You are on page 1of 13

Phase and Rheological Behavior of Cetyldimethylbenzylammonium Salicylate (CDBAS) and Water

Journal of Surfactants and Detergents ISSN 1097-3958 Volume 14 Number 2 J Surfact Deterg (2011) 14:269-279 DOI 10.1007/ s11743-010-1223-6

1 23

1 23 .Your article is protected by copyright and all rights are held exclusively by AOCS. provided it is not made publicly available until 12 months after publication. please use the accepted author’s version for posting to your own website or your institution’s repository. If you wish to self-archive your work. You may further deposit the accepted author’s version on a funder’s repository at a funder’s request. This eoffprint is for personal use only and shall not be self-archived in electronic repositories.

Below Tk and concentrations B2 wt%. surfactant concentration. Universidad de Departamento de Ingenierı ´a Barraga ´ n #1451. whereas the viscous modulus (G00 ) collapses only at reduced frequencies lower than 0. cosmetic formulations.e.1.t is the critical chain length of the tail [14–29]. *0.. e. ionic strength.005 wt%) was detected at a temperature of 35 °C. armandosolteros@yahoo. and by external fields such as shear deformations. The elastic (G0 ) modulus collapses in a concentration–time master curve in the whole reduced frequencies range xsc examined. such as drug delivery. Gonza ´as Balleza Á J. pressure. in medical diagnostics. Guadalajara.5 wt%. San Luis Potosı ´. Garcı ´ xico Jalisco *0. Universidad Auto ´ noma de San Luis Potosı ´. wormlike micelles form and the elastic behavior predominates (G0 [ G00 ). Av. The Krafft temperature (Tk = 33 ± 1 °C) was measured by differential scanning calorimetry. This phenomenon can be described based on the packing   parameter. a lamellar (L1) phase forms. additives like alcohol. and electric fields [14]. conductimetry. Guadalajara. ´ lvarez Á ´ lez-A F. Valdez-Pe ´sica.75 wt%). forming spontaneously a large variety of structures (micelles. wormlike micelles. Selforganization behavior of surfactants in solutions is a spontaneous process that is thermodynamically driven. From 12. P ¼ ahvltc. SLP 78000. A.Author's personal copy J Surfact Deterg (2011) 14:269–279 DOI 10. Me ´ xico Ocotla 123 . 13]. Me e-mail: jfasm@hotmail. Fe ´ lix Armando Soltero Martı ´nez (&) E. Reduced stress plotted as a function of the reduced shear rate yields a good superposition of the curves at the different concentrations up to the onset of the non-linear behavior. and rheometry. This parameter is used to predict the most presumable shapes that a surfactant can form. At higher concentrations. i. At higher concentrations and up to 12 wt%. Ferna ´ gicas. magnetic. R. and in the food industry [2–11]. liquid crystals. changes in temperature. Roger Vega-Acosta ´ lez-A Francisco Carvajal-Ramos • Alejandro Gonza ´ rez • Vı ´ ndez Escamilla • ´ctor Vladimir Amilcar Ferna Donato Valdez-Pe ´ lix Armando Soltero Martı ´as Balleza • J. Me ´ xico A ´ ndez Escamilla V. Departamento de Ciencias Tecnolo Universidad de Guadalajara. and lc. Macı ´a Quı ´mica.) [1].t . salts. Roger Vega-Acosta Á D. Instituto de Fı ´ lvaro Obrego ´ n #64. a second lamellar phase (L2) is detected. an emulsion phase (E) is formed. pH. polarizing microscopy. V.1007/s11743-010-1223-6 ORIGINAL ARTICLE Phase and Rheological Behavior of Cetyldimethylbenzylammonium Salicylate (CDBAS) and Water ´ lvarez • J.4 to 15. Jalisco. and hydrotropes [12.002 wt%) and a vesicle–micellar transition (cvm. etc. where vt is the volume of the hydrocarbon tail of the surfactant in the core. a transparent solution is formed (I). vesicle.5 wt%. Above 2– ´ rez J. Fe ´nez Emma Rebeca Macı • Received: 27 May 2010 / Accepted: 6 July 2010 / Published online: 4 August 2010 Ó AOCS 2010 Abstract The temperature–composition phase diagram in the diluted region of the cationic surfactant cetyldimethylbenzylammonium salicylate/water system was studied with a battery of techniques. Rheological dynamic measurements for the I phase indicate that the system exhibits a predominantly viscous behavior (G0 \ G00 ) for concentrations lower than the overlap or entanglement concentration (Ce. Universidad #1115.. These structures are of fundamental interest in science research and in many technological applications. Keywords Phase behavior Á Vesicle Á Wormlike Á Hydrotropic counterion Á Rheology Á Shear banding flow Introduction Surfactants are amphiphile substances that self-organize in solvents.g. viscosimetry. Carvajal-Ramos Á A. ´ n. Boul. The critical vesicle concentration (cvc. *0. The structure transitions in surfactants solution systems can be induced by using a great variety of parameters. ah is the optimal head group area. M.

