ESR and NMR studies of poly (amidoamine) dendrimers with ionic surfactants in different media

The electron paramagnetic resonance (EPR) study has been carried out for the micellar solutions of various ionic surfactant solutions as well as various generations of aqueous dendrimer both in their respective presence as well as their absence at 25°C and in different media. From these measurements, the rotation correlation time (τ_B) have been calculated for all the ionic surfactant + PAMAM + water system. A variation in the τ_Bvalue remains mostly constant for the dodecyltrimethyammonium bromide (DTAB) and tetradecyltrimethylammonium bromide (TTAB) + PAMAM + water ternary mixtures. The τ_Bvalue shows an increase with the increase in the amount of PAMAM for SDS in basic medium and for 12-2-12 in acidic medium. It has been concluded from these results that SDS undergo complexation with all generations of PAMAM in basic medium and 12-2-12 in acidic medium and produce stronger hydrophobic environment. The nuclear magnetic resonance study (NMR) allowed us to evaluate the spin–spin relaxation (T₁) times of SDS in the presence of all generations of PAMAM. The T₁ values for all the tail protons of SDS showed a slight decrease with the increase in the constant amount of PAMAM suggesting the adsorption of PAMAM molecules on the micelle surface.     

Mixed Micellization of Dimeric (Gemini) Surfactants and Conventional Surfactants

The aqueous solutions of mixtures of various conventional surfactants and dimeric anionic and cationic surfactants have been investigated by electrical conductivity, spectrofluorometry, and time-resolved fluorescence quenching to determine the critical micelle concentrations and the micelle aggregation numbers in these mixtures. The following systems have been investigated: 12-2-12/DTAB, 12-2-12/C(12)E(6), 12-2-12/C(12)E(8), 12-3-12/C(12)E(8), Dim3/C(12)E(8), and Dim4/C(12)E(8) (12-2-12 and 12-3-12=dimethylene-1,2- and trimethylene-1,3-bis(dodecyldimethylammonium bromide), respectively; C(12)E(6) and C(12)E(8)=hexa- and octaethyleneglycol monododecylethers, respectively; Dim3 and Dim4=anionic dimeric surfactants of the disodium sulfonate type, Scheme 1; DTAB=dodecyltrimethylammonium bromide). For the sake of comparison the conventional surfactant mixtures DTAB/C(12)E(8) and SDS/C(12)E(8) (SDS=sodium dodecylsulfate) have also been investigated (reference systems). Synergism in micelle formation (presence of a minimum in the cmc vs composition plot) has been observed for the Dim4/C(12)E(8) mixture but not for other dimeric surfactant/nonionic surfactant mixtures investigated. The aggregation numbers of the mixed reference systems DTAB/C(12)E(8) and SDS/C(12)E(8) vary monotonously with composition from the value of the aggregation number of the pure C(12)E(8) to that of the pure ionic component. In contrast, the aggregation number of the dimeric surfactant/C(12)E(8) mixtures goes through a minimum at a low value of the dimeric surfactant mole fraction. This minimum does not appear to be correlated to the existence of synergism in micelle formation. The initial decrease of the aggregation number of the nonionic surfactant upon addition of ionic surfactant, up to a mole fraction of ionic surfactant of about 0.2 (in equivalent per total equivalent), depends little on the nature the surfactant, whether conventional or dimeric. The results also show that the microviscosity of the systems containing dimeric surfactants is larger than that of the reference systems. Copyright 2001 Academic Press.     

