42

Langmuir 2006, 22, 42-45

Articles
Aggregation Properties of Cationic Gemini Surfactants with Partially Fluorinated Spacers in Aqueous Solution
Yajuan Li, Peixun Li, Chuchuan Dong, Xiaoyong Wang, Yilin Wang,*, Haike Yan, and Robert K. Thomas
Key Laboratory of Colloid and Interface Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, Peoples Republic of China, and Physical and Theoretical Chemistry Laboratory, Oxford UniVersity, South Parks Road, Oxford OXI 3QZ, United Kingdom ReceiVed June 10, 2005. In Final Form: September 29, 2005
The aggregation properties of cationic gemini surfactants alkanediyl-R,-bis(dodecyldimethylammonium bromide), [C12H25(CH3)2N(CH2)m(CF2)n(CH2)mN(CH3)2C12H25]Br2 [where 2m + n ) 12 and n ) 0, 4, and 6; designated as 12-12-12, 12-12(C4F)-12, and 12-12(C6F)-12, respectively] have been studied by microcalorimetry, time-resolved fluorescence quenching, and electrical conductivity. Compared with a fully hydrocarbon spacer of 12-12-12, the fluorinated spacer with a lower ratio of CF2 to CH2 in 12-12(C4F)-12 tends to disfavor the aggregation, leading to larger critical micelle concentration (cmc), lower micelle aggregation number (N), and less negative Gibbs free energy of micellization (Gmic). However, the fluorinated spacer with a higher ratio of CF2 to CH2 in 12-12(C6F)-12 may prompt the aggregation, resulting in lower cmc, higher N, and more negative Gmic. It is also noted that enthalpy change of micellization (Hmic) for 12-12(C4F)-12 is the most exothermic, but the values of Hmic for 12-12-12 and 1212(C6F)-12 are almost the same. These results are rationalized in terms of competition among the enhanced hydrophobicity and the rigidity of the fluorinated spacer, and the variation of immiscibility of the fluorinated spacer with the hydrocarbon side chains.

Introduction
Gemini surfactants have been attracting increased attention owing to their superior properties to those of conventional singlechain surfactants.1-3 These novel surfactants consist of two hydrophobic side chains and two polar headgroups covalently attached through a spacer group. The most widely investigated gemini surfactants are made of hydrocarbon side chains and hydrocarbon spacer. Recently, gemini surfactants with fluorinated side chains have been reported to hold many special properties.4 Oda et al.5 synthesized a series of gemini surfactants with partially fluorinated hydrophobic chains. These fluorinated gemini surfactants exhibit very low critical micelle concentration (cmc) and unusually slow exchange rates of surfactants between aggregates and solution. Our group6 has investigated the thermodynamics of partially chain-fluorinated cationic gemini surfactants. The irregularities in enthalpy change of micellization have been found to be associated with variations in the architecture of the fluorocarbon chain segments. As is well-known, many previous studies7-13 have shown that the hydrophobicity of spacer
* To whom correspondence should be addressed: e-mail yilinwang@ iccas.ac.cn. Chinese Academy of Sciences. Oxford University.
(1) Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1991, 113, 1451-1452. (2) Rosen, M. J. CHEMTECH 1993, 23, 30-33. (3) Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1993, 115, 10083-10090. (4) Monduzzi, M. Curr. Opin. Colloid Interface Sci. 1998, 3, 467-477. (5) Oda, R.; Huc, I.; Danino, D.; Talmon, Y. Langmuir 2000, 16, 9759-9769. (6) Li, Y. J.; Li, P. X.; Wang, J. B.; Wang, Y. L.; Yan, H. K.; Dong, C. C.; Thomas, R. K. J. Colloid Interface Sci. 2005, 287, 333-337. (7) Danino, D.; Talmon, Y.; Zana, R. Langmuir 1995, 11, 1448-1456. (8) Song, L. D.; Rosen, M. J. Langmuir 1996, 12, 1149-1153. (9) De, S.; Aswal, V. K.; Goyal, P. S.; Bhattacharya, S. J. Phys. Chem. B 1998, 102, 6152-6160.

