共查询到20条相似文献,搜索用时 15 毫秒
1.
Li Y Li P Wang J Wang Y Yan H Dong C Thomas RK 《Journal of colloid and interface science》2005,287(1):333-337
A series of partially fluorinated cationic gemini surfactants and their corresponding monomeric surfactants have been studied by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaH(mic)) were obtained from calorimetric curves. The CMCs of the gemini surfactants are much lower than those of the corresponding monomeric surfactants and decrease with an increase in the number of fluorine atoms on the hydrophobic chain. The micellization of partially fluorinated cationic gemini surfactants is much more exothermic than that of the corresponding monomeric surfactants. Because of the incompatibility of hydrocarbon spacer and partially fluorinated chain, DeltaH(mic) values of the surfactants with a C6 spacer are more negative than those of the surfactants with a C12 spacer. The variations in the architecture of the fluorocarbon chain segments may be the reason of the irregularities in the change of DeltaH(mic) for the gemini surfactants. Moreover, the contribution of the enthalpy generally increases with an increase in the number of fluorine atoms. 相似文献
2.
Guangyue Bai António Lopes Margarida Bastos 《The Journal of chemical thermodynamics》2008,40(10):1509-1516
Alkylimidazolium salts are a very important class of compounds. So far, calorimetry has hardly been used to characterize their solution behaviour. The enthalpies obtained from indirect methods have an intrinsic large uncertainty, and nowadays it is clear that calorimetry is the most sensitive technique for directly measuring the thermodynamic properties of aggregation.In this work, isothermal titration calorimetry (ITC) was used along with conductivity to determine the thermodynamics of aggregation of 1-alkyl-3-methylimidazolium chlorides ([Cnmim]Cl, n = 8, 10, 12, and 14) in aqueous solution. The critical micelle concentrations, cmc, were obtained from conductivity and calorimetry, and the enthalpies of micelle formation, ΔHmic, were derived from the calorimetric titrations. From conductivity, we could also derive the values for the degree of ionisation of the micelles (α), the molar conductivity (ΛM) of the [Cnmim]Cl micellar species and the molar conductivity at infinite dilution (Λ∞) for the [Cnmim]+ cations.Values are therefore reported for the enthalpy (ΔHmic), the Gibbs free energy (ΔGmic) and entropy (ΔSmic) changes for micelle formation. Further, the aggregate sizes and aggregation numbers were obtained by light scattering (LS) measurements.The observed variation of the thermodynamic properties with the alkyl chain length is discussed in detail and compared with the traditional cationic surfactants 1-alkyl-trimethylammonium chlorides, [CnTA]Cl. The difference in the values of the thermodynamic parameters for both types of surfactants is here related to the structure of their head groups. 相似文献
3.
Lakhdar Berriche Samir Habi BenHariz Amine Gharbi Walid Talhi 《Journal of Dispersion Science and Technology》2019,40(3):378-389
We investigate the surface properties of aqueous binary mixtures of our cationic surfactant O-dodecyl-N,N′-diisopropylisourea hydrochloride (ISO-DIC C12) with commercially available nonionic surfactant polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether (TritonX-100) at different temperatures (288 to 303?K). The micellization behavior of the binary systems is studied by determining the surface tension and other important physicochemical parameters, such as the critical micelle concentration (CMC), surface tension at the CMC(γcmc), Krafft Temperature (TK), maximum excess concentration (Γmax), minimum surface area per molecule (Amin), surface pressure at the CMC (Пcmc), and the adsorption efficiency (pC20) at the air/water interface. The study has additionally covered the calculation of thermodynamic parameters of micellization, including the standard Gibbs free energy, the standard enthalpy, the standard entropy, the free energy, and the Gibbs free energy of adsorption at air/water interface. The CMC values of the binary systems determined by experimental data are used to evaluate the micellar composition in the mixed micelle, the interaction parameter β and the activity coefficients f1(ISO-DIC C12) and f2 (polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether) using the theoretical treatment proposed by Clint and Rubingh. Our results reveal that the proposed binary systems possess enhanced surface activity compared to those of the individual surfactants. 相似文献
4.