MICELLE FORMATION BY ANIONIC AND CATIONIC SURFACTANTS IN AQUEOUS 18-CROWN-6 ETHER,P-CYCLODEXTRIN,AND 1,10-PHENANTHROLINE SOLUTIONS AT DIFFERENT TEMPERATURES

The conductances of sodium perfluorooctanoate (SPFO), sodium dodecylsulphate (SDS), dodecyltrimethylammonium bromide (DTAB), and tetradecyltrimethylammonium bromide (TTAB) in 18-crown-6 ether + water (CR+W), p-cyclodextrin + water (CY+W), and 1,10-phenanthroIine + water (Phen+W) mixtures with fixed 4 mM of each additive were determined over the temperature range of 5-55 °C. The conductivity plots for all the surfactants showed single break from which the critical micellization concentration (cmc) and degree of micelle ionization (x) were computed. From the pre and the post micellar slopes of the conductivity curves, the equivalent conductivities of the monomeric (Aass) and the micellar states (Amjc), respectively, were calculated and discussed with respect to the surfactant-additive complexation. It was observed that the micelle formation of all the ionic surfactants irrespective of the nature of their head groups were delayed in CYC+W in comparison to that in CR+W and Phen+W systems over the temperature range studied. The micelle formation of SPFO and SDS in CR+W and Phen+W systems showed stabilization of the respective micelles due to the adsorption of Na⁺-CR and Na+-Phen complexes at the micelle solution interface in comparison to that of DTAB and TTAB.     

Interactions between zwitterionic and conventional anionic and cationic surfactants

Critical micelle concentration (cmc) values have been determined for the mixed zwitterionic/anionic surfactant systems of N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (ZW3-12)/sodium dodecyl sulfate (SDS), N-dodecyl-N,N-(dimethylammonio)butyrate (DDMAB)/SDS, N-octyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (ZW3-08)/sodium octyl sulfate (SOS), and the zwitterionic/cationic systems of ZW3-12/dodecyltrimethylammonium bromide (DTAB), DDMAB/DTAB. Conductivity studies and nuclear magnetic resonance (NMR) spectroscopy were the methods employed for cmc determinations. The degree of nonideality of the interaction in the micelle (beta(m)), for each system, was determined according to Rubingh's nonideal solution theory. Evidence was found for the existence of strong interactions between zwitterionic and anionic surfactants in each of the zwitterionic/anionic systems. The ZW3-08/SOS and DDMAB/SDS systems behaved synergistically at all mole fractions studied while the ZW3-12/SDS system exhibited synergistic behavior above mole fractions of 0.30. Greater negative deviations from ideal behavior were demonstrated in the DDMAB/SDS system than in the other two zwitterionic/anionic systems. The zwitterionic/cationic systems of ZW3-12/DTAB and ZW3-08/OTAB displayed only slight deviations from ideal behavior, therefore indicating near ideal mixing.     

卵清蛋白与离子型表面活性剂的相互作用

本文通过荧光光谱法、紫外-可见吸收光谱法和透射电镜并结合电导率测定分别研究了水中卵清蛋白与阴离子表面活性剂十二烷基硫酸钠（SDS）和阳离子表面活性剂十二烷基三甲基溴化铵（DTAB）和十六烷基三甲基溴化铵（CTAB）之间的相互作用。研究结果表明卵清蛋白可以增加SDS和CTAB的临界胶束浓度,但对DTAB的临界胶束浓度没有影响。阴离子表面活性剂可以使卵清蛋白构象完全伸展,而阳离子表面活性剂却不具备此种作用。表面活性剂单体与卵清蛋白的相互作用强于表面活性剂胶束与卵清蛋白的相互作用。     

Mixed Micellization Behavior of 12-2-12 Gemini Surfactant with Some Alkyltrimetyl Ammonium Bromide Surfactants

Mixed micellization behavior of dimeric cationic surfactant ethanediyl-1,2-bis (dimethyldodecylammonium bromide) (12-2-12) with a series of monomeric cationic surfactants dodecyltrimethyl ammonium bromide (DTAB), tetradecyltrimethyl ammonium bromide (TTAB), and cetyltrimethyl ammonium bromide (CTAB) has been studied in aqueous and aqueous polyvinylpyrrolidone (PVP) solutions at 298.15, 308.15, and 318.15 K, respectively, using conductometric method. Various thermodynamic parameters like mixed micelle concentration (C_m), micelle mole fraction (X₁), interaction parameter (β), and free energy of mixing (ΔG_ex) of the mixed systems have been determined and analyzed using Rubingh's regular solution theory. The results indicate that in aqueous solutions the binary mixtures of 12-2-12 with DTAB/TTAB behave nonideally with mutual synergism whereas that with CTAB shows almost ideal behavior at 298.15 K. At 318.15 K, all these binary mixtures exhibit antagonistic behavior. The effect of variation in chain length of alkyltrimethyl ammonium bromide surfactants on the interactions with 12-2-12 have also been evaluated and discussed.     

