Time-resolved Fluorescence Quenching Research Articles

Studies on the self-aggregation, interfacial and thermodynamic properties of a surface active imidazolium-based ionic liquid in aqueous solution: Effects of salt and temperature

The influence of four sodium salts (NaCl, NaBr, Na2SO4, and Na3PO4) on the self-aggregation, interfacial, and thermodynamic properties of a surface active ionic liquid (1-hexadecyl-3-methylimidazolium chloride, C16MImCl) has been explored in aqueous solutions by conductometry, tensiometry, spectrofluorimetry, isothermal titration calorimetry and dynamic light scattering (DLS). Analyses of the critical micellar concentration (cmc) values indicate that the anions of the added salts promote the self-aggregation of C16MImCl in the order: Cl− < Br− < PO43−< SO42−. Dehydration of imidazolium head groups, in general, governs the process of micellization of aqueous C16MImCl in presence of the investigated salts within the investigated temperature range (298.15–318.15 K), while the melting of iceberg takes the leading role below 303.15 K for the C16MImCl-Na3PO4 system. The results indicate that addition of salt leads to a greater spontaneity of micellization, and that exothermicity prevails in these systems. Differential effect of the salts on the interfacial properties of C16MeImCl has been interpreted on the basis of the coupled influence of the electrostatic charge neutralization of surfactants at the interface, and the van der Wa-als repulsion of surfactant tails and electrostatic repulsion of surfactant head groups. C16MeImCl has been predicted to form spherical micelles in presence of varying amounts of NaCl, Na2SO4 and Na3PO4, while there occurs probably a transition in the micellar geometry from spherical to non-spherical shape when added NaBr concentration exceeds 0.01 mol.kg−1. Fluorescence studies demonstrate that a combined quenching mechanism is operative for the quenching of pyrene fluorescence in the investigated C16MImCl-salt systems. Micellar aggregation numbers obtained from Steady State Fluorescence Quenching method have always been found be somewhat smaller than those estimated from Time Resolved Fluorescence Quenching method. The order of instability of the C16MImCl-micelles ascertained from Zeta potential measurements conform to what has been inferred from the cmc values. The hydrodynamic diameters of C16MImCl-micelles, obtained from DLS studies, have been found to increase with increasing salinity of the solutions.

Micelle growth of cationic gemini surfactants studied by NMR and by time-resolved fluorescence quenching

The micelle growth of a series of five cationic gemini surfactants has been investigated by time-resolved fluorescence quenching (TRFQ) and by two NMR techniques, line width analysis and diffusometry. The surfactant series was designed such that the effect of a number of variables could be assessed: length of the spacer unit, presence of ester bonds in the tails close to the head groups, and presence of a hydroxyl group in the spacer. For the gemini with long spacer, the micelles remained relatively small in size upon an increase of the concentration. The gemini surfactants with short spacer, on the other hand, showed a considerable micellar growth as the concentration was raised. It is of particular interest that the relatively simple line width analysis of one dimensional 1H NMR spectra gave qualitatively the same results as the more sophisticated TRFQ and NMR diffusometry techniques.

Application of Fluorescent Probe Technology in Self-Assembly Systems of Amphiphile Aqueous Solutions

In this paper,we review the application of fluorescent probe technology in self-assembly systems of amphiphile aqueous solutions.Fluorescence technology,especially fluorescence probe technology has been extensively employed to explore local information about various molecular assemblies.The following contents are covered:(1) The critical aggregate concentration,microviscosity,and micropolarity may be obtained from fluorescence parameters such as emission maxima,fluorescence intensity,and lifetime etc.(2) Probe quenching,especially,timeresolved fluorescence quenching (TRFQ) can give information about aggregation number and surface charge density which can be used as the indication on aggregate transition.(3) Fluorophore-labeled amphiphiles which can take part in the formation of aggregates reveal more precise information,so that an in situ investigation of local environments is possible.Moreover,fluorescence resonance energy transfer (FRET) and excited state proton transfer (ESPT) are also useful in this field.Therefore,fluorescence probe technology provides us with a simple and effective method to study organized amphiphiles systems.

