Supporting Information
Metallosurfactant Cn-Cu-Cn: Vesicle Formation and Its Drug Controlled-Release Properties
Quanwen Zha, Qiulan Xie, Yimin Hu, Jie Han,* Lingling Ge, Rong Guo*
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, Jiangsu, P. R. China,
*Corresponding Author:
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Synthesis of sodium alkyliminodiacetate (SAIDA)
The SAIDA was synthesized according to Eq. 1 by reacting CnH2n+1NH2 (n = 8, 12, 16) with ClCH2COOH in water and stirred overnight at 90 ºC with pH = 12 adjusted by NaOH solution. After removal of the solvent, the residues were refluxed in ether for 0.5 h three times. The crude products were extracted with ethanol/water three times.
(1)
Synthesis of Cn-Cu-Cn
The Cn-Cu-Cn was synthesized according to Eq. 2, whereby CuCl2·2H2O solution was added dropwise into SAIDA solution in water and ethanol. The mixture was stirred overnight at 60 ºC. Then, the reaction mixture was cooled to room temperature and precipitated by adding excess amount of acetone. The solvents were removed under reduced pressure. The residues were washed with ethanol and acetone for several times, and then dried in vacuo at room temperature.
(2)
Characterization of metallosurfactants.
Na2{Cu[C8H17N(CH2COO)2]2} (C8-Cu-C8), IR (cm-1): 1606 (νas(COO-)), 1385 (νs(COO-)), 551 (ν(Cu-N)), 443 (ν(Cu-O)), Δν(COO-) = 221. 1H-NMR (600 MHz, D2O, δ-ppm): 0.741-0.761 (t, 6H), 1.154-1.272 (m, 20H), 1.560-1.576 (m, 4H), 3.097-3.120 (t, 4H), 3.650 (s, 8H). LC-MS Calcd (m/z): 596. Found, 550 [M-2Na+]. Anal. Calcd for C8-Cu-C8：C 48.35, H 7.10, N 4.70. Found: C 48.69, H 7.25, N 4.55.
Na2{Cu[C12H25N(CH2COO)2]2} (C12-Cu-C12), IR (cm-1): 1607 (νas(COO-)), 1379 (νs(COO-)), 527 (ν(Cu-N)), 434 (ν(Cu-O)), Δν(COO-) = 228. 1H-NMR (600 MHz, D2O, δ-ppm): 0.717-0.739 (t, 6H), 1.147-1.216 (m, 36H), 1.570-1.594 (m, 4H), 3.094-3.107 (t, 4H), 3.650 (s, 8H). LC-MS Calcd (m/z): 708. Found, 662 [M-2Na+]. Anal. Calcd for (C12-Cu-C12): C 54.26, H 8.25, N 3.95. Found: C 54.38, H 8.32, N 3.92.
Na2{Cu[C16H33N(CH2COO)2]2} (C16-Cu-C16), IR (cm-1): 1614 (νas(COO-)), 1385 (νs(COO-)), 528 (ν(Cu-N)), 441 (ν(Cu-O)), Δν(COO-) = 229. 1H-NMR (600 MHz, D2O, δ-ppm): 0.708-0.743 (t, 6H), 1.150-1.212 (m, 52H), 1.567-1.596 (m, 4H), 3.091-3.193 (t, 4H), 3.658 (s, 8H). LC-MS Calcd (m/z): 820. Found, 774 [M-2Na+]. Anal. Calcd: C 58.55, H 9.09, N 3.41. Found: C 58.62, H 9.10, N 3.47.
Fig. S1. 1H NMR spectra of SDIDA(C12) and C12-Cu-C12
Fig. S2. Variation of surface tension with the Cn-Cu-Cn (n = 8, 12, 16) concentrations at 25 oC
Fig. S3. Electrical conductivity of the Cn-Cu-Cn aqueous solution with concentration.
Fig.S4. Volume weighted distribution functions of C8-Cu-C8 system at different concentration (mM): (a) 8, (b) 10, (c) 15, (d) 20, and (e) 30.
Fig. S5. Volume weighted distribution functions of C16-Cu-C16 system at different concentration: (mM): (a) 0.5, (b) 0.8, (c) 1.0, (d) 1.2, and (e) 1.5.
Fig. S6. Negative-staining TEM images for Cn-Cu-Cn systems: (a) 20 mM C8-Cu-C8, (b) 1.5 mM C16-Cu-C16.
Fig. S7. Negative-staining TEM images for C12-Cu-C12 system (10 mM) at 85 oC with different time (min): (a) 30, (b) 60, (c) 120, and (d) 180.
Fig. S8. FT-IR spectra of C12-Cu-C12 system after dialysis.
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