2062 Langmuir 2000, 16, 2062-2067

Gemini Surfactants with Acetylenic Spacers

F. M. Menger,* J. S. Keiper, and V. Azov
Department of Chemistry, Emory University, 1515 Pierce Drive, Atlanta, Georgia 30322

Received August 5, 1999

A total of 24 dicationic geminis surfactants were synthesized, having a 2-butynyl spacer and chain
lengths varying from 8 to 18 carbons. Geminis with more flexible butyl spacers were also synthesized for
comparison purposes. Tensiometry gave critical micelle concentration (cmc) values, surface activity, and
Gibbs areas. Film studies on the C18 geminis gave liftoff and collapse areas. The acetylenic geminis behave
normally with the log cmc values decreasing linearly with chain length for all the dibromide salts. Anomalous
behavior occurred, however, with the C18 gemini having a butyl spacer. It was found that cmc data correlate
with spacer area, a relationship ascribed to packing constraints on curved surfaces and, possibly, to steric
inhibition of ion binding. The effects are accentuated with the C18 surfactants. Geminis with heterocyclic
headgroups were examined.

Introduction these motifs allowed us to address two issues. First, we

In the early 1970s Bunton and co-workers published a could determine the viability among gemini surfactants
series of papers on micellar catalysis of nucleophilic of heterocyclic headgroups such as pyrrolidine and pip-
substitution and decarboxylation reactions using di- eridine. Heterocycles have been commonly used as surf-
cationic detergentsscompounds containing two quater- actant headgroups, but such surfactants are often
nary ammonium surfactant monomers connected at the nonionic9-11 and of low water solubility, or else they are
headgroup level by an alkyl or 2-butynyl spacer.1-3 Nearly asymmetrically quaternized at the positively charged
nitrogen.12 The gemini structure, however, can lead to a
symmetrical disposition of charged heterocyclic groups.
Second is the issue of spacer flexibility or rigidity. It has
been shown both experimentally13-15 and theoretically16-19
that the spacer occupies a major role in the colloidal
properties of geminis. To date, however, most studies have
involved fully saturated alkyl groups as flexible spac-
ers6,13-15,20,21 or aryl groups as rigid spacers.4,5,22,23 Thus,
the 2-butynyl group provides a spacer of “intermediate”
bending stiffness. Using these geminis, we will show how
the distinction between flexible and rigid spacers is not
three decades later, research into such surfactants, now necessarily clear-cut in regard to micellization, especially
commonly referred to as gemini4,5 (or dimeric)6 surfactants, at chain lengths where dicationic geminis deviate from
has resurged as their exceptional surface activity and “classical” critical micelle concentration (cmc) behavior.
widening utility have become apparent.7 Additionally, the To pursue this study, we prepared five series of cationic
gemini format allows for expanded structural diversity in gemini surfactants with four-carbon spacers and alkyl
surfactant chemistry, as headgroups, hydrophobic units, chains between 8 and 18 carbons in length (shown below).
spacers, and counterions can each be varied in a search In addition to the two heterocyclic gemini forms (A and
for enhanced performance. B), dibromide and dichloride versions of an acetylenic
In the present work, we revisit the 2-butynyl spacer for dicationic surfactant (C and D) were synthesized, along
gemini surfactants, inspired in particular by the skeleton with so-called m-s-m geminis (E) (where m and s
structures of two hypotensive agents:8 1,4-bis(pyrrolidino)- (9) Rosen, M. J.; Zhu, Z. H.; Gu, B.; Murphy, D. S. Langmuir 1988,
2-butyne (3, commonly known as tremorine) and 1,4-bis- 4, 1273.
(piperidino)-2-butyne (4). Preparing geminis based on (10) Rosen, M. J.; Gu, B.; Murphy, D. S.; Zhu, Z. H. J. Colloid Interface
Sci. 1989, 129, 468.
(11) Zhu, Z. H.; Yang, D.; Rosen, M. J. J. Am. Oil. Chem. Soc. 1989,
66, 998.
(12) Savelli, G.; Focher, B.; Bunton, C. A. Colloids Surf. 1990, 48, 29.
(13) Hirata, H.; Hattori, N.; Ishida, M.; Okabayoshi, H.; Frusaka,
M.; Zana, R. J. Phys. Chem. 1995, 99, 17778.
3 4 (14) De, S.; Aswal, V. K.; Goyal, P. S.; Bhattacharya, S. J. Phys.
Chem. 1996, 100, 11664.
(15) Aswal, V. K.; De, S.; Goyal, P. S.; Bhattacharya, S.; Heenan, R.
(1) Bunton, C. A.; Robinson, L.; Schaak, J.; Stam, M. F. J. Org. Chem. K. Phys. Rev. E 1998, 57, 776.
1971, 36, 2346. (16) Diamant, H.; Andelman, D. Langmuir 1994, 10, 2910.
(2) Bunton, C. A.; Kamego, A.; Minch, M. J. J. Org. Chem. 1972, 37, (17) Diamant, H.; Andelman, D. Langmuir 1995, 11, 3605.
1388. (18) Maiti, P. K.; Chowdhury, D. Europhys. Lett. 1998, 41, 183.
(3) Bunton, C. A.; Minch, M. J.; Hidalgo, J.; Sepulveda, L. J. Am. (19) Maiti, P. K.; Chowdhury, D. J. Chem. Phys. 1998, 109, 5126.
Chem. Soc. 1973, 95, 3262. (20) Alami, E.; Beinert, G.; Marie, P.; Zana, R. Langmuir 1993, 9,
(4) Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1991, 113, 1451. 1465.
(5) Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1993, 115, 10083. (21) Esumi, K.; Taguma, K.; Koide, Y. Langmuir 1996, 12, 4039.
(6) Zana, R.; Benrraou, M.; Rueff, R. Langmuir 1991, 7, 1072. (22) Song, L. D.; Rosen, M. J. Langmuir 1996, 12, 1149.
(7) Rosen, M. J.; Tracy, D. J. J. Surfactants Detergents 1998, 1, 547. (23) Karthaus, O.; Shimomura, M.; Hioki, M.; Tahara, R.; Nakamura,
(8) Biel, J. H.; DiPierro, F. J. Am. Chem. Soc. 1958, 80, 4609. H. J. Am. Chem. Soc. 1996, 118, 9174.