affects the aggregation of gemini surfactants significantly. Because of the larger volume and higher electronegativity of fluorine than those of hydrogen, the introduction of fluorine atoms greatly increases the amphiphilic character of surfactant molecules, resulting in enhanced surface activity and lower cmc. Therefore, it is of great interest to see how introducing fluorine to the spacer will influence the aggregation properties of gemini surfactants. In the present paper, we focus on the aggregation properties of a series of alkanediyl-R,-bis(dodecyldimethylammonium bromide) gemini surfactants with the structure [C12H25(CH3)2N(CH2)m(CF2)n(CH2)mN(CH3)2C12H25]Br2 [where 2m + n ) 12 and n ) 0, 4, and 6; referred to as 12-12-12, 12-12(C4F)-12, and 12-12(C6F)-12, respectively]. Isothermal titration microcalorimetry, time-resolved fluorescence quenching, and electrical conductivity are used to investigate the effect of partially fluorinated spacer on the aggregation of gemini surfactants. Materials and Methods
Materials. The gemini surfactants used in this study were synthesized and purified according to the method of Menger and Littau.3 Starting materials were obtained as follows. Br(CH2)12Br was purchased from Aldrich. Br(CH2)4(CF2)4(CH2)4Br was synthesized by three steps. 1,4-Diidooctafluorobutane (Apollo Scientific Ltd.) was first reacted with excess 3-buten-1-ol (Aldrich) to produce the iodo adduct,14 which was then reduced by dehalogenation.15 The
(10) Menger, F. M.; Keiper, J. S.; Azov, V. Langmuir 2000, 16, 2062-2067. (11) Wettig, S. D.; Verrall, R. E. J. Colloid Interface Sci. 2001, 235, 310-316. (12) Wettig, S. D.; Nowak, P.; Verrall, R. E. Langmuir 2002, 18, 5354-5359. (13) Wettig, S. D.; Li, X.; Verrall, R. E. Langmuir 2003, 19, 3666-3670. (14) Huang, W. H.; Wang, W.; Huang, B. N. Acta Chim. Sin. 1986, 44, 488494.

10.1021/la051544n CCC: $33.50 2006 American Chemical Society Published on Web 11/15/2005

Aggregation Properties of Gemini Surfactants resulting Br(CH2)4(CF2)4(CH2)4Br was synthesized by brominating the dehalogenated product using tetrabutylammonium bromide as phase transfer catalysis.16 Br(CH2)3(CF2)6(CH2)3Br was synthesized in a similar way as Br(CH2)4(CF2)4(CH2)4Br from 1,6-diiodoperfluorohexane (Apollo Scientific Ltd.) and allyl alcohol (Aldrich). Dodecyldimethylamine was prepared by direct reaction of bromododecane with dimethylamine in methanol. Then, a large excess of dodecyldimethylamine was reacted with Br(CH2)12Br, Br(CH2)4(CF2)4(CH2)4Br, or Br(CH2)3(CF2)6(CH2)3Br in warm acetone (<40 C) until precipitations of the products were completed. The products were recrystallized several times from a mixture of ethanol and ethyl acetate. The obtained gemini surfactants were confirmed by NMR and mass spectrometry (MS). The fluorescence probe pyrene (Aldrich) and a quencher of the fluorescence probe N-dodecylpyridinium chloride (DPC, Aldrich) were recrystallized from ethanol and acetone, respectively. All the surfactant solutions were prepared with triply distilled water. Isothermal Titration Microcalorimetry. Both critical micelle concentration (cmc) and enthalpy change of micellization (Hmic) were obtained from calorimetric measurements, which were conducted on a TAM 2277-201 microcalorimetric system (Thermometric AB, Jarfalla, Sweden) with a stainless steel sample cell of 1 mL at 298.15 ( 0.01 K. The sample and reference cells of the calorimeter were initially loaded with 0.5 mL and 0.7 mL of pure water, respectively. The concentrated gemini surfactant solutions of 5 mM were injected into the stirred sample cell via a 500 L Hamilton syringe controlled by a 612 Thermometric Lund pump. A series of injections, each 10 L, was made until the desired range of concentration had been covered. The system was stirred at 50 rpm with a gold propeller. The accuracy of the calorimeter was periodically calibrated electrically and verified by measuring the dilution enthalpies of concentrated sucrose solution.17 The observed enthalpy (Hobs) was obtained by integrating the area of the peak in the plot of heat flow against time. Time-Resolved Fluorescence Quenching. This method was used to determine micelle aggregation number (N)18-20 by use of a FLS920 lifetime measurement spectrometer of Edinburgh Analytical Instruments at 298.15 ( 0.1 K. Pyrene was used as a fluorescence probe and DPC as a quencher of the fluorescence probe. The concentration of pyrene was kept at 10-6 mol/L. The concentration of DPC was approximately equal to the micelle concentration. The fluorescence decay curves were determined and analyzed as in previous studies.21,22 Electrical Conductivity Measurement. Electrical conductivity was used to determine cmc and micelle ionization degree (R).23 The conductivity () of surfactant solution was measured as a function of concentration by use of a Jenway conductivity meter (model 4320). All measurements were performed in a double-walled glass container at 298.15 ( 0.1 K.