Haldar J Aswal VK Goyal PS Bhattacharya S 《Journal of colloid and interface science》2005,282(1):156-161
The aggregation properties of single-chain surfactants bearing one (H1), two (H2), and three (H3) trimethylammonium head groups have been studied by small-angle neutron scattering (SANS). Growth of aggregates was observed to decrease dramatically with an increase in the number of head groups in the surfactants. The micelles grow progressively smaller with every increase in the number of head groups of the surfactants. Aggregation number (N) continuously decreases and the fractional charge (alpha) gradually increases with the increase in the number of head groups. The semiminor axis (a) and semimajor axis (b=c) of the micelle decrease strongly with the increase in the number of head groups. In the case of H1, dramatic micellar growth is observed on addition of salts such as KBr and sodium salicylate, but this type of micellar growth is not observed in the cases of H2 and H3 when the above salts are added to their micellar solutions. Aggregation number and size of the micelles remain almost the same, even after addition of KBr at a concentration as high as 100 mM. This observation with multiheaded cationic surfactants is unusual. Clearly, the charge density at the head group level of surfactants markedly influences their micellar aggregation properties. 相似文献
5.
The enthalpies of micellization of the following surfactant series have been determined by calorimetry: benzyl (2-acylaminoethyl)dimethylammonium chlorides, RABzMe2Cl, and alkyldimethylbenzylammonium chlorides, RBzMe2Cl, where A, Bz and Me refer to amide, benzyl, and methyl groups, respectively and the acyl (for RABzMe2Cl) and/or the alkyl (for RBzMe2Cl) groups C10, C12, C14, and C16, respectively. For both series, the shapes of the calorimetric titration curves (enthalpograms) depend on the following micellar parameters: critical micelle concentration, aggregation number, and degree of counterion binding. The calorimetric-based critical micelle concentrations are in excellent agreement with those determined by conductivity. The Gibbs free energy, the enthalpy and the entropy of micellization were calculated, and divided into contributions from the CH2 groups of the hydrophobic tail, and the terminal CH3 plus head group of the surfactant. For both surfactant series, all thermodynamic parameters per CH2 group were found to be similar, since their transfer (from bulk solution to the micelle) is independent of the surfactant head-group structure. The Gibbs free energy, the enthalpy, and the entropy of transfer of the head group of RABzMe2Cl are more favorable than their counterparts for RBzMe2Cl, because of direct and/or water mediated hygrogen bonding of the amide groups in the micelle. 相似文献
6.
The importance of studying mixed micellization lies in tuning the performance of an amphiphile to bend through variation of
stoichiometry of the blend. In this study, the binary and ternary mixed systems of cetylpyridinium chloride (CPC), tetradecyltrimethylammonium
bromide, and dodecylpyridinium chloride (DPC) have been studied at 30°C using tensiometry and conductometry. In most cases,
the cmc observed from either method is in close proximity whereas in CPC/DPC mixtures, tensometric cmc precedes conductometric
cmc which may arise from a lowering in degree of counterion binding on micellar interface in the mixed system with lower stoichiometric
mole fraction of CPC. Various existing theories have been used and the results were compared with the experimental observations. 相似文献
7.