Cetyldimethylbenzylammonium chloride (CDBAC) is a cationic surfactant that forms in water spherical micelles with low aggregation numbers at low concentrations [52– 54]. conductimetry. changing the structure. P = 1/3 . Great effort has been placed into understanding and controlling the stability of this self-assembled structure [12]. polarizing microscopy. [49] studied the influence of aromatic hydrotropes on singlechain amphiphiles aqueous solutions. Kaler et al. Then. salicylate. HPLCgrade water was used. Hydrotropes are molecules that were described first by Neuberg [32]. Phase behavior was determinated by visual observations. Many studies have been performed in the past two decades into understanding the effect of hydrotropes in the phase behavior of surfactants/water systems [32–34]. viscosimetry. The cell was calibrated with standard KCl solutions of known conductivity. Critical concentrations were determinated by viscosimetry and conductimetry at 35 °C. tosilate. vesicles [30. The precipitate was filtrated and recrystallized three times from a water–acetone mixture (10:90 by volume) and the surfactant was dried using phosphorous pentoxide for 1 week. Electrical conductivities were measured with a conductimeter (Oakton Model 510) and an immersion cell (YSI) with cell constant = 1 cm-1. and rheometry. observing that hydrotropes modify the packing parameter by interacting with the amphiphiles head. They have an amphiphilic structure and the ability of increasing the solubility of scarcely soluble organic molecules in water [32]. These catanionic surfactants are a cheaper option compared to lipids for spontaneous vesicles formation.Author's personal copy 270 J Surfact Deterg (2011) 14:269–279 P \ 1/3 for spherical micelles.0 wt% and sodium salicylate (NaSal) with a purity of 99. 51]. the vesicular-to-sphere. The most interesting property of vesicles is their capacity to incorporate hydrophilic and lipophilic substances [14]. where they were frequently shaken. 31]. For the critical vesicular concentration (cvc).01 °C for temperature. thereby. which can interact with the hydrocarbon chains and with the counterions that are around the micelles [54].e. samples were prepared by weighing appropriate amounts of CDBAS and water in glass vials. differential scanning calorimetry. [16] reported the spontaneous formation of vesicles from single-chain mixed cationic and anionic surfactants. P = 1/2 .1 wt% stock solution.5 wt% were purchased from Fluka and used as received. Buwalda et al. and sphere-to-rod concentrations transitions. 123 .1 for flexible bilayer.2 9 10-3 M) and CDBAC (20. The spontaneous formation of vesicles and their application in drug delivery and DNA compacting have been reported in numerous articles [50. samples in a range from 5 9 10-4 to 5 9 10-2 wt% were prepared by dilution from a 0.1/2 for rodlike micelles. Experimental Materials Cetyldimethylbenzylammonium chloride (CDBAC) with a purity of 97. Salicylate is a highly hydrophobic counterion that is able to reduce the effective head-group area (ah) by shielding the positive charge of the surfactant head. polarized light microscopy. this produces an increase in the packing parameter value and the possibility of forming lamellar or vesicular structures. Methods The surfactant structure was confirmed by NMR spectroscopy (Advance DMX500 Bruker spectrometer). Studies were performed by using a battery of analytical techniques. For phase and rheological studies.. In order to discriminate between isotropic and liquid crystalline phases. Besides interacting with the benzyl group as a second hydrophobic tail. Hydrotropes cause profound decreases in critical micelle concentration (cmc) and induce the formation of viscoelastic wormlike micelle solutions at lower surfactant concentrations (i. The cetyldimethylbenzylammonium salicylate (CDBAS) was prepared by mixing the solutions and standing at 40 °C for 48 h. Viscosity measurements were performed in an Anton Paar AMVn microviscometer with a repeatability of \0. Over the last two decades. when a white precipitate would be observed.0 9 10-3 M) were prepared at 40 °C and sonicated for 1 h. we studied the effect of the hydrotrope counterion salicylate on the phase and rheological behavior of the cetyldimethylbenzylammonium ion (CDBA?) in water from diluted concentrations of up to 15 wt% surfactant. Cationic surfactants are very sensitive to changes in the molecular structure of aromatic hydrotropes [35–45]. the samples were allowed to reach equilibrium at the examination or measurement temperature. All samples were centrifuged to remove suspended air bubbles before being tested. Two aqueous solutions (100 mL each) of NaSal (20. mostly natural and synthetic double-chain amphiphiles have been used for forming vesicles [14]. since even small changes in the organic counterion structure can dramatically modify the phase and rheological behavior [46]. samples were viewed through crossed polarizers.1% for viscosity and 0. In this work. The benzyl group can act as a second hydrophobic chain. such as: differential scanning calorimetry (DSC). p-vinylbenzoate) [46–48] compared to that of the respective halide counterions [36]. transmission electron microscopy (TEM). and rheometry. Samples were placed in a water batch at 60 °C for a week.