Steady State and Time Resolved Fluorescence Quenching and Chemical Modification Studies of a Lectin from Endophytic Fungus Fusarium solani

The solute quenching studies of a lectin from endophytic fungus Fusarium solani were carried out using different quenchers such as acrylamide, succinimide, potassium iodide and cesium chloride. The lectin showed emission maximum at 348 nm indicating relative exposure of tryptophan. The quenchable fraction of the fluorophore was 100% with acrylamide, whereas it was only 50% with succinimide. The ionic quenchers iodide and cesium showed opposite effects at different pH. In the case of cesium, raising the pH resulted in increased quenching and accessibility of typtophan residue, while the iodide showed just opposite effect. These studies showed that the single tryptophan residue of the lectin (per monomer) is relatively exposed, and might be in the vicinity of positively charged amino acid residues. Various amino acids of the F. solani lectin were modified using different reagents to obtain information about the hemagglutinating site. The chemical modification studies suggested tyrosine residues can be modified using N-acetylimidazole, which results in complete loss of hemagglutination activity of the lectin. Kinetics of chemical modification suggested involvement of only 2 tyrosine residues. Modification of arginine, cysteine, histidine, lysine, aspartate, glutamate and tryptophan did not result in loss of hemagglutinating activity of the lectin.

Amphiphilic Lauryl Ester Derivatives from Aromatic Amino Acids: Significance of Chemical Architecture in Aqueous Aggregation Properties

Lauryl esters of L-tyrosine (LET) and L-phenylalanine (LEP) were, in a previous interface adsorption study, found to adopt very different interfacial conformations. The present study is an investigation of their aqueous aggregation properties with the goal of elucidating the effects of the presence in LET and absence in LEP of the phenolic OH group on their aqueous aggregate structures and micellar conformations of the surfactant monomers. The measured properties included aggregation numbers from time-resolved fluorescence quenching (TRFQ), interface hydration index and microviscosity by electron spin resonance (ESR), chemical shifts of (1)H resonance lines by NMR, and Krafft temperatures and enthalpies of structural transitions by differential scanning calorimetry (DSC). The TRFQ, ESR, and NMR experiments were conducted at various temperatures from 23 to 70 degrees C for various surfactant concentrations from 0.050 to 0.200 M. Markedly different temperature dependences of aggregation number and (1)H NMR chemical shifts are exhibited by LET and LEP micelles. LET and LEP form ionic micelles. The aggregation number of LEP decreases as is characteristic of ionic micelles, but that of LET increases slightly with temperature. The changes with temperature in the NMR chemical shifts and width of the resonance lines are significantly greater for the various LEP protons than for those of LET. The differences in these properties and other fluorescence decay characteristics of fluorophores incorporated into the micelles could be attributed to the difference in the micellar conformations of LET and LEP which are postulated to be similar to that at oil-water interfaces. The phenolic group is hypothesized to be in the micelle-water interface as part of the headgroup in LET micelles, and its location does not change with temperature. On the other hand, in LEP micelles, the phenyl ring is folded into the core overlapping with the flexible hydrophobic chains. The resulting closer proximity between the phenyl ring and the flexible hydrocarbon chain causes interdependence of the phenyl ring and chain proton resonances, leading to the observed temperature dependence of the chemical shifts in LEP. The TRFQ and ESR data are combined together in a molecular space-filling model, referred to as the polar shell model, to derive the geometrical properties of the micelle. The DSC scans in the temperature range 10-55 degrees C showed the presence of distinctly different endotherms for LET and LEP. The Krafft temperatures, K(T), and the enthalpies were determined. The higher K(T) and broader peak of the DSC endotherm of LET as compared to LEP are attributed to the stabilization of fiberlike structures below the Krafft temperature due to its chirality and the hydrogen bonding capability of the phenolic OH and also to the ion-dipole interactions. Thus, all of the observed differences between LET and LEP could be attributed to the difference in their chemical architecture.