Comparative studies on interactions of bovine serum albumin with cationic gemini and single-chain surfactants 总被引:3,自引:0,他引:3
The interactions of bovine serum albumin (BSA) with cationic gemini surfactants alkanediyl-alpha,omega-bis(dodecyldimethylammonium bromide) [C12H25(CH3)2N(CH2)(S)N(CH3)2C12H25]Br2 (designated as C12C(S)C12Br2, S = 3, 6, and 12) and single-chain surfactant dodecyltrimethylammonium bromide (DTAB) have been studied with isothermal titration microcalorimetry, turbidity, fluorescence spectroscopy, and circular dichroism at pH 7.0. Comparing with DTAB, C12C(S)C12Br2 have much stronger binding ability with BSA to induce the denaturation of BSA at very low molar ratio of C12C(S)C12Br2/BSA, and C12C(S)C12Br2 have a much stronger tendency to form insoluble complexes with BSA. The binding of C12C(S)C12Br2 to BSA generates larger endothermic peaks. The first endothermic peak is much stronger than that of the second endothermic peak. The double charges and strong hydrophobicity of the gemini surfactants are the main reasons for these observations. In addition, the spectra results show that the binding of DTAB to BSA only promotes BSA unfolding and aggregation, whereas the secondary structure of BSA is possibly stabilized by a small amount of C12C(S)C12Br2 , even if the small amount of binding C12C(S)C12Br2 could induce the loss of the tertiary structure of BSA. This result may be related to the double tails of gemini surfactants, which may generate the hydrophobic linkages between the nonpolar residues of BSA. 相似文献
8.
9.
Md. Sayem Alam A. Mohammed Siddiq R. Ragupathy 《Journal of Dispersion Science and Technology》2017,38(2):280-287
In the present study, we have investigated the self-association, mixed micellization, and thermodynamic studies of a cationic gemini (dimeric) surfactant, hexanediyl-1,6-bis(dimethylcetylammonium bromide (16-6-16)) and a cationic conventional (monomeric) surfactant, cetyltrimethylammonium bromide (CTAB). The critical micelle concentration (CMC) of pure (16-6-16 and CTAB) and mixed (16-6-16+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), Amin (the minimum area per surfactant molecule at the air/water interface), etc.) of micellar (16-6-16 or CTAB) and mixed micellar (16-6-16+CTAB) surfactant systems were evaluated. The thermodynamic parameters of the micellar (16-6-16 and CTAB) and mixed micellar (16-6-16+CTAB) surfactant systems were also evaluated. 相似文献
10.
López-Fontán JL González-Pérez A Costa J Ruso JM Prieto G Schulz PC Sarmiento F 《Journal of colloid and interface science》2006,297(1):10-21
Conductivity, density, and sound velocity measurements as functions of temperature were made on tetraethylammonium perfluorooctylsulfonate solutions to determine the Krafft point, the dependence on temperature of the critical micelle concentration, the micellar ionization degree, and several thermodynamic properties: Gibbs free energy, enthalpy and entropy of micellization, apparent molar partial volume, thermal expansion coefficient, and the adiabatic compressibility factor of both micellized and unmicellized surfactants. Important changes occur at about 30 degrees C. Results are interpreted on the basis of dehydration of surfactant on micellization and on temperature increase. 相似文献
11.
Jusufi A Hynninen AP Panagiotopoulos AZ 《The journal of physical chemistry. B》2008,112(44):13783-13792
We propose a method for parametrization of implicit solvent models for the simulation of the self-assembly of ionic surfactants into micelles. The parametrization is carried out in two steps. The first step involves atomistic molecular dynamics simulations of headgroups and counterions with explicit solvent to determine structural properties. An implicit solvent model of the headgroup/counterion system is obtained by matching structural quantities between explicit solvent and implicit solvent systems. In the second step, we identify the solvophobic attractions between the tail beads. We determine the solvophobic parameters using grand canonical Monte Carlo simulations with histogram reweighting techniques. The matching objective for the identification of solvophobic attractions is the critical micelle concentration (cmc). We choose sodium dodecyl sulfate as the reference system. On the basis of hydrophobic parameters obtained from this particular model, we study specific ion effects (lithium and potassium instead of sodium) as well as the effect of cationic headgroups (dodecyltrimethylammonium bromide/chloride). Furthermore, the chain length dependence of micellization properties is investigated for sodium alkyl sulfate, with alkyl lengths between 6 and 14. All cases considered give results in broad agreement with experimental data, confirming the transferability of parameters and the generality of the approach. 相似文献
12.