Sodium dodecyl sulfate-poly(amidoamine) interactions studied by AFM imaging, conductivity, and Krafft temperature measurements

The conductivity, kappa, and Krafft temperature, TK, of sodium dodecyl sulfate (SDS) with poly(amidoamine) dendrimers (PAMAM) of 0.0, 0.5, and 1.0 generations (G) have been determined at different surfactant as well as PAMAM concentrations. The critical micelle concentration of SDS increases with the increase in the amount of each generation and the additive effect of 0.5G is maximum. TK of SDS shows a systematic decrease with maximum reduction in the presence of 0.5G. Atomic force microscopy (AFM) captures a layered pattern of 1.0G in the form of nanorods and no AFM images are detected for 1.0G in the presence of SDS. All results demonstrate that SDS has favorable interactions with ester-terminated 0.5G PAMAM rather than amine-terminated 0.0G and 1.0G.     

Partitioning of macrocyclic compounds in a cationic and an anionic micellar solution: a small-angle neutron scattering study

Following a previous investigation on partitioning of some macrocycle compounds in sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) aqueous solutions and their effect on the micellar structure, a small-angle neutron scattering (SANS) study has been performed at fixed surfactant content (0.20 mol/L) and varying macrocycle concentrations from 0.20 up to 1.0 mol/L. Conductivity measurements have been also performed in order to evaluate the effect of the presence of macrocycles on the critical micellar concentration (cmc) of the two surfactants. SANS experimental data were fitted successfully by means of a core-plus-shell monodisperse prolate ellipsoid model. It has been found that 1,4,7,10,13,16-esaoxacyclooctadecane (18C6) and 4,7,13,16-tetraoxa-1,10-diazacyclooctadecane (22) do not interact with DTAB micelles whereas their sodium complexes interact with SDS aggregates and partially localize, as a consequence of electrostatic interaction, on the micellar surface or in the Stern layer. 2,5,8,11,14,17-Hexaoxabicyclo[16.4.0] dicosane (B18C6), as a consequence of the increased hydrophobic character with respect to 18C6, interacts with DTAB hydrocarbon chains and partially localizes in the inner part of micelles. This finding has been successfully used to justify the higher amount of B18C6 compared to the 18C6 one found in the SDS micellar phase. The substituted crown ether has been found localized both on the micelle surface via complex formation and in the inner part of micelles as a consequence of the increased hydrophobic character. For all systems, the aggregate size primarily decreases with the amount of macrocycle in the micellar phase. The interpretation of cmc trends as a function ofmacrocycle concentration gives information on its distribution between micellar and aqueous phases that is in line with SANS results.     

Favorable interactions of amine- and ester-terminated PAMAM with cationic surfactants: photophysical and transport studies

Conductivity (kappa), turbidity (tau), and fluorescence (I1/I3) studies of hexadecyltrimethylammonium bromide (HTAB), hexadecylpyridinium bromide (HPyBr), and hexadecylpyridinium chloride (HPyCl) in aqueous poly(amido amine) (PAMAM) dendrimers of generations 0 to 2.5 G have been carried out. The complexation of surfactant monomers with the PAMAM surface groups is demonstrated by the critical aggregation concentration (cac), which is two to three orders of magnitude less than the micellization of cationic surfactants in aqueous PAMAM and denoted by critical micelle concentration (cmc*). In the presence of aqueous amine-terminated PAMAM, the cmc* value for each surfactant was much lower than the cmc in pure water, while they remain close to each other in the presence of aqueous ester-terminated PAMAM for each surfactant. The fluorescence studies demonstrated that both amine- and ester-terminated PAMAM interact with the cationic surfactants, though the mode of interaction varied due to the different nature of surface groups.     