10.1021/la9910576 CCC: $19.00 © 2000 American Chemical Society

Published on Web 12/10/1999
Gemini Surfactants with Acetylenic Spacers Langmuir, Vol. 16, No. 5, 2000 2063

Scheme 1

represent alkyl chain and spacer carbon number, respec- having 8-18 carbon chains were obtained by reacting an
tively) having completely saturated butyl spacers. appropriate 1,4-dihalo compound with N,N-dimethyl-
alkylamines. Acetone was an optimal medium for the
diquaternization step, as in most cases the dialkylated
product precipitated from solution while the monoalkyl-
ated compound (the major side product) remained dis-
solved. Difficulty in the workup of the shorter chain
analogues (8-12 carbons) was often encountered owing
to their hygroscopic nature. Further details on the
synthesis and characterization (1H and 13C NMR, high-
resolution mass spectra, elemental analyses) of these
compounds can be found in the Supporting Information.
Suffice it to mention here that all analytical methods
indicated high levels of purity.
Surface tensiometry on the gemini surfactants (carried
out by the du Nuoy method) is profiled in Table 1 and
Results and Discussion Figure 1. Solubility properties allowed tensiometry to be
Gemini surfactants A and B having 8-18 carbon chains performed at 23 °C for surfactants with C8-C14 chains,
were prepared in two-step procedures starting with 1,4- while 50 °C was necessary for C12-C18 chain lengths. As
dichloro-2-butyne as shown in Scheme 1. Surfactants C-E expected, the cationic gemini surfactants gave critical
2064 Langmuir, Vol. 16, No. 5, 2000 Menger et al.

