Headgroup Size Research Articles

Cationic surfactants for micellar electrokinetic chromatography: 1. Characterization of selectivity using the linear solvation energy relationships model

MEKC and the linear solvation energy relationship (LSER) model have been applied to two series of cationic surfactants. The synthetic flexibility of the quaternary ammonium group is exploited to generate the two series, one consisting of linear substitutions and the other incorporating the ammonium into ring structures of varying size. The effects of the head group structure on the CMC, aggregation number, and electrophoretic properties of the surfactants were determined. These surfactants were also characterized with the LSER model, which allowed the contributions of five chemical factors to the interactions between solutes and the micelles to be evaluated. Trends were observed in the cohesivity and polarity of the linear surfactant series, with both increasing with the size of the head group. No trends in the LSER parameters were observed in the cyclic series, but the LSER results do show that the surfactants with cyclic head groups provide a significantly different solvation environment from the linear series. Additional trends were observed in the aggregation behavior and chromatographic properties of the surfactants. These included changes in the CMCs, aggregation numbers, EOF, and electrophoretic mobility of the micelles that correlate to changes in head group size.

Improved activity of enzymes in mixed cationic reverse micelles with imidazolium-based surfactants

This work reports the significant enhancement in performance of interfacially active enzymes, Chromobacterium viscosum (CV) lipase and horseradish peroxidase (HRP) in mixed reverse micelles of cetyltrimethylammonium bromide (CTAB) and imidazolium-based amphiphiles having varying tail lengths. Lipase activity in these mixed systems was always higher than that in the individual cationic reverse micelles of CTAB or any imidazolium surfactant, highest being observed in the mixed system of CTAB (50 mM) and 6 (1-tetradecyl-3-methyl imidazolium bromide, 40 mM)/water/isooctane/ n-hexanol (0.24 M), second-order rate constant, k 2 = 1301 ± 5 cm 3 g −1 s −1, ∼200% higher compared to that in CTAB and ∼65% more than the most popular AOT-microemulsion. Activity increased with concentration of imidazolium surfactant and also with its alkyl tail length. To have a more profound view on the structure–activity relationship, CTAB was replaced by cetyltriethylammonium bromide (CTEAB) and cetyltripropylammonium bromide (CTPAB) with subsequent increase in the headgroup size. The generalized influence of these mixed cationic systems on surface-active enzyme was also verified using HRP, where the activity improved ∼100%. This enhancement in enzyme activity is presumably due to the activating effect of the imidazolium cation in the enzymatic reactions by improving the nucleophilicity of interfacial water in vicinity of enzyme through hydrogen bonding.

Electrolyte effect on mixed micelle and interfacial properties of binary mixtures of cationic and nonionic surfactants

In the present work, the adsorption behavior at the liquid–air interface and micellization characteristics of mixtures of cetyltrimethylammonium bromide (CTAB) and p-(1,1,3,3-tetramethylbutyl) polyoxyethylene (TritonX-100) in aqueous media containing different concentrations of NaBr were investigated by surface tension and potentiometry measurements. From plots of surface tension ( γ) as a function of solution composition and total surfactant concentration, we determined the critical micelle concentration (CMC), minimum surface tension at the CMC ( γ CMC ), surface excess ( Γ max ), and mean molecular surface area ( A min ). On the basis of regular solution theory, the compositions of the adsorbed film ( Z) and micelles ( X M ) were estimated, and then the interaction parameters in the micelles ( β M ) and in the adsorbed film phase ( β σ ) were calculated. For all mole fraction ratios, the results showed synergistically enhanced ability to form mixed micelles as well as surface tension reduction. Furthermore β was calculated by considering nonrandom mixing and head group size effects. It was observed that, for both the planar air/aqueous interface and micellar systems, the nonideality decreased as the amount of electrolyte in the aqueous medium was increased. This was attributed to a decrease of the surface charge density caused by increasing the concentration of bromide ions.