Langmuir, Vol. 22, No. 1, 2006 43

Figure 1. Variations of observed enthalpies (Hobs) of dilution of the studied gemini surfactants into water with the final surfactant concentration (C) at 298.15 K.

Figure 2. Determination of cmc and enthalpy change of micellization (Hmic) from the microcalorimetric titration curve of 12-12(C4F)-12 at 298.15 K.

Results and Discussion

Microcalorimetry was used to study the micellization of the three gemini surfactants, 12-12-12, 12-12(C4F)-12, and 1212(C6F)-12. The calorimetric titration curves of the variations of the observed enthalpy (Hobs) with the final surfactant concentration (C) at 298.15 K are given in Figure 1. The dilution curves are all approximately sigmoidal in shape and each can be subdivided into two concentration ranges with an intermediate
(15) Barton, D. H. R.; Jang, D. O.; Jaszberenyi, J. C. J. Org. Chem. 1993, 58, 6838-6842. (16) Dakka, G.; Sasson, Y. Tetrahedron Lett. 1987, 28, 1223-1224. (17) Gucker, F. T., Jr.; Pickard, H. B.; Planck, R. W. J. Am. Chem. Soc. 1939, 61, 459-470. (18) Tachiya, M. Chem. Phys. Lett. 1975, 33, 289-292. (19) Infelta, P. Chem. Phys. Lett. 1979, 61, 88-91. (20) Almgren, M. AdV. Colloid Interface Sci. 1992, 41, 9-32. (21) Wang, X. Y.; Wang, J. B.; Wang, Y. L.; Yan, H. K. Langmuir 2004, 1, 53-56. (22) Wang, X. Y.; Wang, J. B.; Wang, Y. L.; Ye, J. P.; Yan, H. K.; Thomas, R. K. J. Phys. Chem. B 2003, 107, 11428-11432. (23) Zana, R. J. Colloid Interface Sci. 1980, 78, 330-337.

transition region indicating micelle formation, corresponding to critical micelle concentration (cmc). When C is below cmc, the enthalpy change results from the breakup of the added micelles and from the further dilution of the monomers. When C is above cmc, only the added micelles are diluted and finally Hobs drops toward zero. The cmc can be identified as the extreme of differentiating observed enthalpy curves with respect to C.24 Meanwhile, enthalpy change of micellization (Hmic) is obtained from the enthalpy difference between the two linear segments of the enthalpy curves extrapolated to the cmc,25 as shown in Figure 2. All cmc and Hmic values, expressed per mole of gemini surfactant, are listed in Table 1. Time-resolved fluorescence quenching is used to determine the micelle aggregation number (N) of the gemini surfactants. Figure 3 shows the variations of N with C. It is evident from the experimental results that N increases with C for the three gemini surfactants, reflecting the growth of micelles with increasing C. From extrapolating the curves to cmc by the method of polynomial fitting, we can get the approximate values of N at the cmc, which are shown in Table 1. To obtain micelle ionization degree (R), conductivity measurement is also employed. Figure 4 shows the plot of the electrical
(24) Kiraly, Z.; Dekany, I. J. Colloid Interface Sci. 2001, 242, 214-219. (25) Johnson, I.; Olofsson, G.; Jonsson, B. J. Chem. Soc., Faraday Trans. 1 1987, 83, 3331-3344.