Effect of Catechol on the Size and Shape of CTAB Micelles in Aqueous Solutions

Abstract The effects of catechol on the change of cetyltrimethylammonium bromide (CTAB) micelles in aqueous solutions have been studied by Ultramicroelectrode (UME) cyclic voltammetry and Time-Resolved Fluorescence Quenching (TRFQ). It has been shown that the diffusion coefficient decreases and the micelle aggregation number increases with the addition of catechol. This indicates that catechol has influence on the size or shape of CTAB micelles. In order to analyze the change of the micelles, other micelle parameters like the effective radius (a), surface area of micelle (S), area of single CTAB molecule (A) and packing parameter (P) were calculated. The values of P which is relative to the shape of the micelles are consistent with the change of the diffusion coefficient. All the results show that catechol can accelerate the increase of the aggregate size and sphere-to-rod morphology change of CTAB micelles even with lower concentration of CTAB. This is because that hydrophobic force makes catechol insert into CTAB micelles between CTAB molecules, which leads to the increase of the radius of curvature. The increase of aggregate size and the sphere-to-rod morphology change are also promoted as a result.

Aggregate Properties of Sodium Deoxycholate and Dimyristoylphosphatidylcholine Mixed Micelles

Mixed micelles of the phospholipid dimyristoylphosphatidylcholine (DMPC) and bile salts of sodium deoxycholate (NaDC) were investigated by a combination of techniques, including time-resolved fluorescence quenching (TRFQ), electron spin resonance (ESR), viscometry, pulsed-gradient spin-echo NMR (PGSE-NMR), and surface tensiometry. Aggregation numbers, and bimolecular collision rate constants of guest molecules confined in the micelles (by TRFQ), interfacial hydration index and microviscosity, (by ESR), axial ratio (from solution viscosity), micelle self-diffusion coefficient (by PGSE-NMR), and the critical micelle concentrations (from surface tension) were determined for various molar compositions defined by the ratio R identical with [NaDC]/[DMPC] and concentrations ([NaDC]+[DMPC]). The data interpretation showed the micelles to be polydisperse rods. Aggregate properties depend on the ratio, R and reveal behavior unlike that in micelles of surfactants with aliphatic nonpolar chains. With increase in concentration from [NaDC] = 0.010 M to [NaDC] = 0.200 M, the hydration index and the aggregation number exhibit non-monotonic variations. Formulation of a polar shell model for cylindrical micelles yielded a set of nonlinear equations for the structural features of the micelle. The solutions give the microstructural description of the mixed micelle that includes the length, diameter, number of water molecules in the hydration shell, and the monomer organization in the micelle.

Physicochemical Characterization of Phospholipid Solubilized Mixed Micelles and a Hydrodynamic Model of Interfacial Fluorescence Quenching

Mixed micelles of solubilized dimyristoyl phosphatidylcholine (DMPC) and the zwitterionic detergent dodecyldimethylammoniopropane sulfonate are characterized employing time-resolved fluorescence quenching (TRFQ), electron spin resonance (ESR), and surface tensiometry toward the goal of investigating interfacial reactions using these micelles as host reaction media. The properties measured are the micelle aggregation numbers, interfacial hydration index, microviscosity, and the critical micelle concentrations for various molar fractions, XDMPC, of DMPC, 0<or=XDMPC<0.35. A complementary interpretation of the experimental results from TRFQ and ESR within the framework of a polar shell model for the mixed micelle yields some microstructural features, including the micelle core radius, polar shell thickness, and the fraction of the total hydrocarbon that overlaps with the micelle-water interface. The results of the characterization are applied in investigating an interfacial reaction; namely, micellar fluorescence quenching. A bulk hydrodynamic model when modified appropriately so as to be applicable to reaction within the interface is shown to describe micellar fluorescence quenching kinetics and also provides some insight into the location of guest molecules in micelles.