Conductometry and Thermodynamics Study of Metal Dodecyl Sulfates in Aqueous Solution

The aggregation behavior of metal dodecyl sulfates (MDS), [Na1+, Mg2+, Mn2+, Co2+, and Ni2+] in water has been studied by electrical conductivity (at 293.15–333.15 K) and surface tension methods (at 303.15 K). Critical micelle concentrations (CMCs), degree of counterion dissociation (β) evaluated from conductivity data. Using law of mass action model, the thermodynamic parameters viz. Gibbs energy (ΔGm 0), enthalpy (ΔHm 0), and entropy (ΔSm 0) were evaluated. The enthalpy of micellization decreases strongly with increasing temperature. ΔG is always negative (thermodynamically favored process) and slightly temperature and counterion dependent. Gibbs energy and entropy exploit micellization as thermodynamic favorable process. The electrostatic repulsions between ionic head groups, which prevent the aggregation, are progressively screened as the ionic character decreases with the size of the counterion. The plots of differential conductivity, (dk/dc) T,P , versus the total surfactant concentration enables us to determine the CMC values more precisely than the conventional method. Surfactants with strong condense counterion are adapted to rodlike micelle better than to a spherical micelle. The data are explained in terms of molecular characteristics of surfactants viz. degree of dissociation, polar head group size and counterion.

Role of the Spacer Stereochemistry on the Structure of Solid-Supported Gemini Surfactants Aggregates

Energy dispersive X-ray diffraction was applied to investigate the role of the spacer stereochemistry on the structure of the solid supported aggregates of three stereoisomeric cationic gemini surfactants, 2,3-dimethoxy-1,4-bis-(N-hexadecyl-N,N-dimethylammonio)butane dibromide. Solid-supported Gemini surfactant aggregates self-assemble into highly interdigitated multibilayer stacks. Structural properties, such as the bilayer thickness, the headgroup size, the thickness of the hydrophobic core, and the size of the interbilayer water region, were derived from electron density profiles. Results show that the stereochemistry of the spacer controls the structural properties of the solid-supported interfacial aggregates.

Purification, Surface Tensions, and Miscibility Gaps of Alkyldimethyl and Alkyldiethylphosphine Oxides

AbstractAlkyldimethyl (CnDMPO) with chain lengths of n = 8 (octyl), 10 (decyl), 12 (dodecyl), and 14 (tetradecyl) as well as alkyldiethyl (CnDEPO) phosphine oxides with chain lengths of n = 10, 12, and 14 were synthesized and purified to study how the adsorption properties and the location of the miscibility gap of these surfactants depend on the size of the head group and on the length of the alkyl chain. After surfactant purification, the surface tension isotherms were determined from which the cmc, the minimum surface tension σcmc, the maximum surface concentration Γmax, and the minimum surface area Amin were obtained. As expected, for one homologous series, a decrease in the cmc and an increase in Γmax was observed with increasing alkyl chain length. For two surfactants of the same alkyl chain length, the cmc values of the CnDEPO surfactants are approximately two times lower than those of the CnDMPO surfactants. However, the Γmax values of CnDEPO are lower than those of CnDMPO as two ethyl chains are sterically more demanding than two methyl chains. In addition to the adsorption properties, the location of the miscibility gap as a function of the alkyl chain length and the head group size was studied. Its location depends on the total number of carbon atoms and not primarily on the length of the main alkyl chain. This observation reflects the decreasing water solubility which can be tuned by increasing the length of either the main alkyl chain or of the shorter head group chains.

On the Propensity of Phosphatidylglycerols to Form Interdigitated Phases

We have determined the phase behavior of disaturated phosphatidylglycerols (PGs) of chain lengths nCH2=14–18 at high pH and ionic strength using calorimetry, dilatometry, as well as x-ray diffraction. PGs with nCH2=14 and 16 show thermotropic behavior similar to that of phosphatidylcholines (PCs). The area/lipid obtained in the gel phase is smaller than that reported for PCs despite the expected larger effective headgroup size. This can be explained by the tilting of the PG headgroup out of the bilayer plane, and we provide experimental evidence for a headgroup tilt transition. For distearoyl PG, we further find that the “usual” gel phase coexists with an interdigitated phase, which exhibits a transition from an orthorhombic into a hexagonal chain packing. The total amount of the interdigitated phase depends significantly on the temperature but is found to be largely independent of temperature equilibration time and different sample preparation protocols. Thus, the development of the interdigitated phase appears to be kinetically trapped. The formation of interdigitated phases in PGs at much smaller chain lengths than in PCs is of high relevance to interaction studies with antimicrobial peptides, as it provides a mechanism for the discrimination of membranes composed of different lipid species.