44 Langmuir, Vol. 22, No. 1, 2006

Table 1. Critical Micelle Concentration, Micelle Aggregation Number, Micelle Ionization Degree, and Thermodynamic Parameters of the Gemini Surfactants at 298.15 K cmca (mM) Nb R Hmic Gmic TSmic (kJ/mol) (kJ/mol) (kJ/mol) -15.66 -17.09 -15.84 -44.04 -42.26 -47.30 28.38 25.17 31.43

Li et al.

12-12-12 0.39, 0.36 12 0.31 12-12(C4F)-12 0.84, 0.73 9 0.22 12-12(C6F)-12 0.27, 0.22 13 0.28

a First value listed was determined by microcalorimetry; second value listed was determined by conductivity. b Values at cmc.

Figure 3. Variations of the micelle aggregation number (N) with the surfactant concentration (C) at 298.15 K.

Figure 4. Variations of the electrical conductivity () with the surfactant concentration (C) at 298.15 K.

conductivity () against C. For all the surfactants and the range of surfactant concentration studied, increases with increasing C. However, the rates of increase in with C are different below and above cmc. Below cmc, surfactant molecules are completely ionized. Above cmc, parts of counterions are bound to micelles, causing a reduction in the effective charge of micelles. Thus, the slope of versus C above cmc is smaller than the slope below cmc, and each versus C curve furnishes two straight lines, which intersect at cmc. There is excellent agreement between cmc values obtained from microcalorimetry and conductivity, as shown in Table 1. According to the method of Evans,26 R can be obtained by combining the slopes of the two straight lines in the electrical conductivity curves with the N values at cmc. The R values obtained by the method of Evans are also listed in Table 1.
(26) Evans, H. C. J. Chem. Phys. 1956, 579-586.

On the basis of the cmc values from microcalorimetry and R, Gibbs free energy of micellization (Gmic) for these gemini surfactants can be calculated by the equation G ) RT(1 + 2) ln (2cmc) - RT ln 2,27,28 where the degree of counterion association to micelle () was obtained by the relationship ) 1 - R. Then, the entropy of micellization (Smic) can be derived from Gmic and Hmic by Gmic ) Hmic - TSmic. The obtained thermodynamic parameters are all listed in Table 1. For the three surfactants, the contribution of Hmic and Smic to Gmic is comparable. So, the micellization is driven by both entropy and enthalpy. From Table 1, it is shown that 12-12(C4F)-12 has larger cmc, while 12-12(C6F)-12 has smaller cmc compared with 12-12-12. The value of Hmic for 12-12(C4F)-12 is the most exothermic, but the value of Hmic for 12-12(C6F)-12 is almost the same as that of 12-12-12. Moreover, it is noted that at the same surfactant concentration, the aggregation number N increases only slightly following the order 12-12(C4F)-12, 12-12-12, and 12-12(C6F)12. Zana et al.29 reported that the long hydrocarbon spacer of 12-12-12 might loop into the micellar core owing to strong hydrophobic interaction of the long spacer with hydrocarbon side chains. Their results indicated that the looped long spacer aggregates with hydrophobic side chains, which does promote the aggregation of gemini surfactants. As we know, the fluorinated spacer should become more hydrophobic with an increase in the amount of fluorine atoms because of lower polarizability and larger volume of fluorine atom than those of hydrogen atom.5 Therefore, the micellization for these gemini surfactants is expected to be promoted upon increasing the substitution number of fluorine atoms in the long spacer. However, the experimental results do not coincide with the above anticipation. All the micellization properties in the present study do not vary following the increase of the substitution degree of fluorine atoms, that is, the increase in the hydrophobicity of the long spacer. On this basis, it may be inferred that the morphology of spacer may not be affected only by the length and the hydrophobicity of the spacer when hydrogen atoms are substituted by fluorine atoms. On one hand, the increased hydrophobicity of the partially fluorinated spacer may reinforce looping of the spacer into the micellar core. On the other hand, a unique characteristic of fluorocarbon chains is their simultaneous hydrophobic and lipophobic nature.30,31 Thus, fluorocarbon chains exhibit immiscibility with hydrocarbon chains, which may tend to hinder the partially fluorinated spacer looping into the micellar core. That is to say, the hydrophobicity causes both fluorocarbon spacer and the hydrocarbon side chains to release water and aggregate with each other, whereas the immiscibility tends to bring about the fluorocarbon spacer and hydrocarbon side chain to be apart from each other. In addition, the fluorocarbon chain is much stiffer than the hydrocarbon chain, which may also make looping of the spacer difficult; that is, the difficult aggregation of the fluorocarbon spacer with hydrocarbon side chain. Thus, these competitive factors should all contribute to the observed differences in the aggregation. For 12-12-12, 12-12(C4F)-12, and 12-12(C6F)-12, the hydrophobicity and the rigidity of the spacer and the immiscibility of the spacer with hydrocarbon side chains all increase with increasing fluorine substitution. But the increased extent of these factors may not be equivalent. For 12-12(C4F)-12, the ratio of
(27) Zana, R. Langmuir 1996, 12, 1208-1211. (28) Jiang, N.; Li, P. X.; Wang, Y. L.; Wang, J. B.; Yan, H. K.; Thomas, R. K. J. Phys. Chem. B 2004, 108, 15385-15391. (29) Zana, R.; Benrraou, M.; Rueff, R. Langmuir 1991, 7, 1072-1075. (30) Bedford, R. G.; Dunlap, R. D. J. Am. Chem. Soc. 1958, 80, 282-285. (31) Gilmour, J. B.; Zwicker, J. O.; Katz, J.; Scott, R. L. J. Phys. Chem. 1967, 71, 3259-3270.

