d6) d (ppm) 172.48, 167.61, 144.06, 131.02, 125.49, 118.89, 78.65,
78.64, 66.04, 37.17, 31.99, 29.70, 29.64, 29.55, 29.40, 29.34, 29.28,
29.08, 29.01, 28.88, 28.85, 28.40, 28.38, 25.63, 22.79, 18.97, 14.64.
FAB HRMS m/z ¼ 494.3634 [M + H]+, calc. for C32H48O3N ¼
494.3636.
Fluorescence titrations
Stock solutions of PDAs (100 mM) were prepared by mixing
100 mL PDAs (1 mM) and 900 mL of HEPES buffer (10 mM,
pH 7.4). Both the excitation and emission slit widths were 5 nm
per 5 nm.
Dynamic light scattering (DLS) and transmission electron
microscopy (TEM)
Synthesis of 4-(2-pentacosa-10,12-diynamidoethyl)benzoic acid (3)
The diacetylene monomer was prepared from commercially
available 10,12-pentacosadiynoic acid by amide formation. To
a solution containing 0.50 g (1.34 mmol) of 10,12-pentacosa-
diynoic acid in 20 mL of methylene chloride, 0.35 mL
(4.14 mmol, 3.1eq) of oxalyl chloride was added dropwise at
room temperature. The resulting solution was stirred at room
temperature under N2. After 1 hour, a catalytic amount of DMF
was added to the solution. The resulting solution was stirred for
an additional 3–4 hours. After evaporation of the solvent in
vacuo, the residue was redissolved in 10 mL of THF. The
resulting solution was added dropwise to the solution containing
0.40 g (1.99 mmol) of 4-(2-aminoethyl)benzoic acid dissolved in
5 mL THF and 5 mL pyridine in an ice bath. The resulting
mixture was stirred overnight at room temperature under N2.
The solvent was dropped to DW to give 0.47 g (67.22%) of the
The apparent sizes of PDA solutions in HEPES (10 mM, pH 7.4)
were observed byꢂa dynamic light scattering instrument (ALV
5000-60X0) at 25 C. Transmission electron microscopy (TEM)
images were acquired on a JEM-2100F TEM operating at an
acceleration voltage of 200 kV. TEM samples were prepared by
depositing several drops of diluted solution onto standard
carbon-coated copper grid, followed by drying under ambient
conditions overnight.
Acknowledgements
This work was supported by the National Research Foundation
(NRF) grants (2011-0020450, 20110001334) and WCU
(R31-2008-000-10010-0) Seoul R&BD Program (10816). The
work at SKKU was supported by the NRF grant (no.
20110001211).
1
desired monomer. H NMR (300 MHz, DMSO-d6): d (ppm):
0.78–0.83 (t, J ¼ 6.3 Hz, 3H), 1.24–1.48 (m, 32H), 1.98–2.03 (t, J
¼ 7.5 Hz, 2H), 1.26–2.21 (t, J ¼ 7.5 Hz, 2H), 2.25–2.29 (t, J ¼ 6.9
Hz, 4H), 2.44–2.92 (t, J ¼ 7.2 Hz, 2H), 7.30–7.33 (d, J ¼ 8.4 Hz,
2H), 7.84–7.87 (d, J ¼ 8.4 Hz, 2H), 12.05 (s, 1H). 13C NMR
(500 MHz, CDCl3) d (ppm) 173.48, 171.19, 145.58, 130.77,
129.17, 127.87, 76.99, 65.54, 65.45, 40.44, 36.99, 14.06, 32.15,
29.88, 29.86, 29.84, 29.71, 29.58, 29.33, 29.29, 29.22, 29.10, 28.98,
28.52, 24.88, 22.92, 19.44, 19.42, 14.35. FAB HRMS m/z ¼
522.3947 [M + H]+, calc. for C34H52O3N ¼ 522.3949.
Notes and references
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Preparation of diacetylene assembly and photopolymerization
Preparation of lipid solution in aqueous solution was achieved by
the following method. A monomer was dissolved in 1 mL of
DMSO. While shaking 19 mL of HEPES buffer (10 mM, pH
7.4), the dissolved monomer was slowly added dropwise to yield
a total monomer concentration of 1 mM. The solution was
sonicated at 80 ꢂC for 40 min and then was passed through
a syringe filter to remove the lipid aggregates, and was cooled and
stored at 0 ꢂC overnight. The diacetylene monomer was poly-
merized by irradiation with 254 nm of UV light (1 mW cmꢀ2).
Liposome containing 4-hydroxybenzoic acid was named PCDA-
HBA, liposome containing 4-aminobenzoic acid was named
PCDA-ABA, and liposome containing 4-aminoethyl benzoic
acid was named PCDA-EBA.
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UV titrations
In a typical experiment, 100 mM of stock solution was prepared
by placing 100 mL of the PDAs (1 mM) into a test tube, diluting
the solution to 900 mL with 10 mM HEPES (pH 7.4). UV titra-
tion was performed using 100 mM solution of PDA-DPA in
HEPES (10 mM, pH 7.4).
This journal is ª The Royal Society of Chemistry 2011
J. Mater. Chem., 2011, 21, 17160–17166 | 17165