EHD1 and Eps15 Interact with Phosphatidylinositols via Their Eps15 Homology Domains

The C-terminal Eps15 homology domain-containing protein, EHD1, regulates the recycling of receptors from the endocytic recycling compartment to the plasma membrane. In cells, EHD1 localizes to tubular and spherical recycling endosomes. To date, the mode by which EHD1 associates with endosomal membranes remains unknown, and it has not been determined whether this interaction is direct or via interacting proteins. Here, we provide evidence demonstrating that EHD1 has the ability to bind directly and preferentially to an array of phospholipids, preferring phosphatidylinositols with a phosphate at position 3. Previous studies have demonstrated that EH domains coordinate calcium binding and interact with proteins containing the tripeptide asparagine-proline-phenylalanine (NPF). Using two-dimensional nuclear magnetic resonance analysis, we now describe a new function for the Eps15 homology (EH) domain of EHD1 and show that it is capable of directly binding phosphatidylinositol moieties. Moreover, we have expanded our studies to include the C-terminal EH domain of EHD4 and the second of the three N-terminal EH domains of Eps15 and demonstrated that phosphatidylinositol binding may be a more general property shared by certain other EH domains. Further studies identified a positively charged lysine residue (Lys-483) localized within the third helix of the EH domain, on the opposite face of the NPF-binding pocket, as being critical for the interaction with the phosphatidylinositols.

Calorimetric, X-Ray Diffraction, and Spectroscopic Studies of the Thermotropic Phase Behavior and Organization of Tetramyristoyl Cardiolipin Membranes

The thermotropic phase behavior and organization of aqueous dispersions of the quadruple-chained, anionic phospholipid tetramyristoyl diphosphatidylglycerol or tetramyristoyl cardiolipin (TMCL) was studied by differential scanning calorimetry, x-ray diffraction, 31P NMR, and Fourier-transform infrared (FTIR) spectroscopy. At physiological pH and ionic strength, our calorimetric studies indicate that fully equilibrated aqueous dispersions of TMCL exhibit two thermotropic phase transitions upon heating. The lower temperature transition is much less cooperative but of relatively high enthalpy and exhibits marked cooling hysteresis, whereas the higher temperature transition is much more cooperative and also exhibits a relatively high enthalpy but with no appreciable cooling hysteresis. Also, the properties of these two-phase transitions are sensitive to the ionic strength of the dispersing buffer. Our spectroscopic and x-ray diffraction data indicate that the lower temperature transition corresponds to a lamellar subgel (L c′) to gel (L β ) phase transition and the higher temperature endotherm to a L β to lamellar liquid-crystalline (L α ) phase transition. At the L c′/L β phase transition, there is a fivefold increase of the thickness of the interlamellar aqueous space from ∼11 Å to ∼50 Å, and this value decreases slightly at the L β /L α phase transition. The bilayer thickness (i.e., the mean phosphate-phosphate distance across the bilayer) increases from 42.8 Å to 43.5 Å at the L c′/L β phase transition, consistent with the loss of the hydrocarbon chain tilt of ∼12°, and decreases to 37.8 Å at the L β /L α phase transition. The calculated cross-sectional areas of the TMCL molecules are ∼79 Å 2 and ∼83 Å 2 in the L c′ and L β phases, respectively, and we estimate a value of ∼100 Å 2 in the L α phase. The combination of x-ray and FTIR spectroscopic data indicate that in the L c′ phase, TMCL molecules possess tilted all- trans hydrocarbon chains packed into an orthorhombic subcell in which the zig-zag planes of the chains are parallel, while in the L β phase the untilted, all- trans hydrocarbon chains possess rotational mobility and are packed into a hexagonal subcell, as are the conformationally disordered hydrocarbon chains in the L α phase. Our FTIR spectroscopic results demonstrate that the four carbonyl groups of the TMCL molecule become progressively more hydrated as one proceeds from the L c′ to the L β and then to the L α phase, while the two phosphate moieties of the polar headgroup are comparably well hydrated in all three phases. Our 31P-NMR results indicate that although the polar headgroup retains some mobility in the L c′ phase, its motion is much more restricted in the L β and especially in the L α phase than that of other phospholipids. We can explain most of our experimental results on the basis of the relatively small size of the polar headgroup of TMCL relative to other phospholipids and the covalent attachment of the two phosphate moieties to a single glycerol moiety, which results in a partially immobilized polar headgroup that is more exposed to the solvent than in other glycerophospholipids. Finally, we discuss the biological relevance of the unique properties of TMCL to the structure and function of cardiolipin-containing biological membranes.