At 35 °C and for surfactant concentrations lower than 0. On the other hand. where a maximum appears (arrow b). The formation of structures larger than monomer ions is indicated by the viscosity increase and the conductivity drop detected at 0. In this picture. indicating a third structural transition. Steady and oscillatory simple-shear experiments were performed in a strain-controlled TA Instruments Ares-22 rheometer with a cone-and-plate geometry of 0. with a digital temperature controller (±0. on the other hand. The second transition observed from 0.1 °C during the measurements. water. Results from the samples that lost weight were discarded.0024 wt% (arrow a).0050 wt%. All scans were made with heating and cooling rates of 0. This behavior is similar to that exhibited by wormlike micellar solutions of single- 123 . An environmental control unit was placed around the cone-and-plate fixture to prevent water evaporation. it is evident that vesicles coexist with spherical micelles. samples were examined with an Olympus BX51 optical microscope equipped with polarizers and a Linkam CSS450 heatingand-cooling stage. the conductivity increases linearly. This micrograph affirmably proved the existence of vesicles.0085 wt%. Samples in the sealed pans were weighed before and after each test. the viscosity increases as the concentration augments. The conductivity. the conductivity decreases steeply (arrow a) and then increases linearly again up to 0.0024 wt%. This decrease in viscosity indicates a transition to a smaller structure. where the viscosity decreases and the conductivity increases with surfactant concentration. where the conductivity increases steeply (arrow b). At temperatures lower than 33 °C. At around developed by Ne 0. From 0. Transition temperatures were determined to within 0.1 °C/min. Results and Discussion Phase Behavior Figure 1 shows plots of the conductivity and viscosity as a function of CDBAS concentration measured at 35 °C. Transmission electron microscopy (TEM) was performed following the negative staining technique with uranyl acetate using a HRTEM FEI TECNAI F30 STWIN G2.5 °C upon heating from the point where the base line changed slope significantly. Measurements of TEM were performed in order to discriminate the structures that are formed in these transitions. Details of the procedure have been described elsewhere [55].0050 to 0. suggests that there is a transition from larger to smaller structures. At higher concentrations and up to around 2. CDBAS is quite soluble in water above 33 ± 1 °C.0024 wt% (arrow a). the third slope change in conductivity. but they show streaming birefringence that increases in intensity upon increasing concentration and decreases as temperature increases. the solutions are isotropic and transparent. At low surfactant concentrations below the cmc. detected at concentrations higher than 0. This behavior was explained in terms of the theory ´ methy and Scheraga [59. This slope change is due to the formation of structures larger than the monomeric ions. At higher surfactant concentrations. and n-octane standards. CDBAS/water samples exhibit a white. aluminum pans for volatile samples (TA Instruments) were used. the viscosity decreases slightly with increasing concentration and it is Fig. There are several reports about the reduction of water viscosity due to the addition of surfactants in the premicellar range [56–58]. 1 Electrical conductivity (filled squares) and viscosity (open squares) as a function of CDBAS measured at 35 °C smaller than the viscosity of pure water.005 wt%. the viscosity begins to increase up to 0.Author's personal copy J Surfact Deterg (2011) 14:269–279 271 To identify the liquid crystalline phases. the viscosity increases sharply.0085 wt%. Figure 2 shows the negative-staining TEM photograph for the sample with a concentration of 0. increases linearly with surfactant concentration up to 0. with viscosities similar to that of water. The temperature was controlled to within 0. the viscosity decreases as the surfactant concentration augments and a minimum is observed (arrow c). At this concentration. granular appearance due to the presence of CDBAS crystals dispersed in an isotropic saturated surfactant solution. After this minimum. In order to minimize any loss due to evaporation. is probably due to the micelle-to-rod transition.1 radian and a diameter of 50 mm. We believe that the first transition is due to the formation of vesicles and the second one is a vesicles-to-micelle transition.75 wt%.0050 to 0.1 °C). Thermograms were obtained with a TA Instruments Q2000 differential scanning calorimeter that was previously calibrated with indium. Samples are transparent and isotropic when viewed through crossed polarizers.0050 wt%. 60].3 wt%.0085 wt%.