Study on the Structure Transition of CTAB/1-Butanol/Heptane/Water Microemulsions by Pt Ultramicroelectrode

Summary Ultramicroelectrode voltammetric measurements have been used in the microemulsions of CTAB/1-butanol/heptane/water to calculate the diffusion coefficient which can reflect the structure transition of the microemulsions. It is found that with increasing water content of microemulsions, the apparent diffusion coefficient (D app) of the probe decreases monotonically with three transition points. The first two transition points indicate the change in the structure of microemulsions, that is from water in oil region to bicontinuous phase and then to oil in water region, while the third one differs from previous reports. The time resolved fluorescence quenching (TRFQ) technique has been carried out to obtain the aggregation number of the microemulsions in order to analyze the abnormal transition point. According to the TRFQ experiment, we find that the aggregation number of the microemulsion decrease with water content increasing between 50%–60%, and then tend to identical. These results suggest that the last transition point of the diffusion coefficient is because of the forces between oil droplets. The self-diffusion coefficient of oil droplet in the o/w region is calculated simultaneously. Based on these experimental results, we analyze the composition of the interface between oil and water.

Characterization of the kinetics of phospholipase C activity toward mixed micelles of sodium deoxycholate and dimyristoylphosphatidylcholine

Phospholipase C catalyzed hydrolysis of dimyristoyl phosphatidylcholine (DMPC) in phospholipid–bile salt mixed micelles was studied with particular attention on the relationship between interfacial enzyme activity and the physicochemical properties of substrate aggregates. Steady state kinetics is observed and it is argued that conditions for steady state exist because the enzyme encounters a steady supply of substrate by hopping between micelles at a rate faster than the chemical reaction rate. An existing kinetic model is reformulated to a more usable form. This presents a new approach to treating the kinetic data and allows extraction of the kinetic parameters of the model from the activity dependence on micellar lipid substrate surface concentration. The kinetic parameters were found to depend on the physicochemical properties of substrate aggregates, but remain constant over a range of lipid and bile salt concentrations. The substrate aggregates were characterized by time-resolved fluorescence quenching (TRFQ). The activity values and the micelle sizes group into two sets: (i) larger micelles for bile salt/lipid ≤ 5 showing higher activity and shorter steady state duration (≤ 4 min) and (ii) smaller micelles for bile salt/lipid > 5 with lower activity and longer steady state (≈ 10 min). At least two sets of parameters, for bile salt/lipid ≤ 5 and > 5, characterize the kinetics. Higher enzyme–micelle dissociation constant and lower catalytic rate are found for the group of smaller micelles. An explanation supporting our finding is that as micelles become smaller the overlap area for enzyme–micelle binding decreases, leading to weaker binding. Consequently the enzyme dissociation constant increases. Extension of the present approach to other phospholipases and substrates to establish its generality and correlation between micelle size and the catalytic rate are areas for future investigations.

Interaction between Covalent DNA Gels and a Cationic Surfactant

The interaction of covalently cross-linked double-stranded (ds) DNA gels and cetyltrimethylammonium bromide (CTAB) is investigated. The volume transition of the gels that follows the absorption of the oppositely charged surfactant from aqueous solution is studied. As do other polyelectrolyte networks, DNA networks form complexes with oppositely charged surfactant micelles at surfactant concentrations far below the critical micelle concentration (cmc) of the polymer-free solution. The size of the absorbed surfactant aggregates is determined from time-resolved fluorescence quenching (TRFQ). At low surfactant concentrations, small discrete micelles (160 < N < 210) are found, whereas large micelles (N > 500) form at surfactant concentrations of 1 mM. When the DNA is in excess of the surfactant, the surfactant binding is essentially quantitative. The gel volume decreases by 90% when the surfactant to DNA charge ratio, beta, increases from 0 to 1.