Rodríguez JR González-Pérez A Del Castillo JL Czapkiewicz J 《Journal of colloid and interface science》2002,250(2):438-443
Specific conductivities of alkyldimethylbenzylammonium chlorides (alkyl=decyl-, dodecyl-, tetradecyl-, and hexadecyl-) in aqueous solutions were measured as a function of molality and temperature. Critical micelle molalities (cmc) and degrees of ionization of the micelles, beta, were estimated from the dependence of the specific conductivity on molality. It was found that temperature dependence of cmc is U-shaped with a minimum shifting toward higher temperatures with a decrease in the chain length of the alkyl group. The temperature dependence of ln xcmc (where xcmc is the cmc in mole fraction units) was fitted to the equation of Muller, which we modified by taking into account the temperature dependencies both of beta and of change in heat capacity upon micellization. From the fitting parameters, Gibbs free energies, enthalpies, and entropies of micellization as a function of temperature were estimated. 相似文献
13.
Andreea Pasc-Banu Maura Belloni Christophe Mingotaud Thomas Labrot 《Journal of fluorine chemistry》2005,126(1):33-38
The synthesis and physico-chemical investigation of a cationic, water-soluble surfactant of formula C8F17CH2CH(OH)CH2NH2+CH2CH(OH)CH2OH, Lac− (Lac = lactobionate), bearing a single-fluorocarbon tail and the lactobionate moiety as a counterion is reported. It forms spontaneously in water bilayer vesicles with a polydisperse distribution in size. This behavior could be attributed to a possible asymmetry of the bilayers due to an excess of the counterion outside the vesicles and possible stabilization by hydrogen bond interactions between the aminoalcohol polar heads of the cationic surfactant inside the vesicle. 相似文献
14.
Sakai K Umezawa S Tamura M Takamatsu Y Tsuchiya K Torigoe K Ohkubo T Yoshimura T Esumi K Sakai H Abe M 《Journal of colloid and interface science》2008,318(2):440-448
The adsorption and micellization behavior of novel sugar-based gemini surfactants (N,N(')-dialkyl-N,N(')-digluconamide ethylenediamine, Glu(n)-2-Glu(n), where n is the hydrocarbon chain length of 8, 10 and 12) has been studied on the basis of static/dynamic surface tension, fluorescence, dynamic light scattering (DLS) and cryogenic transmission electron microscope (cryo-TEM) data. The static surface tension of the aqueous Glu(n)-2-Glu(n) solutions measured at the critical micelle concentration (cmc) is observed to be significantly lower than that of the corresponding monomeric surfactants. This suggests that the gemini surfactants, newly synthesized in the current study, are able to form a closely packed monolayer film at the air/aqueous solution interface. The greater ability in the molecular association is supported by the remarkably (approximately 100-200 times) lower cmc of the gemini surfactants compared with the corresponding monomeric ones. With a combination of the fluorescence and DLS data, a structural transformation of the Glu(n)-2-Glu(n) micelles is suggested to occur with an increase in the concentration. The cryo-TEM measurements clearly confirm the formation of worm-like micelles of Glu(12)-2-Glu(12) at the concentration well above the cmc. 相似文献
15.