At concentrations higher than 2. and only a few positive spherulites are observed. such as tosilate [47] and p-vinylbenzoate [48]. For concentrations lower than 2 wt% (see thermogram for 0.g. as expected. at higher concentrations. with textures typical of lamellar liquid crystals. these textures are consistent with the lamellar phase [61]. the peak area of which diminishes with surfactant concentration.Author's personal copy 272 J Surfact Deterg (2011) 14:269–279 Fig.3 to 8. Recently. observed by temperature sweeps in the polarizing 123 .. For a 9 wt% CDBAS sample (Fig. b 9 wt% crossed polarizers. At concentrations higher than 12 wt% and up to 15 wt%. positive. this temperature coincides with that observed visually when the surfactant begins to be soluble in water. the large peak (peak a) that appears at 0 °C is due to the melting of free water. an isotropic solution is formed. We noted this phase as emulsion (E). cetyltrimethylammonium tosilate (CTAT)/water system [47]. a suspension of small and isotropic droplets dispersed in an isotropic solution is detected. For pure surfactant. Figure 3a depicts photograph of a 7 wt% CDBAS sample taken through crossed polarizers in the polarizing microscope at 35 °C. In this picture. and for higher temperatures. With increasing temperature. the micrographs show changes in textures. only two peaks are detected. 3 Photograph of CDBAS/water samples taken at 35 °C through crossed polarizers in a polarizing microscope: a 7 wt%. samples are birefringent. e. From 35 and up to 45 °C. Figure 4 shows DSC thermograms at different CDBAS concentrations. the samples turned bluish and turbid. the samples are completely milky and isotropic. This confirms that this temperature corresponds to the Krafft temperature (Tk = 33 °C). 3b). three transitions were detected in the polarizing microscopy with Fig.5 wt% are milky and opalescent. a cloudy texture. these solutions are named pseudo-solutions by Ravin et al. To the naked eye. which is bigger than that observed in surfactants with the same length tail and with different hydrotropes. they do not crystallize for months. When samples are observed in the polarizing microscopy with parallel polarizers. hydrated crystals of surfactant (Ch) are observed. up to around 23 °C. 2 Negative-staining TEM photograph for 0. oily streaks are observed. When diluted samples (C \ 12 wt%) are cooled at temperatures lower than Tk. At concentrations higher than 2 wt% and up to 12 wt% (see thermogram for 4 wt% sample). [62]. waxy crystals (Cw) are detected. Benedini et al. At temperatures lower than 35 °C. [63] reported this behavior in the amiodarone/water system. and negative spherulites are detected. negative spherulites are predominant.005 wt% CDBAS concentration tail surfactants with aromatic hydrotropes. which coincides with the transition L1 to I.3 wt% and up to 12 wt%. but the streaming birefringence intensity and viscosity values for solutions with the same concentration are much lower for CDBAS/water than those of the CTAT/water system [47]. The second smaller peak (peak b) begins at around 33 °C and increases in intensity with surfactant concentration. samples with concentrations from 2.5 wt%). the lamellar phase texture disappears slowly in the polarizing microscopy at around 80 °C for a 6 wt% CDBAS sample. indicating a transition into an isotropic phase. a third peak (peak c) is detected at 73 °C.