Micelle-vesicle transitions in catanionic mixtures of SDS/DTAB induced by salt,temperature, and selective solvents: a dissipative particle dynamics simulation study

Dissipative particle dynamics (DPD) simulations are performed to study the factors that lead to the transition between micelle and vesicle in catanionic mixtures composed of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB), with the aim of understanding and controlling the structures of this system. The phase behavior, kinetics of vesicle formation, and micelle–vesicle transitions induced by salt, temperature, and selective solvents are investigated systematically. In this research, phase diagram of SDS/DTAB mixture is constructed by simulations at different concentrations and composition fractions. It is consistent with experimental results. The kinetic process of catanionic vesicle formation is illustrated. It is clarified that the transition between micelle and vesicle can be controlled by properly adjusting the external conditions. More interestingly, the evolution condition and transition mechanism between micelle and vesicle induced by various conditions are revealed. The membrane thickness differences between vesicles formed at different external conditions are compared. Here, the predicted phenomenon is compared with experimental results whenever possible, and we try to make a connection between the simulation model and the reality of the experiments. These studies help to shed light on the microscopic details of micelle–vesicle transition in catanionic mixtures.     

Femtosecond study of ultrafast fluorescence resonance energy transfer in a catanionic vesicle

Ultrafast fluorescence resonance energy transfer (FRET) in a catanionic [sodium dodecyl sulfate (SDS)-dodecyltrimethyl ammonium bromide (DTAB)] vesicle is studied by femtosecond up-conversion. The vesicles (diameter ～400 nm for SDS-rich and ～250 nm for DTAB-rich vesicles) are much larger than the SDS and DTAB micelles (diameter ～4 nm). In both micelle and vesicles, FRET occurs in multiple time scales and the time scales of FRET correspond to a donor-acceptor distance varying between 12 and 36 A?.     

Interactions of 3, 3.5, 4, and 4.5 generations of poly(amido amine) dendrimer with cationic surfactants

The conductivity (κ), turbidity (τ), NMR, and Krafft temperature (T _K) studies have been carried out for hexadecylpyridinium bromide (HPyBr), hexadecylpyridinium chloride (HPyCl), and hexadecyltrimethylammonium bromide (HTAB) in the presence of 3G, 3.5G, 4G, and 4.5G generations of poly(amido amine) dendrimers (PAMAM) in aqueous phase. The cmc of all present surfactants were evaluated from κ and τ measurements, both in the presence as well as in the absence of PAMAM. The cmc values decrease in the presence of PAMAM in comparison to that in pure water, especially in the presence of amine terminated PAMAM. Krafft temperature values of pure surfactants also decrease in the presence of various generations of PAMAM. A comparison of all present results from different techniques indicates that HPyBr interacts more strongly with all generations of PAMAM rather than HPyCl and HTAB.     

Binary mixtures with novel monomeric and dimeric surfactants: influence of the head group nature and number of hydrophobic chains on non-ideality

The micellization and micellar growth in the mixtures of N,N-dimethyl, N-phenyl,N-dodecylammonium bromide, PH12, N,N-dimethyl,N-ciclohexylmethyl,N-dodecylammonium bromide, CH12, and their two dimeric counterparts m-dimethylphenyl-α-ω-bis(dodecyldimethylammonium) bromide, 12PH12, and m-dimethylciclohexyl-α-ω-bis(dodecyldimethylammonium) bromide, 12CH12, with dodecyltrimethylammoniumbromide, DTAB, and with N-decanoyl N-methylglucamide, MEGA10, were investigated at 303 K. Circular dichroism, CD, experiments showed the formation of mixed micelles. Two-dimensional, 2D, rotating frame nuclear Overhauser effect spectroscopy (ROESY) experiments indicated that the arrangement of the rings in the pure and mixed micelles is similar, with the rings bent into the micelle interior avoiding contact with water. Application of different theoretical approaches shows that PH12 and CH12 mixtures with DTAB and with MEGA10 behave almost ideally. The binary systems of 12PH12 and 12CH12 with DTAB and with MEGA10 show a non-ideal behavior. An increment in the solution mole fraction of MEGA10 and DTAB diminishes the tendency of the micellar aggregates to grow.     