Table 1. Values of the cmc, γcmc, and C20 for Geminis Table 2. Gibbs Equation-Derived Molecular Areas,
A-E MM2-Estimated Fully Extended, “All-Anti” Conformation
Areas, and Fully Compressed, “Vertical Tails” Areas for
γcmc temperature
C12-Chain Geminis
surfactant cmc (M) (mN/m) C20 (M) (°C)
Gibbs area
A-8 3.45 × 10-2 42.8 1.18 × 10-2 23
(Å2/molecule)
A-10 5.31 × 10-3 40.0 1.59 × 10-3 23 “all-anti” area “vertical tails” area
A-12 9.10 × 10-4 39.7 2.69 × 10-4 23 surfactant 23 °C 50 °C (Å2/molecule) (Å2/molecule)
1.27 × 10-3 39.9 6.15 × 10-4 50 A-12 121 121 163 94.7
A-14 1.30 × 10-4 40.4 5.21 × 10-5 23 B-12 132 131 163 111
2.68 × 10-4 39.5 1.26 × 10-4 50 C-12 128 163 76.9
A-16 4.40 × 10-5 39.4 2.18 × 10-5 50 D-12 132 127 163 76.9
A-18 1.05 × 10-5 46.2 8.78 × 10-6 50 E-12 127 135 168 81.3
B-8 4.78 × 10-2 43.1 1.75 × 10-2 23
B-10 5.96 × 10-3 39.6 1.52 × 10-3 23 It is seen that heterocyclic geminis A and B possess surface
B-12 8.92 × 10-4 38.5 2.08 × 10-4 23
1.14 × 10-3 39.1 4.75 × 10-4 50
activities comparable to or better than the acyclic dibro-
B-14 2.07 × 10-4 35.0 5.62 × 10-5 50 mide surfactants C and E. Dipiperidinium geminis B have
B-16 5.97 × 10-5 37.9 2.46 × 10-5 50 γcmc values modestly lower than the other geminis. This
B-18 1.66 × 10-5 41.5 8.50 × 10-6 50 may be a manifestation of the additional hydrocarbon
C-8 2.55 × 10-2 41.8 1.08 × 10-2 23 content at the interface provided by the rings.
C-10 1.39 × 10-3 41.1 6.01 × 10-4 23 Molecular areas of C8-C16 geminis, determined by
C-12 1.13 × 10-3 38.7 4.64 × 10-4 50 applying the Gibbs equation to the tensiometric data,
C-14 2.50 × 10-4 38.8 1.09 × 10-4 50 revealed few differences among geminis of equivalent
C-16 4.78 × 10-5 44.7 3.97 × 10-5 50 chain length (Table 2). Thus, little variance was detected
C-18 1.71 × 10-5 45.8 1.36 × 10-5 50
regardless of headgroup, spacer type, or temperature. As
D-8 7.40 × 10-2 46.2 3.69 × 10-2 23 also seen from Table 2, the empirical surface areas fall
D-10 9.38 × 10-3 45.9 4.99 × 10-3 23 between areas estimated by molecular mechanics (MM2)
D-12 1.57 × 10-3 44.6 7.05 × 10-3 23
for two possible conformational extremes of these gemi-
1.43 × 10-3 42.6 8.57 × 10-3 50
D-14 2.97 × 10-4 45.7 1.49 × 10-4 23 nis: (a) a fully extended, “all-anti” conformation and (b)
3.93 × 10-4 42.5 1.94 × 10-4 50 a fully compressed, “vertical tails” configuration reflecting
D-16 7.59 × 10-5 43.0 4.76 × 10-5 50 mainly the spacer/headgroup area. Both possibilities are
D-18 4.33 × 10-5 46.8 3.72 × 10-5 50 shown for E-12 (Chart 1).
E-8 5.61 × 10-2 41.6 1.98 × 10-2 23 While the models exclude factors such as counterions,
E10 8.78 × 10-3 40.2 2.49 × 10-3 23 electrostatic headgroup repulsion, and hydration, they
E-12 9.31 × 10-4 39.9 2.62 × 10-4 23 are useful for establishing reasonable limits. For example,
1.36 × 10-3 39.1 5.56 × 10-4 50 some previously published Gibbs-derived molecular areas