Above 15 °C. For temperatures higher than Ts. which is associated to the waxy crystal-to-isotropic transition seen at 45 °C in the polarizing microscopy. This sharp increase in moduli with temperature is a sign of the Krafft temperature. a slope change is detected. At temperatures higher than 34 °C (arrow c). both G0 123 . only both the melting (a) and Tk (b) peaks are observed. the rheological behavior at temperatures lower than Tk is similar to that shown for 1 and 3 wt% samples. For temperatures above Tk. G00 [ G0 for temperatures lower than 15 °C. where a maximum is observed (arrow b). a transition from a milky and opalescent solution to an isotropic non-birefringent solution was visually detected. Above Tk and up to the temperature of the G0 and G00 crossover (Ts). At temperatures higher than Tk. G0 and G00 cross over (arrow a) and a predominantly elastic response is observed (G0 [ G00 ). b 3. both G0 and G00 increase sharply by around two magnitude orders. For more concentrated solutions (see thermogram for 15 wt% sample). 5c.1 °C/min microscopy. 5a) exhibits a slightly predominant viscous behavior. the rheological behavior is predominantly viscous. 3 (b). and entanglement of wormlike micelles. in this temperature range. and 6 (c) wt% samples. The reduction exhibited for the moduli from 23 to 34 °C is due to the melting of waxy crystals into a transparent. 4 DSC thermograms of CDBAS/water samples as a function of CDBAS concentration. both moduli diminish gradually with increasing temperature. where both moduli decrease with temperature and around 70 °C. This response is observed for concentrations up to 2 wt% CDBAS. The heating rate was 0. 1 (c). The slope change detected at 15 °C is due to the transition from hydrated crystals (Ch) to a mixture of waxy crystal (Cw) and isotropic phase (I). This increase in the elastic modulus is due to the formation. the sample becomes viscous again. that is. At this temperature. Rheological Behavior Figure 5 depicts G0 and G00 as a function of temperature for selected CDBAS concentrations. The first one (peak d) appears at 35 °C and is due to the surfactant hydrocarbons chain melting when waxy crystals are formed. the sample response is dominantly elastic. this transition was seen by the naked eye.Author's personal copy J Surfact Deterg (2011) 14:269–279 273 Fig. Above 23 °C and up to 34 °C. as confirmed by polarizing light microscopy. both moduli increase with temperature up to around 23 °C. 5 Storage G0 (filled squares) and loss G00 (open squares) moduli at 10 rad/s within the linear viscoelastic region as a function of temperature for CDBAS concentrations of: a 1. which was observed by polarizing light microscopy. The sample with 3 wt% concentration (Fig. which are within the linear viscoelastic regime (LVR). and c 6 wt% Fig. 5b) and for temperatures lower than Tk (arrow c) exhibits a similar behavior. Measurements were performed at a frequency of 10 rad/s and a deformation of 20% for the (a) and (b) samples and 0. For concentrations in the range where the lamellar phase was detected. The moduli–temperature dependence for a 6 wt% sample is depicted in Fig. growth. 43 °C. When the pure surfactant is heated. The 1 wt% sample (Fig. two peaks are detected. and two transitions were detected (arrows a and b). the moduli decrease by more than one magnitude order. isotropic phase that exhibits streaming birefringence. and a second sharp peak (peak e) is seen at ca.1% for the (c) sample.

With the data collected visually. At even higher concentration. For Fig. Figure 8 shows the elastic (G0 ) and viscous (G00 ) moduli measured at 35 °C as a function of CDBAS concentration. e. the moduli are temperature-independent. Besides. 6 Temperature sweeps made at 10 rad/s within the linear viscoelastic (20%) region for 3 wt% CDBAS concentration: (filled squares. Interestingly. However. At room temperature and in a concentration range between 27 and 47 wt% CTAT. span from 2 to 12 wt%. The frequency sweeps are made at oscillatory strain deformation within the linear viscoelastic region. tosilate [47] and p-vinylbenzoate [48]. arrow a) without the sample crystallizing. and optical microscopy. For temperatures lower than Tk. thus. the salicylate counterion that is highly hydrophobic reduces the effective head-group area (ah). They suggested that the hydrophobicity of the counterion plays an important role in controlling the curvature of the interface and. 15 wt% (shaded area). From 15 up to 23 °C. L2 lamellar phase. in setting the structure of the supramolecular assemblies [65. The phase behavior of the CDBAS/water system is very different from that reported for surfactants with the same length tail. Between 0 and ca. both G0 and G00 diminish up to 80 °C. 66].5 wt%. open circles) cooling mode and G00 decrease by almost two magnitude orders and a predominantly elastic response is observed. waxy crystals in an aqueous solution are formed. a micellar solution (I) forms. I isotropic micellar solution. where the moduli cross over (Ts) and a predominantly viscous behavior is observed. an aqueous solution (I) and hydrated surfactant crystals are present. Hassan et al. inducing the forming of lamellar or vesicular structures. Cw waxy crystals. by DSC. It is evident that. in the cooling mode data. this phase is transparent. In the temperature range from 18 to 33 °C. in contrast to the system reported here. 15 °C. a micellar solution (I) is formed for temperatures higher than the Krafft temperature (ca. the data for both experiments have the same tendency. from 34 to 70 °C. the hexagonal phase (H-phase) coexists with a viscous–isotropic phase (V1) [47]. At temperatures below 0 °C. the boundary between phase the L1 and L2 phases is around 8. Two lamellar phases. in fact. 23 wt%. a pseudo-solution is formed. with different head (–(CH3)3N? instead of – (CH3)2–CH2C5H6N?) and aromatic counterions. Figure 6 depicts moduli temperature dependence performed in the heating and cooling modes for the sample with 3 wt% in surfactant. open squares) heating mode. It is evident in this figure that. Ch hydrated crystals concentrations between the cvc and ca. G0 and G00 crossover is observed at Ts = 28 °C. rheometry. ice and surfactant crystals coexist..g. In the case of cetyltrimethylammonium p-vinylbenzoate (CTAVB). 33–34 °C) and concentrations between the cvc and up to around 2 wt%. The lamellar phase formed by the CDBAS in water at relatively lower concentrations is due to the benzyl group that acts as a second hydrophobic chain.5 wt% sample exhibit a crossover of 123 . 7 Temperature–composition phase diagram of binary mixtures of CDBAS and water. no lamellar phase was reported for the CTAT/ water system [47]. for temperatures higher than Tk. and a lamellar phase is detected at high concentrations from 80 to near 100 wt% [48]. 7). For temperatures higher than the Krafft temperature (ca. the Krafft temperature is not observed and it is possible to measure moduli data even up to 15 °C lower than Tk (18 °C. a hexagonal phase forms.Author's personal copy 274 J Surfact Deterg (2011) 14:269–279 Fig. The phase diagram of the surfactant with the cetyltrimethylammonium tosilate (CTAT) in water [47] exhibits a larger micellar phase (I) that extends to 25 wt% at 25 °C and to higher concentrations at higher temperatures. a H-phase is detected from 30 to 70 wt%. at 80 °C. but the extent of this region diminishes with increasing temperature. above 70 °C. have observed the formation of vesicles and lamellar phase by substituting the counterion in CTAT by 3-hydroxy-naphthalene 2-carboxylate (HNC). the lamellar phase was reported in CTAT/water by adding some electrolytes [64]. E emulsion. All samples except the 0. the isotropic micellar phase extends to 90 wt% CTAT. by shielding the positive charge of the surfactant head and by interacting with the benzyl group that produces an increase in the packing parameter value. L1 lamellar phase. streaming-birefringent. 17–18 °C) and concentrations between the cmc and ca. the temperature–concentration phase diagram was generated (Fig. (filled circles. L1 and L2. and viscoelastic.