Hydration effect on the structure of dioleoylphosphatidylcholine bilayers

In situ enersgy dispersive x-ray diffraction was used to study the effect of hydration on the structure of dioleoylphosphatidylcholine (DOPC) bilayers in the biologically relevant liquid-crystalline phase. A broad range of relative humidity (RH) was investigated (0.45<RH<1) and two hydration regimes were found. From RH=0.45 up to RH∼0.94, the structure of DOPC bilayers was found to change slightly. At RH∼0.94, a distinctive structural change was observed. From RH∼0.94 up to full hydration, a strong increase in the head group size, coupled with a marked decrease in the hydrophobic core thickness, was observed. Possible molecular mechanisms underlying experimental observations are discussed.

PH-Dependent Phase Behavior of Carbohydrate-Based Gemini Surfactants. The Effects of Carbohydrate Stereochemistry, Head Group Hydrophilicity, and Nature of the Spacer

The pH-dependent phase behavior and hydroxide-ion adsorption ability of a series of (reduced) carbohydrate-based gemini surfactants were studied between pH 2 and 12. Static and dynamic light scattering were employed to address transitions in the aggregate morphologies and cryo-electron microscopy was used to provide further evidence for the morphologies present in solution. Changes in aggregate structure as a result of a change in solution pH and an accompanying change in protonation state or a change in molecular structure can be rationalized in terms of the variations in the packing parameter. In this paper we have focused our attention on the size of the carbohydrate moiety, the carbohydrate stereochemistry and the nature of the spacer (hydrophobic vs hydrophilic). At near neutral pH, most of the gemini surfactants form vesicles. Upon lowering of the pH, the vesicles undergo a transition toward wormlike micelles followed by a transition to spherical micelles. Upon increasing the solution pH, flocculation occurs due to charge neutralization followed at still higher pH by redispersion and charge reversal of the vesicles through the specific adsorption of hydroxide ions to the vesicular surface. Upon decreasing head group size at constant, but low, degrees of protonation, the packing parameter has a tendency to become larger than one resulting in the formation of inverted phases. Upon further decrease in the head group size, oil droplets are observed. In case of a hydrophobic spacer, the carbohydrate stereochemistry affects the pH of the transitions, but not the type of the transitions. By contrast, for a hydrophilic spacer, the pH of the transitions remains unaffected. Adsorption of hydroxide ions at basic pH follows similar trends, but was only found for vesicles and oil droplets. The large range of structural variations that we have examined allows a better understanding of the requirements for the phase transitions for carbohydrate-based gemini surfactants as well as for the physisorption of hydroxide ions to interfaces in general.

Effects of head group size on the reaction methyl 4‐nitrobenzenesulfonate + Br− in water‐ethylene glycol cetyltrialkylammonium bromide micellar solutions

AbstractThe reaction methyl 4‐nitrobenzenesulfonate + Br− has been studied in water‐ethylene glycol cetyltrialkylammonium bromide (alkyl = methyl, ethyl, propyl, and butyl) micellar solutions by changing surfactant concentration as well as the weight percentage of ethylene glycol present in the bulk phase. The pseudophase model was adequate to rationalize quantitatively the micellar kinetic effects. Information about the influence of the head group size on the second‐order rate constant of the process and on the binding equilibrium constant of the organic substrate to the cationic micelles in water–ethylene glycol mixtures was obtained. Kinetic data taken from the literature were compared to those obtained in this work in order to examine the different effects produced by an alcohol that is localized in the bulk phase, such as ethylene glycol, with those caused by an alcohol that distributes between the bulk and micellar pseudophases, such as 1‐butanol. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 346–352, 2007

Probing the Relationship between Interfacial Concentrations and Lipase Activity in Cationic W/O Microemulsions: A Quantitative Study by Chemical Trapping