E-14 1.35 × 10-4 40.5 4.69 × 10-5 23 for p-xylyl diammonium geminis by Song and Rosen22 gave
2.78 × 10-4 39.8 1.28 × 10-4 50
E-16 4.22 × 10-5 41.8 2.44 × 10-5 50
areas (68, 47, 46, and 45 Å2/molecule for di-C12, C14 ,C16,
E-18 4.19 × 10-5 43.4 2.46 × 10-5 50 and C18 analogues, respectively, in 0.1 N NaCl at 50 °C)
well below the MM2-estimated value of 87 Å2/molecule
for the “vertical tails” configuration. In such a case, an
unconventional packing mode must be present.
Conventional single-chain surfactants undergo linear
decreases in log cmc with increasing chain lengths.24 Some
gemini surfactants, however, have shown departures from
“classical” linear trends as cmcs level off or increase with
increasing chain lengths.5,22,25 Geminis with rigid aromatic
or hydroxylated spacers have been reported to behave in
this unconventional manner, but it has been vaguely
proposed by Zana and Lévy26 that m-s-m gemini
surfactants do not deviate from linearity. They based their
suggestion on three m-2-m dicationic geminis (as well
as one system estimated by extrapolation) with chain
Figure 1. Surface tension vs log concentration for C12-chain lengths from C8 to C16. Having on hand a particularly rich
geminis at 50 °C. (9) A-12; (0) B-12; (b) C-12; (O) D-12; (2) array of compounds, we performed measurements on
E-12. geminis A-E from C12 to C18 at 50 °C to test for possible
deviations. The results are given in Table 1 and Figure
micelle concentration (cmc) values significantly lower than 2. Geminis A-C, with 2-butynyl spacers, show linear
their single-chained cousins.7 For corresponding C8-C16 decreases in cmc with increasing chain length (correlation
chain-length geminis, the surface activity among the five coefficients: A series, 0.998; B series, 0.994; C series,
series proved quite similar; two relevant points will be 0.991), while series D slightly deviates from linearity at
mentioned here. (1) Solubilities for the heterocyclic A and its C18 analogue. A more pronounced deviation is shown
B series surfactants exceeded those of the acyclic C series. with the m-s-m gemini E series, where the cmc for E-16
For example, among the C12 surfactants, A-12 has a (4.22 × 10-5 M) is equivalent to that of the longer-chained
solubility in water at 23 °C nearly 400 times that of C-12 E-18 (4.19 × 10-5 M). It would seem, therefore, that
(approximate values: A-12, 0.38 M; B-12, 0.12 M; C-12, nonlinear behavior is not simply a matter of geminis
0.00097 M; D-12, 0.61 M; E-12, 0.16 M). (2) Surface
activities can be judged by the γcmc values (the surface (24) Myers, D. Surfactant Science and Technology, VCH: New York,
1988; p 107.
tension at the cmc) and the C20 values (the concentration (25) Rosen, M. J.; Liu, L. J. Am. Oil Chem. Soc. 1996, 73, 885.
that lowers the surface tension by 20 mN/m) in Table 1. (26) Zana, R.; Lévy, H. Colloids Surf. A 1997, 127, 229.
Gemini Surfactants with Acetylenic Spacers Langmuir, Vol. 16, No. 5, 2000 2065