the reciprocal of which corresponds to the main relaxation time (or disentanglement time) of the system sc. a maximum is exhibited and it then decreases up to a concentration of 2. b relaxation time (sc = 1/xc).75 up to 2. and c zero-frequency complex viscosity (filled squares) and zero-shear viscosity (open squares) measured at 35 °C shows the main relaxation time as a function of concentration. On the other hand. Around 2. where the effects of the entanglements become important.75. however. 10 Dependence on CDBAS concentration with a plateau elastic modulus (G0). This concentration dependence of G0 has been reported for a variety of micellar and polymer solutions with a similar exponent [40. From CCDBAS = 1 wt% to the highest concentration studied (2 wt%).25. (filled triangles) 1. a predominantly elastic behavior is observed.3 wt%. (filled inverted triangles) 1. 10c). the plateau modulus (G0) is not detected in the frequencies range studied. and the complex zero shear viscosity (g* 0) at 35 °C.3 wt%. this gel-like behavior is characteristic of lamellar phase structures [68]. For higher concentrations. 9. where the effect of the entanglements is not important (terminal zone). 9 Storage G0 (filled symbols) and loss G00 (open symbols) moduli versus frequency measured at 35 °C for CDBAS aqueous solutions of (wt%): (filled circles) 6. However. where a departure from the tendency is observed. the departing from the tendency is due to the I-to-L1 transition. G0 exhibits a slope change. The G0 and G00 frequency dependence performed in the linear viscoelastic zone (c = 0. the rheological behavior is predominantly viscous for all frequencies. The same behavior is depicted by g0 and g* 0 (Fig. G0 follows a power law concentration dependence 2:5 of the form: G0 / Csurf (Fig. (filled circles) 0. Figure 10b Fig. A value of Ce & 0.25 wt% at 35 °C. 8 Storage G0 (filled symbols) and loss G00 (open symbols) moduli versus frequency measured at 35 °C for various CDBAS aqueous solutions (wt%): (filled squares) 0. Figure 11 depicts the time–concentration master curves of G0 /G0 and G00 /G0 for CDBAS concentrations from 0. 69.5 wt%. 123 .5 wt%. G00 collapses only at scx B 1 values. The moduli for both samples exhibit a predominantly elastic response and are frequency independent. for CCDBAS B 0. 41. hence. At higher scx. but its slope decreases with concentration. 70].50. the main relaxation time (sc). It is evident that. the zero shear viscosity (g0. It is clear that sc increases with concentration and at around 1. This characteristic concentration is the critical entanglement concentration (Ce) [67].4 wt%. (filled left pointing triangles) 2 Fig. the wormlike micelles begin to overlap and entangle. xc shifts to lower values.75 to 2. G0 collapses in all of the dimensionless frequencies (scx) that were studied.3 wt%.1%) for 6 and 10 wt% samples is shown in Fig. (filled squares) 10 G0 and G00 at a characteristic frequency (xc). Figure 10 shows the concentration dependencies of G0 (estimated as G0 ¼ sc gà 0 ). which coincides with that of the isotropic-to-lamellar transition (see Fig. the elastic modulus (G0 ) increases with frequency. 10a) from 0. 7). xc shifts to higher values. The predominantly elastic behavior region increases with concentration. above this concentration.7 wt% is determined [on the basis of the observed onset of the elastic plateau (G0)]. and. obtained under steady shear rate experiments). For concentrations up to 1.Author's personal copy J Surfact Deterg (2011) 14:269–279 275 Fig. G00 data departs from the master curve.

a stress plateau or a sigmoid behavior in the stress versus shear rate is observed. (open diamonds) 1. Ludtke JJ. Elsevier. Malmsten M (2002) Liposomes.75. producing an increase in the packing parameter value.25 wt% at _ sc \0:3 where the behavior is Newtonian. Budker V. In conclusion. In: Degiorgio V. Fritz JD. (open triangles) 1. at lower concentrations.75 to 2. Sebestyen MG. FC-R acknowledges the scholarship from the CONACYT.5. whereas at higher concentrations. Bologna. 25463). 11 Time–concentration superposition master curves for a G0 and b G00 at 35 °C as a function of CDBAS concentration (wt%): (open squares) 0. pp 547–554 2. trimethylammonium head. all 35 °C.75.25 1. For c shear thinning behavior develops. Papahadjopoulos D (1996) Liposomes and biopolymers in drug and gene delivery. (open triangles) 1. Adv Drug Deliv Rev 16:249–265 4. (open inverted triangles) 1. in which two phases coexist. which is slightly lower than that predicted by the Cates and Fielding’s model [75]. Reduced logarithmic shear stress increases again linearly at higher logarithmic reduced shear rates values.75. (open diamonds) 1. Hagstrom JE. At c _ sc  0:3. pp 87–132 3. (open stars) 2. (open stars) 2. two different patterns can be 123 .. This value is higher than that measured for surfactants with the same tail length. Curr Opin Solid State Mater Sci 1:392–400 Figure 12 shows the steady-shear master dynamic _ sc Þ diagram proposed by Berret et al.. Woodle MC (1995) Sterically stabilized liposome therapeutics.005 wt% is detected at a temperature of 35 °C. micelles. Marcel Dekker Inc. the data depart from the master diagram. [71] for ðr=G0 vs: c samples with concentrations from 0.Author's personal copy 276 J Surfact Deterg (2011) 14:269–279 Fig. 12 Reduced shear stress versus shear rate measured at 35 °C as a function of CDBAS concentration (wt%): (open squares) 0. vesicles and microemulsions. supporting different shear rates. double-tail surfactants. (open circles) 1.75. The inflexion in the shear stress–shear rate curve has been observed in several surfactant systems. In: Malmsten M (ed) Surfactants and polymers in drug delivery. The stress plateau has been associated with the appearance of the shear banding flow. indicating a second Newtonian behavior (g?). the stress continuously increases with the shear rate. which has been associated with the appearance of an unstable region in a critical shear rate value [72–74]. References Fig. where a the data collapse in a single line. e. (open circles) 1. However. and different aromatic counterions.25 discerned. The reduced stress plateau occurs at r=G0  0:62. Tanford Ch (1985) Monolayers. (open inverted triangles) 1. This kind of surfactant is a cheap alternative for spontaneous vesicle formation instead of catanionic surfactants. New York. Biochim Biophys Acta Biomembr 1284:47–55 5. This reduces the effective head-group area (ah) by shielding the positive charge of the surfactant head and by interacting with the benzyl group. (open left pointing triangles) 2. The formation of vesicles is probably due to the salicylate counterion. The CDBAS/water system forms vesicles at 0. which is highly hydrophobic.002 wt% and a vesicle–micellar transition at 0. lipid vesicles and biomembranes. the Krafft temperature for the cetyldimethylbenzylammonium salicylate (CDBAS) in water is 33 ± 1 °C.25.5. tosilate (Tk = 23 °C) and p-vinylbenzoate (Tk = 18 °C).g. Wolff JA (1996) Complexes of non-cationic liposomes and histone H1 mediate efficient transfection of DNA without encapsulation. (open left pointing triangles) 2. or lipids. Lasic DD.25. Acknowledgments This work was supported by a project of the ´ xico (CONACYT National Council of Science and Technology of Me grant no. Corti M (eds) Physics of amphiphiles: micelles.

