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1.
应用表面张力法、NMR法和ESR法研究了全氟辛酸钠(SPFO)-十二烷基三甲基溴化铵(DTAB)混合体系水溶液胶束形成及混合胶束的微环境性质(微观粘度、微观极性等)。结果表明, 碳氟表面活性剂碳氟链和碳氢表面活性剂碳氢链之间具有强烈的相互作用, DTAB与SPFO在水溶液中形成混合胶束。DTAB与SPFO混合体系的表面活性高于单一的DTAB或SPFO, 混合体系cmc较单一的DTAB和SPFO低。DTAB与SPFO混合胶束的微观粘度较DTAB胶束的大, 而微观极性较DTAB的小。  相似文献   

2.
The interactions between oppositely charged surfactant-polymer systems have been studied using surface tension and conductivity measurements and the dependence of aggregation phenomenon over the polyelectrolyte concentration and chain length of cationic ATAB surfactants, cetyltrimethyl ammonium bromide (CTAB), tetradecyltrimethyl ammonium bromide (TTAB), and dodecyltrimethyl ammonium bromide (DTAB) have been investigated. It was observed that cationic surfactants induce cooperative binding with anionic polyelectrolyte at critical aggregation concentration (cac). The cac values of ATAB surfactants in the presence of anionic polyelectrolyte, sodium carboxy methyl cellulose (NaCMC), are considerably lower than their critical micelle concentration (cmc). After the complete complexation, free micelles are formed at the apparent critical micelle concentration (acmc), which is slightly higher in polyelectrolyte aqueous solution than in pure water. Among the cationic surfactants (i.e., CTAB, TTAB, and DTAB), DTAB was found to have least interaction with NaCMC. Surfactants with longer tail size strongly favor the interaction, indicating the dependence of aggregation phenomenon on the structure, morphology, and tail length of the surfactant.   相似文献   

3.
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。  相似文献   

4.
The polymerization of acrylamide in mixed micellar solutions of surfactants, initiated by NaHSO3 has been studied at 20 and 3Q° C with time variable method of thermokinetics for 1. 5-order reaction. The results indicate that the mixed micellar systems of cationic or anionic with zwitterionic surfactants (SLS/ CTAB, SLS/ TTAB, SLS/ SDS) and cationic with nonionic surfactants (Brij 357sol; CTAB, Bri-J35/TTAB, Brij35/ DTAB) have catalytic effect on the polymerization in the order, at 20° C. SLS/ SDS SLS/ TTAB SLS/ CTAB Brij35/ CTAB at 30° C SLS/ SDS SLS/ TTAB≈ / CTAB Bri-j35/ DTAB= sBrij35/ TTAB as Brij35/ CTAB, while Brij35/ SDS mixed micellar system has inhibition. These effects are attributed to the effect of the Stern layer of mixed micelles on the step of initiator (HSOT) to form free radical.  相似文献   

5.
The conductances of sodium perfluorooctanoate (SPFO) and decyltrimethylammoniumbromide (DeTAB) have been determined in 18-crown-6 + water (CR + W). -cyclodextrin + water(CD + W) and in CR + CD + W mixtures with a fixed 0.0151 mol dm–3 concentration of CR andvarying amounts of CD with overall change in the mole fraction range of CD from 0.0 to 0.5 in CR +CD + W mixtures at 30°C. From the conductivity data, the critical micellar concentration (cmc), thedegree of counter-ion association () the free energy of transfer of the surfactant hydrocarbon chainfrom the medium to the micelle (G HP 0 ), and the free energy of transfer of surface contributions(G S 0 ) of SPFO and DeTAB have been computed. It has been found that the micelles of SPFO arestabilized in CR + W mixtures in comparison to pure water, whereas micelles of DeTAB remain comparatively unaffected upon addition of CR in water. On the other hand, micelles of SPFO andDeTAB are denatured upon addition of CD in CR + CD + W mixtures. The denaturation effect isstronger on the micelles of SPFO in comparison to that of DeTAB.  相似文献   

6.
 The conductances of trimethyltetradecylammonium bromide (TTAB) + trimethylhexa decylammonium bromide (HTAB) and TTAB + trimethyldodecylammonium bromide (DTAB) mixtures over the entire mole fraction range were measured in aqueous poly(vinyl pyrrolidone) (PVP) containing 1–10 wt% PVP at 30 °C. Each conductivity (κ) curve for the TTAB + HTAB mixtures showed two breaks corresponding to two aggregation processes over the whole mole fraction range, except in the case of pure TTAB, where a single break corresponding to the conventional critical micelle concentration (cmc) was observed. In the case of TTAB + DTAB mixtures, each κ curve at a particular mole fraction of TTAB showed only one break, which was quite close to a similar one in pure water. In TTAB + HTAB mixtures, the first break is called the critical aggregation concentration. It is close to the conventional cmc and is attributed to the polymer-free micelle formation, whereas the second break is due to the polymer-bound micellar aggregates. However, no polymer-bound micellar aggregation process was observed in the case of TTAB + DTAB mixtures. Therefore, the presence of micelle–PVP interactions in the TTAB + HTAB case have been attributed to the stronger hydrophobicity of HTAB or TTAB + HTAB micelles in comparison to that of single or mixed micelles of TTAB + DTAB mixtures. From the conductivity data, various micelle parameters in the presence of PVP have been computed and discussed in terms of micelle–polymer interactions. The mixing behavior of TTAB +  HTAB corresponding to the first break, and that of TTAB + DTAB mixtures in the presence of PVP, is close to ideal and is also identical to that in pure water. Received: 26 August 1999 Accepted: 6 November 1999  相似文献   