Alzheimer amyloid beta(1-40) peptide: interactions with cationic gemini and single-chain surfactants
The aggregation of amyloid beta-peptide [Abeta(1-40)] into fibril is a key pathological process associated with Alzheimer's disease. The effect of cationic gemini surfactant hexamethylene-1,6-bis-(dodecyldimethylammonium bromide) [C(12)H(25)(CH(3))(2)N(CH(2))(6)N(CH(3))(2)C(12)H(25)]Br(2) (designated as C(12)C(6)C(12)Br(2)) and single-chain cationic surfactant dodecyltrimethylammonium bromide (DTAB) on the Alzheimer amyloid beta-peptide Abeta(1-40) aggregation behavior was studied by microcalorimetry, circular dichroism (CD), and atomic force microscopy (AFM) measurements at pH 7.4. Without addition of surfactant, 0.5 g/L Abeta(1-40) mainly exists in dimeric state. It is found that the addition of the monomers of C(12)C(6)C(12)Br(2) and DTAB may cause the rapid aggregation of Abeta(1-40) and the fibrillar structures are observed by CD spectra and the AFM images. Due to the repulsive interaction among the head groups of surfactants and the formation of a small hydrophobic cluster of surfactant molecules, the fibrillar structure is disrupted again as the surfactant monomer concentration is increased, whereas globular species are observed in the presence of micellar solution. Different from single-chain surfactant, C(12)C(6)C(12)Br(2) has a much stronger interaction with Abeta(1-40) to generate larger endothermic energy at much lower surfactant concentration and has much stronger ability to induce the aggregation of Abeta(1-40). 相似文献
16.
Basílio N Garcia-Rio L Martín-Pastor M 《Langmuir : the ACS journal of surfaces and colloids》2012,28(5):2404-2414
The self-aggregation of five amphiphilic p-sulfonatocalix[n]arenes bearing alkyl chains at the lower rim was investigated by NMR spectroscopy and electrical conductivity. The critical micelle concentration was determined, and the tendency of this special class of surfactants to self-aggregate in aqueous solution was analyzed as a function of the alkyl chain length and the number of aromatic units in the macrocyclic ring. The structure of the surfactants in the monomeric and micellized states was elucidated by means of (1)H NMR and, in the case of the calix[6]arene derivative, with 2D NMR experiments. While all amphiphilic calix[4]arenes studied here are blocked in the cone conformation, in the monomeric state the calix[6]arene adopts a pseudo-1,2,3-alternate conformation and the calix[8]arene is conformationally mobile. These calixarenes undergo an aggregation-induced conformational change, adopting the cone conformation in the micelles. The structure and size of the aggregates were studied by diffusion ordered spectroscopy (DOSY) experiments, and the results indicate that these surfactants self-assemble into ellipsoidal micelles. 相似文献
17.
Sakai H Ebana H Sakai K Tsuchiya K Ohkubo T Abe M 《Journal of colloid and interface science》2007,316(2):1027-1030
Photo-induced isomerization of a newly synthesized surfactant, 1'(6-trimethylammoniododecyl)-3('),3(')-dimethyl-6-nitrospiro-(2H-1-benzopyran-2,2'-indoline) bromide (SP-Me-12), has been characterized on the basis of the UV-vis absorption spectra and the surface tension data. Visible light (lambda>420 nm) incident on the aqueous solution of SP-Me-12 results in the isomerization from the merocyanine (MC) form to the spiropyran (SP) form; this structural change was confirmed by a complete disappearance of a characteristic absorption peak of the MC form. When the surfactant solution is stored in the dark, the isomerized SP form reverts to the original MC form, however, the reverse isomerization rate is observed to be considerably slower than that seen for visible light irradiation (from the MC form to the SP form). A reversible change in the surface tension of the aqueous surfactant solution is observed for the photo-induced isomerization: the surface tension measured below the critical aggregation concentration decreases as a result of the visible light irradiation and it is gradually reversed to the original level during the equilibration in the dark. 相似文献
18.