Zheng SY. Onimaru N. J Non-Newtonian Fluid Mech 28:171–182 42. Rodriguez BE. Bose A (1997) Dynamics of micelle– vesicle transitions in aqueous anionic/cationic surfactant mixtures. Vinson PK. Bakalis S (2010) Alginate-loaded liposomes can protect encapsulated alkaline phosphatase functionality when exposed to gastric pH. Rheol Acta 26:532–542 43. Evidence of vesicle formation from single-chain amphiphiles bearing a disaccharide headgroup. Hoffmann H (2004) Self-assembled structures in excess and salt-free catanionic surfactant solutions. J Phys Chem 96:474–484 46. Mo gene delivery with cationic lipids. Schulz PC (1995) Rheology of cetyltrimethylammonium tosylate–water system. Hoffmann H. Miller WG (1992) Viscoelastic micellar solutions: microscopy and rheology. Verbavatz JM. Villeneuve M. Clausen TM. Bansal D. Ohlendorf D. Proc Natl Acad Sci USA 98:1353–1357 23. J Colloid Interface Sci 57:575–577 47. Langmuir 24:11009–11017 28. Wongwailikhit K. Hirata H. Langmuir 15:4960–4965 34. Iampietro DJ. Langmuir 5:398–405 40. Torchilin VP (2005) Recent advances with liposomes as pharmaceutical carriers. Silva SG. Ninham BW (1976) Theory of selfassembly of hydrocarbon amphiphiles into micelles and bilayers. Kabir-ud-Din (1999) Micellar growth in the presence of salts and aromatic hydrocarbons: influence of the nature of the salt. 2nd edn. Hirata H. Yoshikai Y. Israelachvili JN. Puig JE. Rico-Lattes I (2009) Drug delivery by soft matter: matrix and vesicular carriers. Brito RO. J Phys Chem 97:13792–13802 18. Soussan E. J Phys Chem 89:517–522 36. So ¨ derman O (2008) Spontaneous vesicle ML. Langmuir 12:3802–3818 20. Ohta A. Shigehisa M. Colloid Polym Sci 273:156–164 19. 2. Rehage H (1987) Flow birefringence and rheological measurements on shear induced micellar structures. Bruce BD. Shikata T. Blanzat M. Shikata T. Zasadzinski JA. Yuet PK. Blankschtein D (1996) Molecular-thermodynamic modeling of mixed cationic/anionic vesicles. Viscoelastic properties of aqueous cetyltrimethylammonium bromide-salicylic acid solutions. Davidson PM. Aratono M. Naqvi AZ. J Colloid Interface Sci 324:185–191 277 ´guez-Borges JE. Langmuir 4:354–359 39. Kotaka T (1988) Micelle formation of detergent molecules in aqueous media. Osaki K (1988) Nonlinear viscoelastic behavior of aqueous detergent solutions. Strivens TA (1989) The rheological properties of concentrated cetyltrimethylammonium bromide-salicylic acid solutions in water. Hoffmann H (1985) Viscoelastic detergent 35. Curr Opin Colloid Interface Sci 9:279–293 24. Haselton FR. Takata Y. Shikata T. Thurn H. Langmuir 16:5252–5256 ¨ bl M. Science 245:1371–1374 17. Langmuir 11:3337–3346 123 . Mitchell DJ. Langmuir 3:1081–1086 38. Smith AM. Prog Colloid Polym Sci 84:241–242 45. Kotaka T (1989) Micelle formation of detergent molecules in aqueous media. Gomes P. J Phys Chem 92:4712–4719 41. Kaler EW. J Chem Soc Faraday Trans II 72:1525–1568 31. Bhattacharya S. Tseng WC. J Colloid Interface Sci 319:542–548 25. Bergstro (1999) Small-angle neutron scattering (SANS) study of vesicles and lamellar sheets formed from mixtures of an anionic and a cationic surfactant. London 32. Zhang FM. Biochim Biophys Acta Gene Struct Expression 1445(1):53–64 ¨ nkko ¨ nen J. Langmuir 16:87–97 29. Kabir-ud-Din (2000) Micellar morphology in the presence of salts and organic additives. Taylor TM. Wunderlich AM. Schurtenberger P. Weiss J (2005) Liposomal nanocapsules in food science and agriculture. Hoffmann H (1986) Surfactant systems for drag reduction: physico-chemical properties and rheological behavior. Vlachy N. Rheol Acta 25:468–486 37. Betz G. Zasadzinski JA. Lo solutions. Kumar S. 1. Marques EF. Hodgdon TK. Minter JR. Hoffmann H (1988) Rheological properties of viscoelastic surfactant systems. Soltero JFA. Mitchell DJ. Kaler EW (2001) The origins of stability of spontaneous vesicles. Grover LM. Arau formation in catanionic mixtures of amino acid-based surfactants: chain length symmetry effects. Go structure of lyotropic mesophases. Herrington KL. J Agric Food Chem 58:4719–4724 12. Matsubara H (2007) Spontaneous vesicle formation of single chain and double chain cationic surfactant mixtures. Rehage H. Urtti A (1998) Lipid fusion in oligonucleotide and 7. Pedersen JS. Angew Chem Int Ed Engl 48:274–288 16. Manero O.Author's personal copy J Surfact Deterg (2011) 14:269–279 6. O’Connor AJ. Coldren B. Strey R. Hatton TA. Langmuir 13:6931–6940 ¨ m M. Bertani R. Segota S. Menshutina N. Li H. Koga I. Guo R (2008) Aggregation of single-chained cationic surfactant molecules into vesicles induced by oligonucleotide. Shikata T. Hao JC. Colloid Polym Sci 267:269–280 ¨ bel S. Guo X. Jaime-Fonseca MR. Tezak D (2006) Spontaneous formation of vesicles. Acharya SNG (2000) Vesicle and tubular microstructure formation from synthetic sugar-linked amphiphiles. Interthal W. do Vale 27. Takiue T. Svenson S (2004) Controlling surfactant self-assembly. Gravsholt S (1976) Viscoelasticity in highly dilute aqueous solutions of pure cationic detergents. Takatori E. Israelachvili JN. Rodrı ´ jo MJ.: with application to colloidal and biological systems. Nat Rev Drug Discov 4:145–160 9. Miller DD. Cassel S. Academic Press. Curr Opin Colloid Interface Sci 12:121–128 33. Hiltrop K (1991) Influence of organic counterions on the 44. Murthy AK. Relation to phase behavior. Kaler EW (2007) Hydrotropic solutions. Zhao GX (1995) Formation and coexistence of the micelles and vesicles in mixed solution of cationic and anionic surfactant. Schurtenberger P. Leuenberger H (2005) In vivo comparison of various liposome formulations for cosmetic application. Role of free salicylate ions on viscoelastic properties of aqueous cetyltrimethylammonium bromide-sodium salicylate solutions. Adv Drug Deliv Rev 34:37–49 8. Kunz W (2008) Role of the surfactant headgroup on the counterion specificity in the micelle-to-vesicle transition through salt addition. Touraud D. 3. Ka mixed bile salt–lecithin vesicles: a study of the temperature dependence. Hirata H. Drechsler M. Int J Pharm 296:44–54 10. J Colloid Interface Sci 114:82–87 14. Aeppli A. J Phys Chem B 111:107–115 26. Biochim Biophys Acta 470:185–201 30. Lhoussaine B. Adv Colloid Interface Sci 121:51–75 15. Curr Opin Colloid Interface Sci 9:201–212 ¨ nzig W (1986) Formation of 13. Zasadzinski JA (1989) Spontaneous vesicle formation in aqueous mixtures of singletailed surfactants. Huang JB. Kaler EW. Talmon Y. J Phys Chem B 103:9888–9897 22. Jung HT. Egelhaaf SU 21. Kumar S. Kotaka T (1987) Micelle formation of detergent molecules in aqueous media: viscoelastic properties of aqueous cetyltrimethylammonium bromide solutions. Ninham BW (1977) Theory of selfassembly of lipid bilayers and vesicles. Giorgio TD (1999) Mitosis enhances transgene expression of plasmid delivered by cationic liposomes. A quantitative comparison between theory and experiment. Davis HT. Hirata H. Chiruvolu S (1993) Phase behavior of aqueous mixtures of dodecyltrimethylammonium bromide (DTAB) and sodium dodecyl sulfate (SDS). Israelachvili JN (1985) Intermolecular and surface forces. Crit Rev Food Sci Nutr 45:587–605 11.