7.
The conductances of hexadecyltrimethylammonium bromide (HTAB) + tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of HTAB (αHTAB) were measured in pure water as well as in the presence of various aqueous ethylene glycol oligomers containing 5, 10 and 20 wt% of each additive in their respective binary mixtures at 30°C. From the conductivity data, the critical micellar concentration (cmc), degree of counter ion association (χ) and the standard free energy of transfer of the surfactant hydrocarbon chain from the medium to the micelle (ΔGO HP ) for HTAB and TTAB were computed. From the conductivity data of mixed surfactants systems, apart from cmc and χ, the regular solution theory parameters were also computed in order to explore the non-ideality in the mixed micelle formation in the presence of additives. The micellar parameters of both kind of surfactants and their mixtures show a significant dependence on the amount as well as on the number of repeating units of glycol oligomers. However, the non-ideality of mixed micelle formation remains unaffected in the presence of additives. These results have been explained on the basis of the medium effects of aqueous additive and it has been concluded that there are no significant interactions of glycol oligomers with the micelles of single and mixed surfactants.  相似文献   

8.
In the present study, we investigate the self-association and mixed micellization of an anionic surfactant, sodium dodecyl sulfate (SDS), and a cationic surfactant, cetyltrimethylammonium bromide (CTAB). The critical micelle concentration (CMC) of SDS, CTAB, and mixed (SDS + CTAB) surfactants was measured by electrical conductivity, dye solubilization, and surface tension measurements. The surface properties (viz., C20 (the surfactant concentration required to reduce the surface tension by 20 mN/m), ΠCMC (the surface pressure at the CMC), Γmax (maximum surface excess concentration at the air/water interface), and Amin (the minimum area per surfactant molecule at the air/water interface)) of SDS, CTAB, and (SDS + CTAB) micellar/mixed micellar systems were evaluated. The thermodynamic parameters of the micellar (SDS and CTAB), and mixed micellar (SDS + CTAB) systems were evaluated.

A schematic representation of micelles and mixed micelles.  相似文献   

9.
In this study, (1)H NMR is used to investigate properties of sodium dodecyl sulfate (SDS), tetradecyl trimethyl ammonium bromide (TTAB), and dodecyl trimethyl ammonium bromide (DTAB) adsorbed on kaolin by NMR T(1) and T(2) measurements of the water proton resonance. The results show that adsorbed surfactants form a barrier between sample water and the paramagnetic species present on the clay surface, thus significantly increasing the proton T(1) values of water. This effect is attributed to the amount of adsorbed surfactants and the arrangement of the surfactant aggregates. The total surface area covered by the cationic (DTAB and TTAB) and anionic (SDS) surfactants could be estimated from the water T(1) data and found to correspond to the fractions of negatively and positively charged surface area, respectively. For selected samples, the amount of paramagnetic species on the clay surface was reduced by treatment with hydrofluoric (HF) acid. For these samples, T(1) and T(2) measurements were taken in the temperature range 278-338 K, revealing detailed information on molecular mobility and nuclear exchange for the sample water that is related to surfactant behavior both on the surface and in the aqueous phase.  相似文献   

10.
The conductances of sodium dodecylsulphate (SDS) + sodium decylsulfate (SDeS) and decyltrimethylammonium bromide (DeTAB) + tetradecyltrimethylammonium bromide (TTAB) over the entire mole fraction range of SDS (SDS) or DeTAB (DeTAB) were measured in water, 18-crown-6 ether + water (CR + W) and -cyclodextrin + water (CYC + W) mixtures at fixed 4 mM and 8 mM of CR or CYC in their respective binary mixtures at 30 °C. The conductivity plots for SDS + SDeS mixtures show a single break whereas two breaks are observed at most of the DeTAB for DeTAB + TTAB mixtures. From the break in the conductivity data, the mixed critical micellar concentration (cmc) and degree of counter-ion association () were computed. The first break corresponds to the classical cmc of TTAB is termed as the first cmc (C1) and the second break which is observed at concentrations about 4 times the first one, corresponding to the classical cmc of DeTAB and is considered to be the second cmc (C2). The non-ideality in SDS + SDeS mixtures has been evaluated by using the regular solution theory and it has been observed that the mixture is close to ideal in the absence and presence of additives. The variation in C1, C2 and 1, 2 for DeTAB + TTAB has been discussed in terms of the mixed micelle formation which are predominantly rich in the TTAB and DeTAB monomers respectively.  相似文献   