Shimizu S Pires PA El Seoud OA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(22):9551-9559
The enthalpies of micellization of the surfactant series benzyl(2-acylaminoethyl)dimethylammonium chlorides, RABzMe(2)Cl, have been determined by calorimetry and conductivity measurements in the temperature range 15-75 degrees C. Here R stands for an acyl group containing 10-16 carbon atoms and A, Bz, and Me stand for NH(CH(2))(2)N(+), benzyl, and methyl groups, respectively. The enthalpy of micellization, DeltaH(mic) degrees , and the critical micelle concentration, cmc, were calculated directly from calorimetric data. The free energy of micellization, DeltaG(mic) degrees , was obtained from the cmc and the conductance-based degree of counterion dissociation. There is an excellent agreement between DeltaG(mic) degrees calculated from the data of both techniques, but the DeltaH(mic) degrees , the entropy of micellization, values differ. The dependence of the thermodynamic parameters of micellization on the chain length of the hydrophobic group and on the temperature has been analyzed by considering the delicate balance between the factors that contribute to micelle formation, including transfer of the surfactant hydrocarbon chain from the aqueous environment to the micelle, with concomitant release of the solvating water molecules, and the effect of temperature on the structure of water. DeltaG(mic) degrees is more negative, that is, more favorable for RABzMe(2)Cl than for the structurally related alkylbenzyldimethylammonium chlorides. This is attributed to direct and water-mediated H bonding between the amide groups of molecules of the former series. 相似文献
19.
A series of cationic gemini surfactants butanediyl-1,4-bis(dodecyldialkylammonium bromide), C(12)H(25)N(+)(C(m)H(2)(m)(+1))(2)C(4)H(8)N(+)(C(m)H(2)(m)(+1))(2)C(12)H(25)·2Br(-), where m=1, 2, 3, 4, referred to as C(12)C(4)C(12)(Me), C(12)C(4)C(12)(Et), C(12)C(4)C(12)(Pr), and C(12)C(4)C(12)(Bu), respectively, were synthesized, and their thermodynamic properties of micellization were studied by electrical conductivity measurements. There existed a minimum critical micelle concentration (cmc) in the curve of cmc versus temperature, and the temperature of the minimum of cmc (T(min)) increased with increasing the headgroup alkyl chain length. The values of log (cmc) depended linearly on carbon number of the alkyl chains, but that was not true for the carbon number of the headgroup substituents. The temperature dependence of cmc and degree of counterion association (β) were used to calculate the Gibbs free energy (Δ(mic)G°), enthalpies (Δ(mic)H°) and entropies (Δ(mic)S°) of micelle formation for these gemini surfactants, and well correlated enthalpy-entropy compensation was observed. The analyses showed C(12)C(4)C(12)(Me) and C(12)C(4)C(12)(Et) behaved similarly in terms of thermodynamics of micellization, but they behaved differently from C(12)C(4)C(12)(Pr) and C(12)C(4)C(12)(Bu), which could be ascribed to the hydrophobicity and the location of the headgroup alkyl chains in the aggregates. These initial results indicate the headgroup alkyl chain plays an important role in influencing the thermodynamic properties of gemini surfactants. 相似文献
20.
Microcalorimetric techniques, combined with turbidity measurements, were used to study the thermodynamics of self-assembling of hydrophobically modified cationic polysaccharides and their mixtures with oppositely charged surfactants in aqueous solution. The studied polyelectrolytes were a series of polymers based on dextran having pendant N-(2-hydroxypropyl)-N,N-dimethyl-N-alkylammonium chloride groups randomly distributed along the polymer backbone. The parameters for their micellization process are evaluated from the results of the observed dilution enthalpy curves and compared with those of the related cationic surfactants (DTAC and CTAC). The microcalorimetric results for the mixed systems (polyelectrolytes with oppositely charged surfactants) are used along with turbidity measurements to characterize systematically the thermodynamics of their interaction. The phase behavior is described and the interaction enthalpies are derived from the differences between the observed enthalpy curves with and without polyelectrolyte. Therefore, we discuss in detail the effect of changing the alkyl chain length of polyelectrolyte pendant groups, the molecular weight of the dextran backbone, and the temperature of the measurements on the interactions between polyelectrolyte and surfactant. 相似文献