Micelle‐to‐Vesicle Transition Induced by Organic Additives in Catanionic Surfactant Systems

A micelle-to-vesicle transition (MVT) induced by the addition of a series of apolar hydrocarbons (n-butylbenzene, n-hexane, n-octane, and n-dodecane) to the catanionic surfactant system n-dodecyltriethylammonium bromide/sodium n-dodecylsulfate (DTEAB/SDS) has been investigated for the first time by means of rheology and turbidity measurements, dynamic light scattering (DLS), and transmission electron microscopy (TEM). Interestingly, a MVT can take place within certain micellar regions, which are dependent on the structure and chain length of the hydrocarbon. However, these hydrocarbons are unable to induce a MVT in another catanionic surfactant system, namely, n-dodecyltriethylammonium bromide/sodium n-dodecylsulfonate (DTEAB/SDSO(3)), in which the molecular interactions are weaker than in the DTEAB/SDS system. On the other hand, polar additives, such as n-octanol and n-octylamine, exhibit much higher efficiency and activity in inducing MVT than hydrocarbons in both DETAB/SDS and DTEAB/SDSO(3). Moreover, DLS, TEM, and time-resolved fluorescence quenching (TRFQ) results demonstrate that the ratio of vesicles to micelles in the system can be actively controlled by addition of polar additives. Possible mechanisms for the above phenomena are presented, and the potential application of controllable micelle/vesicle systems in the synthesis of tailored bimodal mesoporous materials is discussed.

Structural organization of cetyltrimethylammonium sulfate in aqueous solution: The effect of Na 2SO 4

We used dynamic light scattering (DLS), steady-state fluorescence, time resolved fluorescence quenching (TRFQ), tensiometry, conductimetry, and isothermal titration calorimetry (ITC) to investigate the self-assembly of the cationic surfactant cetyltrimethylammonium sulfate (CTAS) in aqueous solution, which has SO 2− 4 as divalent counterion. We obtained the critical micelle concentration (cmc), aggregation number ( N agg ) , area per monomer ( a 0 ) , hydrodynamic radius ( R H ) , and degree of counterion dissociation ( α ) of CTAS micelles in the absence and presence of up to 1 M Na 2SO 4 and at temperatures of 25 and 40 °C. Between 0.01 and 0.3 M salt the hydrodynamic radius of CTAS micelle R H ≈ 16 Å is roughly independent on Na 2SO 4 concentration; below and above this concentration range R H increases steeply with the salt concentration, indicating micelle structure transition, from spherical to rod-like structures. R H increases only slightly as temperature increases from 25 to 40 °C, and the cmc decreases initially very steeply with Na 2SO 4 concentration up to about 10 mM, and thereafter it is constant. The area per surfactant at the water/air interface, a 0 , initially increases steeply with Na 2SO 4 concentration, and then decreases above ca. 10 mM. Conductimetry gives α = 0.18 for the degree of counterion dissociation, and N agg obtained by fluorescence methods increases with surfactant concentration but it is roughly independent of up to 80 mM salt. The ITC data yield cmc of 0.22 mM in water, and the calculated enthalpy change of micelle formation, Δ H mic = 3.8 kJ mol −1 , Gibbs free energy of micellization of surfactant molecules, Δ G mic = − 38.0 kJ mol −1 and entropy T Δ S mic = 41.7 kJ mol −1 indicate that the formation of CTAS micelles is entropy-driven.