11.
Thin-layer chromatography (TLC) of three cationic surfactants was performed on silica TLC plates with various solvent systems. The mutual separation of cetylpyridinium chloride (CPC), tetradecyltrimethylammonium bromide (TTAB) and dodecyltrimethylammonium bromide (DTAB) was achieved on silica TLC plates with ethanol: 1% aqueous ammonium chloride (4:6, v/v) as an eluent. Effects of cations and anions in the mobile phase on mobility and separation of CPC, TTAB and DTAB were examined. The interference due to the presence of metal cations as impurities on the resolution in the mixture of CPC, TTAB and DTAB was also examined. The limits of detection of CPC, TTAB and DTAB estimated were 0.015, 0.031 and 0.062 μg zone−1, respectively. The developed method was utilized to identify these surfactants in different spiked water samples after their preliminary separation.  相似文献   

12.
The alkaline hydrolysis of aromatic and normal aliphatic acid esters has been studied at 25°C in micellar solutions of surfactants (DTAB, TTAB, CTAB, SDS, Brij 35 and Triton X—100) with UV spectrophotometry and the method of thermokinetics in this paper. The rate constants of the alkaline hydrolysis of esters in micellar pseudophase, k1m and K2m have been calculated, respectively. The ratios of k2m to k2w or k1w to k1w indicate that the alkaline hydrolysis of esters arc inhibited by all of the surfactants investigated. It was supposed that such inhibition is mostly in relation to the micropolarity of micellar surface. The critical micellar concentrations of the corresponding systems have also been measured with the conductivity method and UV spectrophometry in this paper.  相似文献   

13.
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 (Cm), micelle mole fraction (X1), interaction parameter (β), and free energy of mixing (ΔGex) 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.  相似文献   

14.
The interaction between sodium perfluorooctanoate (SPFO) and dodecyltrimethylammonium bromide (DTAB) was studied by several methods and it was found strongly synergistic. Above a mole fraction of SPFO in the surfactant mixture (alpha(SPFO))=0.38, the interaction is repulsive and increases with the content of SPFO in both, the overall mixture and micelles, whereas the interaction is attractive if DTAB is in excess. At alpha(SPFO)=0.38 the low miscibility between hydrocarbon and fluorocarbon is counterbalanced by the electrostatic attraction between the opposite charged head groups, and the micelle composition is ideal (i.e., the mole fraction of SPFO in micelles X(SPFO)=alpha(SPFO)=0.38). The solubility of fluorocarbon in hydrocarbon is lower than that of hydrocarbon in fluorocarbon. Micelles of DTAB act as a solvent for SPFO without important structural changes, whilst micelles of SPFO undergo important changes when dissolve DTAB. This asymmetry may be interpreted as caused by the difference in chain length that favors the inclusion of the shorter chain in micelles of the longer surfactant, but disfavors the opposite process. Above X(SPFO)=0.5 there is an excess adsorption of bromide ions on the mixed micelles surface, giving rise to a high zeta potential. Micelles of pure SPFO or pure DTAB show an important energy barrier which prevents micelle flocculation. The inclusion of SPFO in DTAB micelles produces a reduction of the energy barrier, which disappeared when alpha(SPFO)=0.5. This produces the flocculation of micelles giving rise to the formation of a non-birefringent coacervate, which is probably formed by unordered isometric clusters of micelles.  相似文献   

15.
The conductances of trimethyltetradecylammonium bromide (TTAB)+triphenyltetradecylphosphonium bromide (TTPB) and TTAB+trimethylhexadecylammonium bromide (HTAB) over the entire mole fraction range of TTAB (alpha(TTAB)) were measured in water and in beta-cyclodextrin+water (CD+W) mixtures at fixed 4 and 8 mM of CD at 30 degrees C. The conductivity plots for both binary mixtures show a single break from which the mixed critical micelle concentration (cmc) and degree of micelle ionization (chi) were computed. From the slopes of the conductivity curves, the equivalent ionic conductivities of the monomeric (Lambda(m)), associated (Lambda(ass)), and the micelle (Lambda(mic)) states were calculated and discussed with respect to the surfactant-CD complexation in the whole mole fraction range of both surfactant binary mixtures. The association constant (K) between the respective monomeric surfactant and CD cavity of fixed 4 mM CD was computed by considering 1:1 association from the surface tension measurements. A comparison among the K values for HTAB-CD, TTAB-CD, and TTPB-CD shows that the former complexation is significantly stronger in comparison to the other ones due to the longer hydrophobic tail. The nonideality in mixed micelle formation in pure water was evaluated by using the regular solution theory, and it was observed that both binary mixtures exhibit close to ideal behavior. Copyright 2000 Academic Press.  相似文献   

16.
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.  相似文献   

17.
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.  相似文献   

18.
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.  相似文献   

19.
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.  相似文献   

20.
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.  相似文献   

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