Interfacial concentrations and/or space: which one is the predominant factor in regulating lipase activity at the water-oil interface? This work is an endeavor toward probing the relationship between lipase activity and interfacial concentrations in cationic water-in-oil (W/O) microemulsions through quantitative study by a chemical trapping method. The interfacial concentrations of water ([H2Oi]), bromide ([Bri-]), and n-hexanol ([HexOHi]) were estimated in the W/O microemulsions of six surfactants with varying headgroup architecture and hydrophilicity across a wide W0 ([H2O]/[surfactant]) range. The surfactants were prepared by the replacement of methyl groups of cetyltrimethylammonium bromide (1) by n-propyl (2-4), one hydroxyethyl (5), and one methoxyethyl (6) group. The estimated [H2Oi] was found not to change much (30.0-36.7 M) with the variation in headgroup hydrophilicity or size from 1-5. However, [Bri-] was found to increase with a decrease in the degree of dissociation (alpha), being higher for 1 and 5 (2.4-3.3 M) and relatively lower (0.9-1.9 M) for others depending on W0. Interestingly, [H2Oi] was found to be little higher (41.5-42.2 M) in the case of 6. The present study elucidates the importance of interfacial water and counterion concentrations in modulating the lipase activity in reverse micelles. In our previous report, the lipase activity was found to increase from 1-4 and in 6, whereas that observed in 5 was comparable with 1, being largely regulated by the surfactant head group size (Das, D.; Roy, S.; Mitra, R. N.; Dasgupta, A.; Das, P. K. Chem.-Eur. J. 2005, 11, 4881). The only other parameter that increased distinctly with lipase activity is the headgroup size, not [H2Oi]. Thus, the role of [H2Oi] in comparison to the surfactant's headgroup size is not found to be that significant. Moreover, the lower [Bri-] in 2-4 and 6 perhaps enhances the probability of enzyme and substrate localization at the interface, leading to higher lipase activity.

Adsorption and micelle formation of alkylammonium chloride–alkyltrimethylammonium chloride mixtures

The surface tension of the aqueous solutions of binary cationic surfactant mixtures of (1) dodecylammnonium chloride (DAC)–tetradecyltrimethylammonium chloride (TTAC), (2) decylammonium chloride (DeAC)–dodecyltrimethylammonium chloride (DTAC), and (3) DAC–DTAC was measured as a function of the total molality and composition of surfactants at 298.15 K. The compositions of surfactants in the adsorbed film and micelle were evaluated and the phase diagram of adsorption and that of micelle formation were constructed. Furthermore the excess Gibbs energies of adsorption and micelle formation were calculated to estimate the deviation from the corresponding ideal mixing. It was found that the surface and micelle are enriched in trimethylammonium salts in (1) and (2), while in ammonium salt in (3) compared to the bulk solution. On the other hand, the micelle is enriched in trimethylammonium salts compared to the surface at the critical micelle concentration (CMC) in all the systems. The miscibility of the surfactants was clarified from the standpoints of the structure of the head group and of the matching between the size of polar head group of surfactants and the difference in hydrocarbon chain length.

Coarse-grained simulation of amphiphilic self-assembly

The authors present a computer simulation study of amphiphilic self-assembly performed using a computationally efficient single-site model based on Gay-Berne [J. Chem. Phys. 74, 3316 (1981)] and Lennard-Jones particles. Molecular dynamics simulations of these systems show that free self-assembly of micellar, bilayer, and inverse micelle arrangements can be readily achieved for a single model parametrization. This self-assembly is predominantly driven by the anisotropy of the amphiphile-solvent interaction, amphiphile-amphiphile dispersive interactions being found to be of secondary importance. While amphiphile concentration is the main determinant of phase stability, molecular parameters such as head group size and interaction strength also have measurable affects on system properties.

Three-component microemulsions formed using pH-degradable 1,3-dioxolane alkyl ethoxylate surfactants