He uses viral protein as nanocontainers and studies different forms of assemblies and techniques of the characterization of materials. Manero O (2003) Shear-banded flow and transient rheology of cationic wormlike micellar solutions. London ´ squez O. He received his M. J Am Oil Chem Soc 31:628–639 62. Allemandi DA. and ´ xico. Kaler EW (eds) Giant micelles: properties and applications. in Chemical Engineering at the University of ´ xico.. and M. Kern F. J Chem Phys 36:3382–3400 ´ methy G. Bandyopadhyay R. Wiley. Duncan BC. Macı JFA. Berret JF. He is currently Head Professor of the Chemical Engineering ´ xico. Puig JE (2007) Phase and rheological behavior of the polymerizable surfactant CTAVB and water. Me focused on scanning probe techniques in the interdisciplinary areas of bio/nanotribology. Alvarez-Ramı ´as ER. So micellar solutions. Pe ´ rez-Lo ´ pez JH. Department of the University of Guadalajara. Messina PV.Sc. Messina P. and his Ph. Alatorre-Meda M. Rattie ES (1975) Micelle formation and its relationship to solubility behavior of 2-butyl-3-benzofuranyl-4[2-(diethylamino)ethoxy]-3. Kushner LM. J Colloid Interface Sci 312:130–138 49. New York 71. Bourdieu L. Bautista F. and transdermal drug delivery.N-dimethyl-N-benzylammonium chloride. Guadalajara. Ravin LJ. Soltero JFA. Schulz PC. Boca Raton. Krajewska B. Ferna ´ ndez VVA.Sc. Palma SD. Manero O (1996) Rheology of the cetyltrimethylammonium tosilate–water system. Monduzzi M. Varela LM.L. in Ge France. Roger Vega-Acosta received his Ph. Manzo RH. Colloid Polym Sci 283:862–871 ´ methy G. Me ´ xico. ´as Balleza received her B. Fielding S (2007) Theoretical rheology of giant micelles. Langmuir 9:2914–2920 65. ´ rez is an invited professor of research at the Donato Valdez-Pe ´ noma de San Luis Potosı ´. Sarmiento F.5-diiodophenyl ketone hydrochloride. in 2006. Puig JE. Langmuir 16:6780–6786 50. Langmuir 12:4350–4357 66.N. In: Zana R. Messina PV.D.Sc. Lo tion of sodium perfluorooctanoate in water. Emma Rebeca Macı from the Universidad de Guadalajara in Chemical Engineering. Olsson U. 1. Marcel Dekker. Valles E (1995) Thixotropic–antithixotropic behavior of surfactant-based lamellar liquid crystals under shear flows. Manohar C (1996) Aggregates from cetyltrimethylammoniumhydroxynaphthalene carboxylate (CTAHNC): a light scattering study. Cornell University Press. Manero O. J Phys Chem B 106:13018–13026 ´as ER. Gonza (2000) Micellization of decyldimethylbenzylammonium chloride at various temperatures studied by densitometry and conductivity. Colloid Surf A 193:129–137 ´ lez Pe ´ rez A. Colloid Polym Sci 280:328–335 ´ pez-Fonta ´ n JL. Salkar RA. Macı Solans C.Author's personal copy 278 ´rez JG. Cierpicki T (1999) 1H NMR studies of 54. De Gennes PG (1979) Scaling concepts in polymer physics. Puig JE. Schulz PC. Ferrat G (2002) The aggregation of sodium dehydrocholate in water. Decruppe JP (1997) Inhomogeneous shear flows of wormlike micelles: a master dynamic phase diagram. and is studying for his Ph. Langmuir 19:6620–6626 74. Soltero 73. A model for the thermodynamic properties of liquid water. Colloids Surf A 339:145–152 ´ lez-Pe ´ rez A. Corona GS.D. and M. Bautista F. Taboada P. Rosevear FBJ (1954) The microscopy of the liquid crystalline neat and middle phases of soaps and synthetic detergents. Soltero JFA. bio/nanomechanics and bio/nanomaterials characterization. Colloids Surf A 277:75–82 56. Ph. Rodrı ´guez JR 53. Me ´ nie des Proce ´ de ´ s from the INPG. Model for the thermodynamic properties of aqueous solutions of hydrocarbons. Me He undertook a stay at the Laboratory of Rheology in Grenoble. Czapkiewicz J. Candau SJ (1996) Vesicle to micelle transition: rheological investigations. Puig JE. Samant SD. Schulz EP. His of the Universidad Auto research interests include the application of viruses to nanotechnology. 2. in Chemical Engineering from Guadalajara University. 2. Soltero JFA. Engberts JBFN (2000) Wormlike micellar and vesicular phases in aqueous solutions of single-tailed surfactants with aromatic counterions. Manero O. in Physics at the Universite 123 . 68. Cevc G (1996) Transfersomes.D. Pe ´ rez-Lo ´ pez JH.D. Morini MA. Scheraga HA (1962) Structure of water and hydro59. at the Institute of Physics ´ noma de San Luis Potosı ´. Ne phobic bonding in proteins. Sierra MB. Valaulikar BS. Sabı ´guez JR (2009) DNA–chitosan complexation: a dynamic Rodrı light scattering study. 48. Escalante JI. She ´ Joseph Fourier at also received her Ph. Menon SVG. Institute of Physics of the Universidad Auto ´ xico. Puig JE (2002) Irreversible thermodynamics approach and modeling of shear-banding flow of wormlike micelles. J Colloid Interface Sci 218:529–534 55. Phys Rev E 55:1668–1676 72. Colloid Surf A 166:161–169 ´ zycka-Roszak B. Shami EG. Ro aqueous micellar solutions of N-dodecyl. pp 109–161 Author Biographies Francisco Carvajal-Ramos received his B. Gonza (2001) Micellar properties of long-chain alkyldimethylbenzylammonium chlorides in aqueous solutions.. J Colloid Interface Sci 342:407–414 ¨ derman O (1993) Bicontinuous 64. Colloids Surf A 117:89–94 J Surfact Deterg (2011) 14:269–279 67. His research interests include the fundamental studies S. and Ph. Ferry JD (1980) Viscoelastic properties of polymers. Manohar C. Ne phobic bonding in proteins. Ruso JM. Langmuir 12:2654–2662 70.. J Res Natl Bur Stan 49:85–90 57. in ´ lez-A Alejandro Gonza ´ xico.P. Prieto G. Scheraga HA (1962) Structure of water and hydro60.Sc. M. Manero O. Chemical Engineering from the University of Guadalajara. Rodrı ´guez JR 52. Robles-Va Tripodi SB. Sarmiento F (2006) The nature of the coacervate formed in the aqueous dodecyltrimethylammonium bromide–sodium 10undecenoate mixtures. Hoffmann JI (1952) A viscometric study of the micelles of sodium dodecyl sulfate in dilute solutions. ´ ndez Escamilla is a research ´ctor Vladimir Amilcar Ferna Vı professor at Guadalajara University. liposomes and other lipid suspensions on the skin: permeation enhancement. 51. Cates ME. Schulz PC (2010) Colloidal properties of amiodarone in water at low concentration. J Pharm Sci 64:1830–1833 63. and applications to bio/nanotechnology. France. Del Castillo JL. J Chem Phys 36:3401–3417 61. Frechero MA. Porte G. Soltero JFA.D. Del Castillo JL. Buwalda RT.D. Schulz PC. Tepale N. Linear viscoelastic regime.Sc. Hassan PA. Benedini L. Hassan PA. J Rheol 39:235–240 69. Me J. Me ´ lvarez received his B. Sood AK (2003) Effect of screening of intermicellar interactions on the linear and nonlinear rheology of a viscoelastic gel.Sc.Sc. Stuart MCA. Bautista F. Narayanan J. Morini MA. Schulz PC (2005) The aggrega58. vesicle penetration. Crit Rev Ther Drug Carrier Syst 13:257–388 ´n J. Langmuir 19:3121–3127 75. Czapkiewicz J. Grenoble.

Sc. M. from the ´ xico. He received his B.Author's personal copy J Surfact Deterg (2011) 14:269–279 Grenoble. Me Chemical Engineering Department. His interests include ionic and non-ionic surfactant properties for consumer product formulation in the food and pharmaceutical industries. She is a Professor at the University of Guadalajara and works in the field of the rheology of complex fluids.. 123 .D. and Ph. He is a research professor in the University of Guadalajara.Sc. ´ lix Armando Soltero Martı ´nez is chief of the Laboratory of J. Fe Rheology in the Chemical Engineering Department of the University 279 of Guadalajara.. France.