Investigation of SDS, DTAB and CTAB micelle microviscosities by electron spin resonance

Electron spin resonance spectroscopy (ESR) of the nitroxide labelled fatty acid probes (5-, 16-doxyl stearic acid) was used to monitor the micelle microviscosity of three surfactants at various concentrations in aqueous solution: sodium dodecyl sulphate (SDS), dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB). At low surfactant concentration, there is no micelle, the ESR probe is dissolved in water/surfactant homogeneous phase and gives his microviscosity. At higher surfactant concentration, an abrupt increase in microviscosity indicates the apparition of micelles and, the solubilization of the probes in micelles. The microviscosity of the three surfactants, in a large surfactant range, was obtained as well as the critical micelle concentration (CMC). The microviscosity increased slightly with the increase in surfactant concentration. Phosphate buffer lowered the CMC value and generally increased the microviscosity.     

Effects of interactions on the formation of mixed micelles of 1,2-diheptanoyl-sn-glycero-3-phosphocholine with sodium dodecyl sulfate and dodecyltrimethylammonium bromide

Mixed micelles of the phospholipid 1,2-diheptanoyl-sn-glycero-3-phosphocholine (DHPC) with sodium dodecyl sulfate (SDS) or dodecyltrimethylammonium bromide (DTAB) in aqueous solutions and the effects of interactions between the components were studied by fluorescence and NMR measurements. The regular solution theory (RST) was applied to analyze the experimental critical micelle concentration values determined from the fluorescence spectra of pyrene in the mixed micelles. Negative values for the interaction parameter (beta12) were obtained for both DHPC + SDS and DHPC + DTAB mixtures, with the value being more negative in the former case. The negative beta12 values for the two systems imply that the interaction between the phospholipid and the two ionic surfactants is attractive in nature, being more intense in the case of DHPC + SDS. The interaction parameter, beta12, varies with composition of the mixtures indicating changes in packing. The proton NMR shifts are quite different for the two systems and also vary with composition. An interpretation of these experimentally determined chemical shifts in terms of the degree of compactness attributed to electrostatic and steric interactions in the mixed micelle supports the conclusions derived from the fluorescence cmc experiments.     

Alkanediyl-alpha,omega-bis(dimethylalkylammonium bromide) surfactants 9. Effect of the spacer carbon number and temperature on the enthalpy of micellization

The enthalpies of dilution of micellar solutions of several 12-s-12 dimeric surfactants of the alkanediyl-alpha,omega-bis(dodecyldi-methylammonium bromide) type, differing by the carbon number s of the alkanediyl spacer, and of dodecyltrimethylammonium bromide (DTAB) have been measured calorimetrically, in a range of concentrations extending from well below to well above the critical micelle concentration (cmc). The results permitted the determination of the enthalpy of micellization, DeltaH degrees (M), of the investigated surfactants at 25 and 35 degrees C. The values of DeltaH degrees (M) were always negative and became more negative as the temperature was increased. The plot of -DeltaH degrees (M) against s showed a shallow minimum at about s=5 and a large decrease of -DeltaH degrees (M) going from 12-2-12 to 12- 4-12. This effect has been attributed to the contribution to DeltaH degrees (M) of the hindered rotation of the dodecyl chains around the spacer C-C bond for 12-2-12. This hindrance is shown to rapidly disappear when s is increased from 2 to above 4. The specific heats of micellization, the free energies of micellization, and the entropies of micellization (DeltaS degrees (M)) have been calculated using the DeltaH degrees (M) values and the reported cmc and micelle ionization degree data for 12-s-12 surfactants and DTAB. For all surfactants the results show that TDeltaS degrees (M)>-DeltaH degrees (M), indicating an entropy-driven micellization.     