Combining precision spin-probe partitioning with time-resolved fluorescence quenching to study micelles: Application to micelles of pure lysomyristoylphosphatidylcholine (LMPC) and LMPC mixed with sodium dodecyl sulfate

Micelles of lysomyristoylphosphatidylcholine (LMPC) and mixed micelles of LMPC with anionic detergent sodium dodecyl sulfate (SDS) have been characterized by spin-probe-partitioning electron paramagnetic resonance (SPPEPR) and time-resolved fluorescence quenching (TRFQ) experiments. SPPEPR is a novel new method to study structure and dynamics in lipid assemblies successfully applied here for the first time to micelles. Several improvements to the computer program used to analyze SPPEPR spectra have been incorporated that increase the precision in the extracted parameters considerably from which micelle properties such as effective water concentration and microviscosity may be estimated. In addition, with this increased precision, it is shown that it is feasible to study the rate of transfer of a small spin probe between micelles and the surrounding aqueous phase by SPPEPR. The rate of transfer of the spin probe di- tert-butyl nitroxide (DTBN) and the activation energy of the transfer process in LMPC and LMPC-SDS micelles have been determined with high precision. The rate of transfer increases with temperature and SDS molar fraction in mixed micelles, while it remains constant with LMPC concentration in pure LMPC micelles. The activation energy of DTBN transfer in pure lysophospholipid micelles does not change with LMPC concentration while it decreases with the increasing molar fraction of SDS in mixed LMPC-SDS micelles. Both this decrease in activation energy and the increase in the rate of transfer are rationalized in terms of an increasing micelle surface area per molecule (decreasing compactness) as SDS molecules are added. This decreasing compactness as a function of SDS content is confirmed by TRFQ measurements showing an aggregation number that decreases from 122 molecules for pure LMPC micelles to 80 molecules for pure SDS micelles. The same increase in surface area per molecule is predicted to increase the effective water concentration in the polar shell of the micelles. This increase in hydration with SDS molar fraction is confirmed by measuring the effective water concentration in the polar shell of the micelles from the hyperfine spacing of DTBN. This work demonstrates the potential to design mixed lysophospholipid surfactant micelles with variable physicochemical properties. Well-defined micellar substrates, in terms of their physicochemical properties, may improve the studies of protein structure and enzyme kinetics.

Aggregation Numbers of Cationic Oligomeric Surfactants: A Time-Resolved Fluorescence Quenching Study

The micelle aggregation numbers (N(agg)) of several series of cationic oligomeric surfactants were determined by time-resolved fluorescence quenching (TRFQ) experiments, using advantageously 9,10-dimethylanthracene as fluorophore. The study comprises six dimeric ("gemini"), three trimeric, and two tetrameric surfactants, which are quaternary ammonium chlorides, with medium length spacer groups (C(3)-C(6)) separating the individual surfactant fragments. Two standard cationic surfactants served as references. The number of hydrophobic chains making up a micellar core is relatively low for the oligomeric surfactants, the spacer length playing an important role. For the dimers, the number decreases from 32 to 21 with increasing spacer length. These numbers decrease further with increasing degree of oligomerization down to values of about 15. As for many conventional ionic surfactants, the micelles of all oligomers studied grow only slightly with the concentration, and they remain in the regime of small micelles up to concentrations of at least 3 wt %.

Sugar-Based Gemini Surfactants with Peptide Bonds─Synthesis, Adsorption, Micellization, and Biodegradability

The sugar-based gemini surfactant with peptide bonds, N,N'-bisalkyl-N,N'-bis[2-(lactobionylamide)ethyl]hexanediamide (2C(n)peLac, in which n represents hydrocarbon chain lengths of 12 and 16), was synthesized by reacting adipoyl chloride with the corresponding monomeric surfactant N-alkyl-N'-lactobionylethylenediamine (C(n)peLac), which was obtained by reacting ethylenediamine with alkyl bromide and lactobionic acid. The adsorption and micellization properties of C(n)peLac and 2C(n)peLac were characterized by the measurement of their equilibrium and dynamic surface tension, steady-state fluorescence using pyrene as a probe, dynamic light scattering (DLS), and time-resolved fluorescence quenching (TRFQ), and their biodegradability was also investigated. The critical micelle concentration (cmc) decreases with an increase in the hydrocarbon chains from monomeric to gemini surfactants, whereas it increases with an increase in the chain length from 12 to 16 for both systems. The increases in both the hydrocarbon chain and the chain length of sugar-based surfactants reduce surface activities such as the ability to lower the surface tension, the occupied area per molecule, and the adsorption rate at the air/water interface. The sugar-based surfactants C(n)peLac and 2C(n)peLac exhibit unique aggregation behavior in aqueous solution. The DLS results indicate that the apparent hydrodynamic diameter of C(n)peLac micelles decreases sharply with increasing concentration, whereas that of 2C(n)peLac micelles decreases gradually. From the TRFQ measurement, it was observed that, as concentration increases, the aggregation numbers are almost constant for C(n)peLac, whereas they increase for 2C(n)peLac. These results imply that loosely packed micelles formed by sugar-based surfactants become tightly packed micelles as the concentration increases. Furthermore, it was found that 2C(n)peLac shows lower biodegradability than does C(n)peLac because it contains tertiary amines in the molecule.