Chart 1

Table 3. Liftoff Area, Collapse Area, and Πcollapse for

C18-Chain Surfactants Determined with Kibron µTrough
S at 23 °C, and Gibbs-Derived Molecular Areas
Determined at 50 °C
surf- liftoff areaa collapse areaa Πcollapsea Gibbs area
actant (Å2/molecule) (Å2/molecule) (mN/m) (Å2/molecule)
A-18 164 ( 8 51.4 ( 3.3 42.7 ( 0.7 133
B-18 168 ( 4 46.3 ( 2.9 39.9 ( 0.6 138
C-18 166 ( 7 42.2 ( 3.1 42.6 ( 1.0 138
D-18 187 ( 11 52.0 ( 7.8 42.1 ( 0.5 171
E-18 181 ( 3 57.5 ( 6.1 40.5 ( 0.6 154
a Average of 10 repeat runs.

Figure 2. Log cmc vs chain carbon number for C12-C18-chain

geminis at 50 °C. (9) A; (0) B; (b) C; (O) D; (2) E.

having rigid or hydroxylated spacers. Indeed, surfactants

A-C contain a rigid acetylenic unit but behave normally,
while surfactants E are flexible and yet ultimately become
nonlinear.
Information on the packing abilities of surfactants can
be obtained from monolayer film studies.27,28 Conse-
quently, pressure-area isotherms were determined for
C18-chain surfactants at 23 °C where the geminis are
sufficiently water-insoluble to carry out the experiments.
Results of 10 averaged repetitions per surfactant are
shown in Figure 3 and Table 3. Liftoff areas for geminis Figure 3. Pressure-area isotherms at 23 °C for C18-chain
A-18, B-18, and C-18 are smaller than those of D-18 and geminis A-E.
E-18, a comparison also true for the Gibbs areas (deter-
mined at 50 °C where C18 geminis are more water-soluble). headgroup repulsion is greater due to its more loosely
All geminis collapsed at surface pressures of 40-43 mN/ bound Cl- counterions, leading to higher cmcs and
m. Two points stand out from these data. First, the larger interfacial area parameters (Tables 1 and 3). Such behavior
liftoff areas were found for D-18 and E-18, which are also is well-known for conventional surfactants,29 and our
the surfactants with unusually high cmcs. In other words, bromide/chloride data show that ion binding effects cannot
those C18 geminis that have difficulty packing at an air/ be ignored with geminis as well.
water interface also possess higher cmcs. Second, there In Table 4 are compiled cmcs (at 50 °C), MM2 energy-
are clear differences in cmc, liftoff area, and Gibbs area minimized N+-N+ distances, and van der Waals spacer
between C-18 and D-18, geminis with bromide and surface areas for C18 geminis. Included in the table are
chloride counterions, respectively. For D-18, headgroup- 18-p-xylyl-18 from our previous study5 and m-s-m
geminis 18-3-18 and 18-5-18. It is seen that all geminis
(27) Menger, F. M.; Wood, M. G., Jr.; Richardson, S.; Zhou, Q.; have N+-N+ distances below the approximate equilibrium
Elrington, A. R.; Sherrod, M. J. J. Am. Chem. Soc. 1988, 110, 6797.
(28) Sumida, Y.; Masuyama, A.; Oki, T.; Kida, T.; Nakatsuji, Y.; Ikeda, (29) Rosen, M. J Surfactants and Interfacial Phenomena, 2nd ed.;
I.; Nojima, M. Langmuir 1996, 12, 3986. Wiley: New York, 1989; p 135.
2066 Langmuir, Vol. 16, No. 5, 2000 Menger et al.

