supporting information inverse pm n cubic micellar ... · inverse pm!n cubic micellar lyotropic...

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Supporting Information

Inverse Pm!n Cubic Micellar Lyotropic Phases from Zwitterionic Triazolium Gemini Surfactants

Dominic V. Perroni and Mahesh K. Mahanthappa*

Department of Chemistry, University of Wisconsin–Madison, 1101 University Ave., Madison, WI 53706

*Corresponding author: [email protected]

Table of Contents! Page!

General Synthetic and Characterization Protocols S2

General Procedures for Synthesis and Characterization data for Compounds 1 and 2 S2-5

Gemini LLC Sample Preparation S6

X-Ray Diffraction Experimental Conditions S6

Retrostructural Analysis S7

Figure S1. Azimuthally integrated synchrotron XRD pattern of a hexagonally packed cylinders phase derived from 79.45 wt% 1 in water at 30 °C.

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Figure S2. Azimuthally integrated synchrotron XRD pattern of a coexistence between the micellar cubosome phase with Pm!n symmetry and a hexagonally packed cylinders phase derived from 69.17 wt% 2 in water at 30 °C.

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Figure S3. Azimuthally integrated synchrotron XRD pattern of a micellar cubosome phase with Pm!n symmetry derived from 59.94 wt% 2 in water at 30 °C.

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Figure S4. Azimuthally integrated synchrotron XRD pattern of a hexagonally packed cylinders phase derived from 79.53 wt% 1 in water at 60 °C.

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Figure S5. Azimuthally integrated synchrotron XRD pattern of isotropic solution derived from 10.06 wt% 1 in water at 80 °C.

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Table S1. The calculated and experimental peak positions for a micellar cubosome phase with Pm!n (space group Q223) symmetry derived from 70.0 wt% 1 in water at 30 °C.

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References !

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Electronic Supplementary Material (ESI) for Soft MatterThis journal is © The Royal Society of Chemistry 2013

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Materials. All materials and reagent grade solvents were purchased from Sigma-Aldrich

Chemical Co. (Milwaukee, WI) and used as received unless otherwise noted.

Molecular characterization. 1H NMR and 13C NMR spectra were obtained at 22 °C using a

Bruker AC+ 300 or Varian INOVA 500 spectrometer in CDCl3. 1H spectra were referenced

relative to a tetramethylsilane internal standard. 13C spectra were referenced using the Unified

Scale method1. IR spectra of powder samples were acquired using a Bruker Tensor FTIR from

4000 – 900 cm-1 equipped with an attenuated total reflectance (ATR) stage. Elemental analyses

(C, H, N, S) were conducted by Atlantic Microlab, Inc. (Norcross, GA, USA).

1-Azidododecane.2 A 250 ml round bottom flask equipped with a stirbar was charged with

sodium azide (4.000 g, 61.53 mmol) and DMSO (135 mL). This mixture was stirred and

occasionally heated to ~80 °C for ~2 h to furnish a homogeneous solution. This solution was

cooled to 22 °C and 1-bromododecane (10.1 mL, 42.06 mmol) was added all at once to give a

clear yellow solution. The reaction mixture was stirred at room temperature for 24 h, after which

this solution was poured into 300 mL of H2O. CAUTION: This dilution step is quite

exothermic!! Once cooled the DMSO/H2O solution was transferred to a separatory funnel and

extracted with ether (2 x 200 mL). The ether portions were combined and washed with H2O (3 x

300 mL). The organic layer was then dried over MgSO4(s) and the solvent was removed under

reduced pressure to yield a clear yellow oil. Yield 8.200 g (92% yield). 1H NMR: (300 MHz,

CDCl3) ! 3.26 (CH2-N3, t, J = 7.0 Hz, 2H), 1.57 (CH2-CH2N3, quin, J = 7.2 Hz, 2H), 1.42–1.21

(CH2, m, 18H), 0.88 (CH3, t, J = 7.0 Hz, 3H).

1-Azidodecane.2 Synthesized from sodium azide (2.216 g, 34.09 mmol) and 1-bromodecane

(4.70 mL, 22.64 mmol) per the above procedure. Yield: 3.578 g (86% yield). 1H NMR: (300


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MHz, CDCl3) ! 3.26 (CH2-N3, t, J = 7.0 Hz, 2H), 1.57 (CH2-CH2N3, quin, J = 7.2 Hz, 2H), 1.43–

1.12 (CH2, m, 14H), 0.883 (CH3, t, J = 7.0 Hz, 3H).