Mixed micelles of monomeric and dimeric cationic surfactants with phospholipids: effect of hydrophobic interactions

Surface tension ( γ) and time resolved fluorescence quenching (TRFQ) measurements have been performed on the binary mixtures of monomeric as well as dimeric alkylammonium bromides with l-α-dimyristoylphosphatidycholine (DMPC) and l-α-dipalmitoylphosphatidycholine (DPPC). The critical micelle concentration (cmc) has been evaluated from the γ measurements. The γ plots show two breaks in the γ versus [total surfactant] curves in most of the cases. The first break ( C 1) has been attributed to the mixed vesicle formation process. The break down of the vesicles leads to the mixed micellization between the surfactant and phospholipid monomers at the second break ( C 2). The amount of surfactant used in the vesicle breakdown process (Δ C) increases linearly with the increase in the amount of phospholipid and depends significantly on the hydrophobicities of the cationic components. The surface area per molecule ( a) evaluated from the γ plots indicates compact monolayer formation in the case of monomeric surfactants with lower hydrophobicities and reverse is observed for dimeric surfactants. The pyrene life time ( τ) of the solubilized pyrene in the hydrophobic environment of mixed micelles, fully supports the conclusion that derived from a.

Effect of the Nature of the Counterion on the Properties of Anionic Surfactants. 5. Self-Association Behavior and Micellar Properties of Ammonium Dodecyl Sulfate

Micelles formed in water from ammonium dodecyl sulfate (AmDS) are characterized using time-resolved fluorescence quenching (TRFQ), electron paramagnetic resonance (EPR), conductivity, Krafft temperature, and density measurements. TRFQ was used to measure the aggregation number, N, and the quenching rate constant of pyrene by dodecylpyridinium chloride, k(Q). N depends only on the concentration (C(aq)) of ammonium ions in the aqueous phase whether these counterions are derived from the surfactant alone or from the surfactant plus added ammonium chloride as follows: N = N0(C(aq)/cmc0)(gamma), where N0 is the aggregation number at the critical micelle concentration in the absence of added salt, cmc0, and is equal to 77, 70, and 61 at 16, 25, and 35 degrees C, respectively. The exponent gamma = 0.22 is independent of temperature in the range 16 to 35 degrees C. The fact that N depends only on C(aq) permits the determination of the micelle ionization degree (alpha) by employing various experimental approaches to exploit a recent suggestion (J. Phys. Chem. B 2001, 105, 6798) that N depends only on C(aq). Utilizing various combinations of salt and surfactant, values of alpha were obtained by finding common curves as a function of C(aq) of the following experimental results: the Krafft temperature, N, k(Q), the microviscosity of the Stern layer determined from the rotational correlation time of a spin probe, 5-doxyl stearic acid methyl ester, and the spin-probe sensed hydration of the micelle surface. The values of alpha, determined from applying the aggregation number-based definition of alpha to all of these quantities, were within experimental uncertainty of the values alpha = 0.19, 0.20, and 0.21 derived from conductivity measurements at 16, 25, and 35 degrees C, respectively. The volume fraction of the Stern layer occupied by water decreases as N increases. For AmDS micelles, both the hydration and its decrease are predicted by a simple theory of micelle hydration by fixing the parameters of the theory for sodium dodecyl sulfate and employing no further adjustable parameters. For a given value of N, the hydration decreases as the temperature increases.