Table 4. Critical Micelle Concentrations at 50 °C, N+-N+ large surface-bound spacer resists the tight packing
Distances, and van der Waals Surface Areas for “desired” by the long C18 chains. Shorter chains, on the
C18-Chain Gemini Surfactants other hand, mean looser packing and easier accommoda-
N+-N+ spacer tion of the spatial requirements of the spacers.
distancea surface areab Mention should be made of the potential role that ion
surfactant cmc (M) (Å) (cm2/mol × 109)
binding may have in the anomalous cmc behavior of the
A-18 1.05 × 10-5 6.15 3.68 C18 surfactants. The differences in cmc and pressure-
B-18 1.66 × 10-5 6.16 3.68 area isotherm data for C-18 and D-18 demonstrate the
C-18 1.71 × 10-5 6.16 3.68 sensitivity to counterion identity. In the work with
18-3-18 5.49 × 10-5 5.23 4.05
18-4-18 (E-18) 4.19 × 10-5 6.51 5.40 C12H25NRMe2+Br- discussed above, an increase in ion
18-5-18 2.22 × 10-4 7.76 6.75 dissociation (R) was found with lengthening of R, implying
18-p-xylyl-18 3.70 × 10-4 c 7.80 8.71 that the variable alkyl group sterically impedes N+/Br-
a
association.32 It is possible that a spacer-induced steric
MM2-calculated values. b Estimated from ref 30. c From ref 5.
effect also operates with the C18 geminis (Figure 4). Thus,
the cmcs should rise as the spacers increase in area, the
counterions have greater difficulty in binding, and the
micelles experience an overall higher cationic charge.
Why should a presumed steric effect on ion-binding
manifest itself only with chain lengths of 18? With
increasing chain lengths, headgroup charge density
becomes greater at the micelle surface.32 This serves to
accentuate the sensitivity to ion binding as affected by
the spacer area. Such speculation is preliminary and
clearly in need of further data, particularly those from
conductivity and interfacial chemical trapping studies that
measure the degree of micelle/counterion association.33
Also badly needed in the gemini arena is NMR information
Figure 4. Log cmc vs estimated spacer volume for C18-chain
geminis. Points correspond to data in Table 4. on spacer conformation and on micelle morphology.13-15
In summary, five sets of C4-spacer dicationic gemini
headgroup separation for CTAB micelles (7.9 Å).14 It is surfactants of variable headgroups, spacers, and coun-
interesting to note that 18-5-18 and 18-p-xylyl-18, terions were prepared and studied for their surface
whose spacers possess N+-N+ distances closest to the activities. Cmcs were quite similar for dibromide surfac-
equilibrium value, have cmc values most similar to that tants from C8 to C16, proving heterocyclic surfactants A
of octadecyltrimethylammonium bromide (2.5 × 10-4 M and B to be viable geminis. At C18 chain-length, m-s-m
at 25 °C).31 For these two C18 surfactants, the “gemini gemini E-18 deviated from the expected logarithmic
effect” on cmcs is essentially eliminated. A clear depend- decrease with increasing chain length, contrary to previous
ence of cmc on N+-N+ distance (i.e., spacer length) is not assumptions of m-s-m geminis. Comparison of cmc
present for this set of seven geminis. Log cmc values plotted values for seven C18 dibromide gemini surfactants indi-
against spacer area, however, create a reasonably smooth cated a possible relationship between this deviatory
curve of increasing cmc with larger spacer area (Figure behavior and spacer area, an effect explained in terms of
4). packing constraints on the micelles.
Since issues of micelle structure and properties are
almost always complex and multifaceted, we can only Experimental Section
speculate as to why cmcs get larger as the C18 gemini
spacers increase in area from 2-butynyl to pentyl in Figure General Methods. 1H NMR and 13C NMR spectra were
4 and Table 4. Note that this runs counter to what one recorded on Varian INOVA 400, Varian Mercury 300, or General
would expect on a purely hydrophobic basis, where larger Electric QE 300 spectrophotometers. Mass spectral data were
spacers should enhance the propensity to self-assemble. obtained from the Emory University Mass Spectrometry Center.
It is relevant in this regard that previous studies on Atlantic Microlabs (Norcross, GA) performed elemental analyses.
C12H25NRMe2+Br- revealed that an increase in R’s chain Melting points were taken on a Thomas-Hoover apparatus and
length diminishes the cmc, an effect explained in terms are uncorrected. Product yields were not optimized.
of actual entry of the R groups into the micellar interior.32 Materials. All solvents and reagents were purchased from
A similar phenomenon for the geminis is not possible Aldrich except for N,N′-dimethyltetradecylamine, N,N′-dimeth-
ylhexadecylamine, and N,N′-dimethyloctadecylamine (Pfaltz and
because spacers (unless they are long and flexible) are Bauer).
more-or-less confined to the micelle surface. In the absence
Surface Tensiometry. Surface tension measurements were
of a compensating internalization, therefore, a larger performed on a Fisher surface tensiomat du Nuoy apparatus
spacer will impede micellization owing to the difficulties with a 6 cm Pt/Ir ring. Milli-Q purified water (18 MΩ‚cm
of packing the spacer on a curved surface. By way of resistance) was used for all preparations. For measurements at
analogy, it is easier to cover a ballroom light reflector 23 °C, 10 measurements were taken for each concentration (at
with small mirrored squares than with large rectangular least eight concentrations per sample to acquire an adequate
ones. As a consequence, the cmcs rise with spacer area in cmc). Measurements at 50 °C were taken with a specially designed
Figure 4. Indeed, as already mentioned, the cmc of 18- water-jacketed flask attached to a Lauda M3 circulating bath to
5-18 is similar to that of its single-chained analogue. control temperatures to (0.5 °C. For C18-chained surfactants,
We can use the same rationale to explain the abnormally solutions were equilibrated for 1 h before single measurements
were taken for each concentration.5 Extra care was taken to avoid
high cmcs of the 18-4-18 gemini E-18 in Figure 2. Its disturbing the interface during measurements.
(30) Bondi, A.; J. Phys. Chem. 1964, 68, 441.
(31) Ouni, S.; Hafiane, A.; Dhahbi, M. J. Chim. Phys. 1998, 95, 911. (33) Chaudhuri, A.; Romsted, L. S.; Yao, J. J. Am. Chem. Soc. 1993,
(32) Zana, R. J. Colloid Interface Sci. 1980, 78, 330. 115, 8362.
Gemini Surfactants with Acetylenic Spacers Langmuir, Vol. 16, No. 5, 2000 2067