1,4-Bis(1-dodecyl-1H-1,2,3-triazole-4-yl)butane. 1-Azidododecane (7.609 g, 36.00 mmol)

and CuSO4• 5H2O (0.2257 g, 0.9039 mmol) were dissolved in MeOH (150 mL). In a separate

vial, ascorbic acid (1.580 g, 8.973 mmol) was mixed with NaOH (0.3775 g, 9.438 mmol) in H2O

(3 mL). This freshly prepared sodium ascorbate(aq )was added to the methanolic solution to

yield a deep brown solution. 1,7-Octadiyne (2.20 mL, 16.58 mmol) was added to this solution in

a single aliquot, and the reaction mixture was heated to 40 °C for 24 h. During this time, the

solution became cream colored. The reaction mixture was subsequently diluted with CHCl3 (150

mL), H2O (150 mL), conc. NH4OH (50 mL), and saturated NaCl(aq) (10 mL). This biphasic

mixture was filtered through a plug of Celite to remove any solid materials. In a separatory

funnel, the resulting filtrate was separated into organic and aqueous layers. The aqueous layer

was extracted additional CHCl3 (2 x 150 mL). The combined organic layers were washed with a

H2O(l) (150 mL) and conc. NH4OH (50 mL) solution three times to remove residual copper salts.

The combined organic layers were repeatedly washed with H2O(l) until the pH of the aqueous

layer was neutral. This layer was dried over MgSO4(s) and the solvent was removed in vacuo.

The resulting off white powder was triturated with ether (50 mL) to remove any unreacted alkyl

azide. The solid was filtered and vacuum dried to yield a white powder. Yield: 5.9737 g (69.79

%). 1H NMR: (300 MHz, CDCl3) ! 7.268 (N-CH=C, s, 2H), 4.29 (CH2-CH2-N, t, J = 7.2 Hz,

4H), 2.75 (C-CH2-CH2, br, 4H), 1.87 (N-CH2-CH2-, br, 4H), 1.75 (C-CH2-CH2, br, 4H), 1.40–

1.16 (-CH2-, br, 36H), 0.879 (-CH3, t, J = 7.0 Hz, 6H) 13C NMR: (75.375 MHz, CDCl3) ! 148.1,

120.7, 50.39, 32.10, 30.56, 29.81, 29.72, 29.59, 29.53, 29.46, 29.22, 29.20, 26.74, 25.64, 22.89,

14.32.


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1,4-Bis(1-decyl-1H-1,2,3-triazole-4-yl)butane. Synthesized from 1-azidodecane (7.348 g,

40.09 mmol), CuSO4•5H2O (0.2547 g, 1.020 mmol), ascorbic acid (1.764 g, 10.02 mmol), NaOH

(0.4127 g, 10.32 mmol), and 1,7-Octadiyne (2.4 mL, 18.08 mmol). Yield: 7.063 g (83.09 %)

NMR: (300 MHz, CDCl3) ! 7.27 (N-CH=C, s, 2H), 4.29 (CH2-CH2-N, t, J = 7.2 Hz, 4H), 2.75

(C-CH2-CH2, br, 4H), 1.87 (N-CH2-CH2-, br, 4H), 1.76 (C-CH2-CH2, br, 4H), 1.43–1.19 (-CH2-,

br, 28H), 0.88 (-CH3, t, J = 7.0 Hz, 6H) 13C NMR: (125.9 MHz, CDCl3) ! 150.6, 123.0, 52.84,

34.40, 33.00, 32.11, 32.03, 31.90, 31.66, 31.63, 29.18, 28.08, 25.30, 16.74.

1,4-Bis(1-dodecyl-1H-1,2,3-triazole-4-yl)butane bis(sulfobetaine).3 A 150 mL Schlenk

tube was charged with a stirbar, followed by 1,4-bis(1-dodecyl-1H-1,2,3-triazole-4-yl)butane

(2.948 g, 5.574 mmol) and 1,3-propanesultone (2.524 g, 20.66 mmol). 2-Butanone (30 mL) was

added to produce a white heterogeneous mixture. The tube was sealed and placed in an oil bath

at 65 °C. Shortly after heating and stirring the solution, it became clear and colorless. Over the

course of 24 h, a white precipitate was observed in the flask. After 48 h, a large amount of white

precipitate had formed. The hot reaction mixture was vacuum filtered to isolate the white

precipitate. The filter cake was washed with acetone (3 x 100 mL) and was freeze dried from a

C6H6 slurry. Yield: 2.802 g (65.08 %). 1H NMR: (500 MHz, CDCl3) 9.31( N-CH-C-, s, 2H), 4.87

( N-CH2-CH2-, t, J = 7.1 Hz, 4H), 4.60 (CH2CH2N-, t, J = 7.1 Hz, 4H), 3.13 (CCH2 CH2-, br,