Phospholipid containing mixed micelles: Characterization of diheptanoyl phosphatidylcholine (DHPC) and sodium dodecyl sulfate and DHPC and dodecyl trimethylammonium bromide

Mixed micelles of l,2-diheptanoyl- sn-grycero-3-phosphocholine (DHPC) with ionic detergents were prepared to develop well characterized substrates for the study of lipolytic enzymes. The aggregates that formed on mixing DHPC with the anionic surfactant sodium dodecyl sulfate (SDS) and with the positively charged dodecyl trimethylammonium bromide (DTAB) were investigated using time-resolved fluorescence quenching (TRFQ) to determine the aggregation numbers and bimolecular collision rates, and electron spin resonance (ESR) to measure the hydration index and microviscosity of the micelles at the micelle–water interface. Mixed micelles between the phospholipid and each of the detergents formed in all compositions, yielding interfaces with varying charge, hydration, and microviscosity. Both series of micelles were found to be globular up to 0.7 mole fraction of DHPC, while the aggregation numbers varied within the same concentration range of the components less than 15%. Addition of the zwitterionic phospholipid component increased the degree of counterion dissociation as measured by the quenching of the fluorescence of pyrene by the bromide ions bound to DHPC/DTAB micelles, showing that at 0.6 mole fraction of DHPC 80% of the bromide ions are dissociated from the micelles. The interface water concentration decreased significantly on addition of DHPC to each detergent. For combined phospholipid and detergent concentration of 50 mM the interface water concentration decreased, as measured by ESR of the spin-probes, from 38.5 M/L of interface volume in SDS alone to 9 M/L when the phospholipid was present at 0.7 mole fraction. Similar addition of DHPC to DTAB decreased the interfacial water concentration from 27 M/L to 11 M/L. Determination of the physicochemical parameters of the phospholipid containing mixed micelles here presented are likely to provide important insight into the design of assay systems for kinetic studies of phospholipid metabolizing enzymes.

A small-angle neutron scattering study of biologically relevant mixed surfactant micelles comprising 1,2-diheptanoyl-sn-phosphatidylcholine and sodium dodecyl sulfate or dodecyltrimethylammonium bromide.

Small-angle neutron scattering (SANS) has been employed to characterize mixed micelles comprising the surfactants 1,2-diheptanoyl--phosphatidylcholine (DHPC)/sodium dodecyl sulfate (SDS) and 1,2-diheptanoyl--phosphatidylcholine (DHPC)/dodecyltrimethylammonium bromide (DTAB) using the classical model of a micelle consisting of a hydrocarbon core surrounded by a polar shell. Various constraints are applied to the data fitting, specifically the volume of the hydrocarbon core using the aggregation number determined from time-resolved fluorescence quenching (TRFQ) and the degree of micelle hydration as determined from an electron paramagnetic resonance (EPR) experiment. The morphologies of the DHPC/SDS and DHPC/DTAB mixed micelles are largely invariant with composition-as might be expected given the similarity in the tail volumes of the respective surfactants, and the observed behaviour of the aggregation number-with a radius comparable to the fully extended length of a dodecyl chain, the longer of the two hydrophobic moieties. The shell thickness is also largely invariant with composition, indicating that the phosphatidylcholine headgroup lies flat at the interface. For both cases, the degree of counter-ion dissociation extracted from the fitting of the SANS data increases significantly on addition of DHPC, in a manner very similar to that observed for related binary surfactant mixtures, provided there is only a small change in micelle aggregation number (micelle curvature). The coincidence of the degrees of counter-ion dissociation for these quite different systems suggests a common underlying behaviour in which the nonionic species merely dilutes the surface charge associated with the ionic headgroups.