A series of three nonionic surfactants which undergo acid-catalyzed hydrolysis, O-[(2,2-dialkyl-1,3-dioxolan-4-yl) methoxy] – O′-methoxy poly(ethylene glycol), or cyclic ketal (CK), were synthesized. The surfactants shared similar HLB values (9.2–9.8) but differed in the relative length of their two alkyl tails. Water/CK/isooctane microemulsion systems formed by each of the three surfactants also shared similar phase behavior, physical properties, and surfactant hydrolysis kinetics. The apparent critical microemulsion concentration for three CK surfactants, 0.060–0.075 g g −1 (in both water and isooctane), and the efficiency, the minimum amount of surfactant required to totally mix water and oil into single microemulsion phase, 0.35–0.40 g g −1, are significantly higher than values possessed by regular, linear, alkyl ethoxylate surfactants. The underlying causes for the high values were investigated. Due to the broad distribution of its ethoxylate head group size, CK surfactants were distributed among all phases within two- and three-phases systems, with CKs possessing shorter ethoxylate groups partitioning to the oil phase and CKs with larger ethoxylate groups to the aqueous phase. Small-angle neutron scattering experiments suggest that CK exists as monomers or very small pre-micellar aggregates in isooctane at 12% and as ellipsoidal aggregates in water at 2.5–25%. Surface pressure versus surface area measurements of CK surfactant monolayers at the water-air interface demonstrate two differences from linear alkyl ethoxylate monolayers: the occurrence of a collapse at moderately low surface pressure (30 mN m −1) and high surface area per molecule (0.59 nm 2) and the inability to undergo dissolution when subjected to a constant, moderately high surface pressure (25 mN m −1). The results suggest that CK molecules are not able to pack as efficiently as linear alkyl ethoxylates at interfaces, and are strongly anchored to monolayers in aqueous media.

Effect of the Head-group Size of C<SUB>12</SUB>(<EM>n</EM>)-4-C<SUB>12</SUB>(<EM>n</EM>)·2Br on the Interfacial Composition and Structure of W/O Microemulsion

Effect of the Head-group Size of C<SUB>12</SUB>(<EM>n</EM>)-4-C<SUB>12</SUB>(<EM>n</EM>)·2Br on the Interfacial Composition and Structure of W/O Microemulsion

Effects of head group size on micellization of cetyltrialkylammonium bromide surfactants in water–ethylene glycol mixtures

Micellization of cetyltrialkylammonium bromide (alkyl = methyl, ethyl, propyl, and butyl) surfactants has been studied in various water–ethylene glycol, EG, mixtures. This study provided the opportunity of investigating how, for a given hydrophobic tail length, the head group size determines the effect of the addition of EG on the micellization process. Conductivity, surface tension, spectroscopic and steady-state fluorescence measurements were carried out. The influence of additional methylenes in the headgroups on the Gibbs energy of micellization, Δ G M ° , was found to derive from changes in the solvophobic Gibbs energy contribution and from variations in the electrostatic headgroups interaction contribution.

Alcohol ethoxylates mediate their bacteriostatic effect by altering the cell membrane of Escherichia coli NCTC 8196

The minimum inhibitory concentration (MIC) of a homologous series of alcohol ethoxylates with the same head group size (E6) but differing in the number of carbon atoms in their ‘tail group’ from 10 to 16 was determined for Staphylococcus aureus NCTC 4163 and Escherichia coli NCTC 8196 using a turbidimetric assay. All the surfactants tested demonstrated bacteriostatic activity against both organisms. A tetrazolium assay showed that C14E6 and C16E6 had little effect on the membrane-bound dehydrogenase enzyme activity of E. coli NCTC 8196 compared with C10E6 and C12E6. C10E6 caused leakage both of K + and nucleotides in a concentration-dependent manner above its MIC of 0.2 mM. C12E6 caused some leakage at concentrations below its MIC (0.12 mM).

Sphere‐to‐Rod Transitions in Cationic Micelles: Quaternary Ammonium Halides+Phenol+Water Systems

Viscosity measurements on aqueous micellar solutions of cationic surfactants containing phenol with and without sodium bromide were made to study the sphere‐to‐rod transitions. Effect of surfactant structure (nonpolar tail, polar head group sizes and counterion), temperature, and phenol and sodium bromide concentration on the viscosity behavior of the surfactant solution is discussed. The sphere‐to‐rod transition is usually indicated by a marked increase in viscosity. While low temperature, high surfactant concentration, presence of salt, and hydrophobic nature of surfactant all favor the formation of rod‐like micelles, the presence of phenol showed peculiar behavior. Initial additions of phenol (up to about 2.5 wt%) showed a marked increase in viscosity, independent of the nature and concentration of surfactant and temperature; lower viscosities were observed at higher phenol concentration. Conductance and sound velocity results support the viscosity results.