaped profile with omega. At pH 7, a maximum value of kcat was observed at omega = 10.6. The kcat values were found to be higher in microemulsion medium than in aqueous medium at both pH's 7 and 8. Activation parameters for the kinetic process were evaluated together with the thermodynamics of the enzyme-substrate Michaelis complex. The deltaG* was lower, whereas deltaH* and deltaS* were higher in microemulsion than in water. The Michaelis constant, KM was also lower in microemulsion. The inhibition effects of the additives, NaNO3 and NaC were studied in both aqueous and microemulsion media by examining their influences on catalytic constant, kcat and Michaelis constant KM. In microemulsion, both the additives NaNO3 and NaC produced non-competitive inhibition.

Studies on surfactant-biopolymer interaction. I. Microcalorimetric investigation on the interaction of cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) with gelatin (Gn), lysozyme (Lz) and deoxyribonucleic acid (DNA).

The interaction of the surfactants cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) with the biopolymers gelatin (Gn), lysozyme (Lz) and deoxyribonucleic acid (DNA) was studied by isothermal titration microcalorimetry at varied biopolymer concentration, pH and temperature. The nature of interaction of the surfactants with the biopolymers was assessed from the observed enthalpy-[surfactant] profiles. The biopolymer-induced aggregation of the surfactants was observed. The enthalpies of aggregation of amphiphiles, binding of aggregates with macromolecules, organisational change of bound aggregates, and threshold concentrations for micelle formation of surfactants in the presence of biopolymers were estimated. The results collected on the three biopolymers were analysed and compared.

Physicochemical investigations of microemulsification of coconut oil and water using polyoxyethylene 2-cetyl ether (Brij 52) and isopropanol or ethanol.

The microemulsification of coconut oil/polyoxyethylene 2-cetyl ether/2-propanol or ethanol/water was investigated. The phase behaviors of the mixed system were examined. The shear viscosity at different temperatures was measured to derive activation parameters for the viscous flow. The diffusion coefficient of the microemulsions at different compositions was determined by the DLS method. The energetics of solubilization of water into oil + Brij + alkanol as well as of oil into water + Brij + alkanol forming w/o and o/w microemulsions, respectively, were calorimetrically determined.

Physicochemical investigations on microemulsification of eucalyptol and water in presence of polyoxyethylene (4) lauryl ether (Brij-30) and ethanol.

The microemulsification of eucalyptol/polyoxyethylene(4)lauryl ether (Brij-30)/ethanol/water has been investigated. The phase behaviours of the mixed system in pseudoternary and tetrahedral representations have been examined to understand the topological nature of the multicomponent mixtures. Phase volumes of the heterogeneous combinations have been estimated to understand the mixing efficacy of the combinations. Shear viscosities of different monophasic compositions have been measured at different shear rates and temperatures, and the activation parameters for the viscous flow have been evaluated. The dimensions of the nanodispersions of w/o and o/w types, their diffusion coefficients and the polydispersity have been determined by the DLS method. The energetics of solubilisation (dissolution) of water in oil+Brij-30+ethanol as well as oil in water+Brij-30+ethanol forming w/o and o/w microemulsions, respectively, have been calorimetrically determined. Considering the phase separation point to be the point of maximum solubility, the energetic parameters (enthalpy, free energy and entropy) of the microemulsification process have been estimated.

Photophysics of thionine dye in aqueous and liposome media in presence of different reducing agents.

The photoelectrochemical and spectral (both absorption and fluorescence) studies of thionine, a cationic phenothiazine dye, have been carried out in aqueous and phosphatidylcholine liposome media in the presence of different reducing agents, such as I(-), Br(-), Cl(-) and Fe(2+). The results show that the photovoltage generation from photoelectrochemical studies and Stern-Volmer quenching constant studied by fluorescence quenching support the photoinduced electron transfer from the reducing agent to the singlet excited thionine dye. Moreover, a good correlation between photovoltages/Stern-Volmer quenching constants vs. reduction potentials of the reducing agents also confirms the above electron transfer in the photoexcited state.

Dispersed Molecular Aggregates.

Colloidal dispersions of tungstic acid (H(2)WO(4)) have been prepared in water/(TX-100+alkanol)/n-heptane water-in-oil microemulsion media by reacting Na(2)WO(4) with HCl. The effects of alkanol chain length, TX-100/alkanol mass ratio, temperature, and dilution at different [water]/[TX-100] mole ratios (omega) have been studied by the dynamic light scattering technique. The formation of H(2)WO(4) in the microwater pool has been established by FT-IR measurements. The particle sizes and shapes in microemulsion media and in isolated states have been measured by TEM and SEM techniques. The enthalpy of formation of H(2)WO(4) in the water pool of the microemulsions has also been determined microcalorimetrically. Copyright 2001 Academic Press.