Small-angle neutron scattering study of the effect of n -alkanols on interacting micelles

Small-angle neutron scattering cross-section distributions of sodium dodecyl sulphate (SDS) and dodecyl trimethyl ammonium bromide (DTAB), each 0·3 M in D₂O were obtained in the absence and presence of 0·1 M 1-pentanol, 1-hexanol, and 1-octanol at 25°C. The Hayter-Penfold type analysis was adopted. An ellipsoidal model with semiminor axis (a=16·5 ?) and semimajor axes (b=40·7 ? and 29·8 ?) for pure SDS and DTAB micelles has produced best fits. On increasing alkanol chain lengths an increase inb values was found. Micellar parameters like effective radius (R), (a, b), fraction of counterions per micelle, and intermicellar distances were obtained. Surfactant aggregation number, additive aggregation number intermicellar interaction potentials and values of Debye screening length were obtained for SDS and DTAB in the presence of alkanols. Implications of partitioning effect, surfactant ionicity and intermicellar potentials on the microstructures are rationalised.     

A new method for simultaneous estimation of micellization parameters from conductometric data

A simple method for determination of the counterion binding parameter (alpha) and aggregation number (N) from conductivity data is proposed. The method is based on fitting the values of the first derivative of conductivity (kappa) versus total surfactant concentration (c(t)) function according to the equation derived from the mass action model (MAM) by using different conductivity models. Sodium dodecylsulphate (SDS) and dodecyltrimethylammonium bromide (DTAB) were chosen for validation of the proposed method. It was shown that the method gives a fairly accurate values for micellisation parameters of SDS (N=51-64, alpha=0.74-0.75) and DTAB (N=56-62, alpha=0.77-0.79), both in good agreement with the literature data. In addition, application of the proposed method does not require the value of the critical micelle concentration (cmc).     

Estimation of degree of counterion binding and thermodynamic parameters of ionic surfactants from cloud point measurements by using triblock polymer as probe

Cloud point (C(P)) was measured for ternary mixtures of different ionic surfactants such as sodium dodecyl sulfate (SDS), dodecyltrimethylammonium bromide (DTAB), and dimethylene bis(dodecyldimethylammonium bromide) (12-2-12) plus triblock polymer (TBP) ((PEO)(2)(PPO)(15.5)(PEO)(2)) plus water, keeping the concentration of TBP constant and varying the surfactant concentration from pre- to postmicellar regions. These experiments were also performed in the presence of different fixed amounts of NaBr to evaluate the salt effect on the clouding behavior of these ternary mixtures. The C(P) value of TBP exhibits a drastic change at the cmc of each surfactant. The cmc values thus obtained both in the absence and in the presence of NaBr were used to evaluate counterion binding (beta) with the Corrin-Harkins method. beta values were also used to evaluate the thermodynamic parameters of these ionic surfactants. The results suggest that the beta values evaluated using this method, especially at low [TBP], are in good agreement with those reported in the literature.     

Characterization of micelle formation of dodecyldimethyl-N-2-phenoxyethylammonium bromide in aqueous solution

Aggregation behavior of dodecyldimethyl-N-2-phenoxyethylammonium bromide commonly called domiphen bromide (DB) was studied in aqueous solution. The Krafft temperature of the surfactant was measured. The surfactant has been shown to form micellar structures in a wide concentration range. The critical micelle concentration was determined by surface tension, conductivity, and fluorescence methods. The conductivity data were also employed to determine the degree of surfactant counterion dissociation. The changes in Gibb's free energy, enthalpy, and entropy of the micellization process were determined at different temperature. The steady-state fluorescence quenching measurements with pyrene and N-phenyl-1-naphthylamine as fluorescence probes were performed to obtain micellar aggregation number. The results were compared with those of dodecyltrimethylammonium bromide (DTAB) surfactant. The micelle formation is energetically more favored in DB compared to that in DTAB. The 1H-NMR spectra were used to show that the 2-phenoxyethyl group, which folds back onto the micellar surface facilitates aggregate formation in DB.