Gibbs molecular areas were determined with tensiometry data water. The solution was applied ∼3 cm from the conducting pin
using in 10-12 droplets. The film was subsequently allowed to dry for
10 min. At that time, the barriers were compressed at a rate of
1 dγ 4 Å2 chain-1 min-1 and the data were recorded. After completion,
Γ)- (
2.30nRT d log C )
T
(1) the apparatus was vigorously cleaned and the protocol was
repeated (10 times for each surfactant).
MM2 Calculations. Calculations were carried out on a Micron
area ) (NAΓ)-1 (2)
PC using CS Chem 3D Pro software. Molecules were energy
minimized in the gas phase using the MM2 force field with a
where Γ ) surface excess concentration, n ) 3 (constant used in minimum root-mean-square gradient of 0.025. To estimate “all-
previous Gibbs analyses of geminis with flexible spacers),20,21 R anti” areas, 180° 1,4-dihedral angles were imposed on the carbon
) 8.32 J mol-1 K-1, T ) temperature in kelvins (here, 296.15 or chains. For “vertical tails” spacer-headgroups area estimations,
323.15 K), γ ) surface tension in newtons per meter, C ) the N-methylenes of the carbon chains were forced perpendicular
concentration in moles per liter, and NA ) 6.022 × 1023 (Avogadro’s to the plane of the spacer-headgroups. Area estimations were
number).34 then based on rectangular cross-sections of the molecules, with
Pressure-Area Isotherms. A Kibron µTrough was used for widths and lengths based upon furthest atomic distances plus
pressure-area isotherm measurements. The general procedure van der Waals radii (2 × 1.20 Å), except for the “all-anti” areas,
was as follows: The trough and Teflon barriers were thoroughly with which the width of geminal hydrogens on the chains plus
cleaned with ethanol and deionized water and dried with van der Waals radii (4.2 Å) was used as the “average” width of
compressed air. The conducting pin was also rinsed in ethanol the fully extended molecule.
and flame-dried. On a level marble table, 18 mL of Milli-Q purified
water (18 MΩ‚cm resistance) was applied as the subphase and Acknowledgment. This work was supported by the
evened manually with the barriers. The instrument was then Army Research Office.
initialized and the air/water interface was calibrated (∆V ∼ 4000
mV). The barriers were adjusted to their starting positions and Supporting Information Available: Details of syn-
the “zero” pressure was set. The monolayer of surfactant was thesis and characterization of 3, 4, and gemini surfactants
formed by application of 10 µL of CHCl3/MeOH solution [9/1 or A-E. Supporting Information is available free of charge via the
7/3 (v/v) for B-18] via a Hamilton syringe to the surface of the Internet at http://pubs.acs.org.
(34) Li, Z. X.; Dong, C. C.; Thomas, R. K. Langmuir 1999, 15, 4392. LA9910576