Aggregation Properties of Gemini Surfactants

Langmuir, Vol. 22, No. 1, 2006 45

CF2 to CH2 is 0.5, whereas the ratio of CF2 to CH2 in the spacer of 12-12(C6F)-12 increases to 1. Owing to the lower fluorine substitution for 12-12(C4F)-12, the enhanced hydrophobicity is somewhat weaker than the variation of immiscibility and the rigidity of the spacer, which may make the spacer of 12-12(C4F)12 hard to loop. As a result, the surfactant molecules have a weaker tendency to aggregate with each other, resulting in larger cmc. Moreover, the weak aggregation ability will induce the 12-12(C4F)-12 molecules to aggregate into smaller aggregates. Accordingly, the N value of 12-12(C4F)-12 is the smallest among the three gemini surfactants. Meanwhile, the conformation of the spacer may bring about a lower configuration energy to overcome its immiscibility with hydrocarbon chains, which will less offset the enhanced hydrophobic interaction by the fluorinated spacer. Thus, the Hmic value of 12-12(C4F)-12 is the most exothermic. However, for 12-12(C6F)-12, the case is reversed; that is, the enhanced hydrophobicity may overcome the increment of the immiscibility, even compensate the rigidity of the spacer, which may lead to the looping of spacer. As a result, the hydrocarbon chains and the spacer can be promoted to aggregate together, making the 12-12(C6F)-12 molecules aggregate at lower cmc. Then the stronger hydrophobic interactions and the resultant strong aggregation tendency allow the 12-12(C6F)-12 molecules to form larger aggregates, exhibiting larger N.

Conclusions
The aggregation behavior of gemini surfactants with partially fluorinated spacers has been investigated. The substitution of hydrogen by fluorine in the spacer may enhance the hydrophobicity and the rigidity of the spacer and brings about the immiscibility of the fluorinated spacer with hydrocarbon chains. For 12-12(C4F)-12, due to its lower ratio of CF2 to CH2 in the spacer, the rigidity and the immiscibility are the main control factors. In contrast, for 12-12(C6F)-12, with a higher ratio of CF2 to CH2 in the spacer, the enhanced hydrophobicity may overcome the immiscibility and the rigidity of the spacer. These different situations result in the quite different tendency of aggregation between the fluorocarbon spacer and the hydrocarbon side chains. Thus, the aggregation properties of gemini surfactants depend strongly on the degree of the fluorine substitution in the spacer. Acknowledgment. We are grateful for financial support from the National Natural Science Foundation of China, the Chinese Academy of Sciences, and the Royal Society (Grants 20233010 and 20473101).
LA051544N