4H), 2.82 (CH2CH2S-, br, 4H), 2.51 (NCH2CH2-, br, 4H), 2.04 (CCH2CH2-, br s, 4H), 2.00

(CH2CH2N-, br, quin., 4H), 1.41–1.18 ( -CH2-, br, 36H), 0.877 (-CH3, t, J = 7.2 Hz, 6H) 13C

NMR: (125.7 MHz, CDCl3) !144.7, 129.9, 54.13, 49.45, 46.73, 31.94, 31.93, 29.62, 29.54,

29.43, 29.36, 28.89, 26.24, 26.20, 25.29, 25.26, 22.73, 22.72, 14.16; IR (powder, cm-1) 3423.4,

3164.0, 3086.9, 2918.8, 2849.9, 1659.30, 1650.0, 15583.9, 1467.0, 1371.9, 1286.0, 1270.4,


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1216.2, 1167.2, 1063.7, 1031.9/ Elemental Analysis. Calc.: C38H74N6O6S2•1.10 H2O: C, 57.56;

H, 9.43: N, 10.60; O, 14.33; S, 8.09; Found: C, 57.56; H, 9.26; N, 10.43; S, 8.01.

1,4-Bis(1-decyl-1H-1,2,3-triazole-4-yl)butane bis(sulfobetaine). Synthesized from 1,4-

Bis(1-decyl-1H-1,2,3-triazole-4-yl)butane (3.044 g, 6.439 mmol), 1,3-propansultone( 2.925 g,

23.95 mmol) and 2-butanone (30 mL). Yield: 2.860 g (61.91 %). 1H NMR: (500.2 MHz, CDCl3

9.32 ( NCHC-, s, 2 H), 4.88 ( NCH2CH2-, t, J = 7.1 Hz, 4H), 4.60 (CH2CH2N-, t, J = 7.1 Hz,

4H), 3.13 (CCH2CH2-, br, 4H), 2.83 (CH2CH2S-, br, 4H), 2.50 (NCH2CH2-, br, 4H), 2.05

(CCH2CH2-, br. s, 4H), 2.00 (CH2CH2N-, br, quin., 4H), 1.38–1.19 ( -CH2-, br, 28H), 0.874 (-

CH3, t, J = 7.2 Hz, 6H) 13C NMR: (125.7 MHz, CDCl3) 144.8, 130.0, 54.23, 49.55, 46.81, 29.57,

29.51, 31.96, 29.43, 29.35, 28.97, 26.32, 26.21, 25.36, 22.81, 22.78, 14.23; IR (powder, cm-1)

3424.2, 3163.3, 3081.7, 2919.0, 2850.2, 1583.7, 1467.0, 1421.3, 1371.4, 1285.6, 1214,9, 1180.5,

1166.8, 1063.7, 1031.9. Elemental Analysis. Calc.: C34H64N6O6S2•1.01 H2O: C, 55.55; H, 9.05:

N, 11.43; O, 15.25; S, 8.72; Found: C, 55.55; H, 8.99; N, 11.25; S, 8.64.


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LLC Sample Prep. Aqueous lyotropic liquid crystalline samples were produced in vials by

the addition of precisely massed amounts of ultra-pure water (Type I) to prescribed amounts of

freeze-dried zwitterionic surfactant. The mixtures were subjected to high-speed centrifugation

(5,000 rpm) for 10 min followed by hand mixing with a spatula iteratively, until homogenous

gels were obtained. Tightly sealed samples were protected from light and allowed to rest for at

least 24 hours before X-ray diffraction analysis to allow relaxation of any residual shear stresses

in the samples.

X-Ray Diffraction Synchrotron X-ray diffraction (XRD) patterns were obtained at the 12-

ID-B beamline at the Advanced Photon Source (Argonne, IL). A beam energy of 12 keV (" =

1.034 Å) was utilized with a sample-to-detector distance of 2.252 m. The sample-to-detector

distance was calibrated against a silver behenate standard sample with d = 58.37 Å. A Pilatus 2M

detector (25.4 cm x 28.9 cm) with 1475 x 1697 pixel resolution was used to collect 2D-XRD

patterns. LLC gels were sealed into hermetically sealed aluminum DSC pans, which were

thermostatted at the desired temperature using a Linkham DSC hot stage for at least 5 min prior

to X-ray exposure (typical exposure times ~1s). 2D XRD patterns were azimuthally integrated

using the DataSqueeze software package (http://www.datasqueezesoftware.com) to produce I(q)

v. q 1D XRD patterns. The latter patterns were indexed using the MDI Jade 5 Software

(http://www.materialsdata.com/products.htm).

Supplementary Laboratory XRD measurements were performed on a Rigaku S-MAX

3000 housed in the Materials Science Center at the University of Wisconsin–Madison. Cu-K# X-

rays were focused with a Max-Flux multilayer confocal optic (Osmic, Inc.) and the resulting

beam was collimated and trimmed to a final diameter of 0.5 mm, after passage through three

collimating pinholes. Temperature-dependent SAXS measurements relied on samples sealed


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between Kapton® sheets mounted in Linkam DSC hotstage. Upon thermal equilibration for at

least 10 min at a given temperature, samples were exposed to the X-ray beam for 15-30 min.

Two-dimensional XRD patterns were recorded on a Gabriel X-ray detector (150 mm circular

area) with a sample-to-detector distance of 42.19 cm (calibrated using a silver behenate standard

with d = 58.37Å).

Retrostructural Analysis. The azimuthally integrated I(q) v. q plot for the Pm!n symmetry

LLC produced from 70.0 wt% 1 in H2O was scaled by a factor of 1/10 in q-value. This scaled

XRD pattern was imported into JANA20064 to extract the structure factor intensities and to

determine the Wyckoff positions associated within the unit cell of this morphology.

Subsequently analysis and modeling of the structure factor intensities using the charge-flipping

algorithms in the SUPERFLIP5 software package enabled the construction of the three-

dimensional electron density maps based on the XRD pattern. Volumetric electron density

models were then constructed using the VESTA6 package.


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Figure S1. Azimuthally integrated synchrotron XRD pattern of a hexagonally packed cylinders phase (space group P6/mm) derived from 79.45 wt% 1 in water at 30 °C. The Miller indices associated with the observed peaks are provided, along with the two-dimensional XRD pattern (inset).

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Figure S2. Azimuthally integrated synchrotron XRD pattern of sample derived from 69.17 wt% 2 in water at 30 °C, which exhibits phase coexistence of the Pm!n (space group #223) symmetry LLC and a hexagonally packed cylinders phase. The Miller indices associated with the observed peaks are provided; peaks associated with the hexagonal phase indicated by filled circles. A two-dimensional XRD pattern is also show in the inset.

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Figure S3. Azimuthally integrated synchrotron XRD pattern of a micellar cubosome phase with Pm!n (space group #223) symmetry derived from 59.94 wt% 2 in water at 30 °C. The Miller indices associated with the 17 observable peaks are provided, along with the two-dimensional XRD pattern (inset).

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Fig S4. Azimuthally integrated synchrotron XRD pattern of a hexagonally packed cylinders phase (P6/mm) derived from 79.53 wt% 1 in water at 60 °C. The Miller indices associated with the five observed peaks are provided, along with the two-dimensional XRD pattern (inset).

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Figure S5. Azimuthally integrated synchrotron XRD pattern of isotropic (disordered) solution derived from 10.06 wt% 1 in water at 80 °C. The broad peak near 0.4 A-1 is due to the Kapton polyimide windows of the sample holder.!

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Table S1. The calculated and experimental peak positions for a micellar cubosome phase with Pm!n (space group #223) symmetry derived from 70.0 wt% 1 in water at 30 °C.!

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Miller Index (hkl)

Calculated Peak Positions

q(Å-1)

Experimental Peak Positions

q(Å- 1)

Difference

110 0.129 0.129 0 200 0.182 0.183 0.001 210 0.204 0.204 0 211 0.223 0.224 0.001 220 0.258 0.258 0 310 0.288 0.289 0.001 222 0.316 0.316 0 320 0.329 0.329 0 321 0.341 0.341 0 400 0.365 0.365 0 410 0.376 0.376 0 411 0.387 0.387 0 330 0.387 0.387 0 420 0.408 0.408 0 421 0.418 0.418 0 332 0.428 0.428 0 422 0.447 extinct N/A 430 0.456 0.456 0 431 0.465 0.463 0.002 432 0.491 0.492 0.001 521 0.500 0.500 0

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References

1. R. K. Harris, E. D. Becker, S. M. C. De Menezes, R. Goodfellow and P. Granger, Pure Appl Chem, 2001, 73, 1795-1818.

2. J. Sinha, R. Sahoo and A. Kumar, Macromolecules, 2009, 42, 2015-2022. 3. Y. R. Mirzaei, H. Xue and J. M. Shreeve, Inorg Chem, 2004, 43, 361-367. 4. V. Petricek, Dusek,M. & Palatinus,L., Jana2006. The Crystallographic Computing

System, http://jana.fzu.cz/. 5. L. Palatinus and G. Chapuis, J. Appl. Crystallogr., 2007, 40, 786-790. 6. K. Momma and F. Izumi, J. Appl. Crystallogr., 2011, 44, 1272-1276.


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