O O H 2 N NH 2 O OH NH 2 1 2 O LiAlH 4 NH 2 NH 2 2 3 NH 2 Boc 2 O 3 4 N H boc N H boc [Pt] HSi(OEt) 3 (EtO) 3 Si N H boc 4 5 Supplementary Figure S1 Synthesis of tri(ethoxy)silane with boc-protected amino group. The 4 step synthesis of compound 5 starting from undec-10-enoic acid is shown.
Supplementary Figure S2 1 H NMR spectrum of the bolaform surfactant. The spectrum shows signals correlating to NH 3 (δ= 7.56 ppm), CH 2 -NH 3 (δ= 2.77 ppm), CH 2 groups of the alkyl chain (δ= 1.7 1.1 ppm) and CH 2 -Si (δ= 0.72 ppm) groups of the POMBOLA surfactant.
Supplementary Figure S3 31 P NMR spectrum of the bolaform POM surfactant. The observed 31 P NMR signal at δ= -13.84 ppm is typical for organically modified [PW 11 O 39 ] polyoxometalates.
Supplementary Figure S4 29 Si NMR spectrum of the bolaform POM surfactant. The chemical shift at δ= -51.2 ppm correlates to [PW 11 O 39 ] cluster modified by organosilanes.
Supplementary Figure S5 183 W NMR spectrum of the bolaform POM surfactant. The signals of the POMBOLA surfactant appear at δ = -97.87 (2W), -103.36 (2W), -107.25 (1W), -120.80 (2W), -198.43 (2W), -251.02 (2W) and exhibit the expecting pattern. The signal at δ = -87 ppm correlates to the [PW 12 O 40 ] Keggin ion. The excessive intensity is caused by the correlation to twelve W-atoms and the exceptional symmetry of the Keggin ion. The intensity of the 31 P NMR (fig. S3) signal of the Keggin ion (δ = -15.6 ppm) is vanishingly low compared to the signal appeared in the 183 W NMR spectrum.
Supplementary Figure S6 FT-Raman spectrum (POM region) of the bolaform surfactant. The Raman spectrum confirms the existence of the organically modified [PW 11 O 39 ] cluster deductive by the vibration of the terminal W=O bonds at 999 and 983 cm -1.
Supplementary Figure S7 FT-IR spectrum of the bolaform surfactant. Typical vibrations of the organically modified [PW 11 O 39 ] head can be observed in the range between 1200 and 650 cm -1.
Supplementary Figure S8 DLS particle size distribution curves of aqueous samples with various amount of POMBOLA. The series of measurements shows the relatively low influence of the concentration on the self-assembly behavior. There are no aggregates below a concentration of 0.01 g/l and above 0.25 g/l there is a second distribution with a hydrodynamic radius of around 2 nm.
Supplementary Figure S9 Additional TEM micrographs. Vesicular aggregates of uniform size and their agglomeration behavior are observable on TEM pictures at lower magnification (top: scalebar 200nm; bottom: scalebar 500 nm).
a b c Supplementary Figure S10 EDX data. (a) STEM image of a POMBOLA sample with the selected five points for line-scan EDX measurement. (b) A typical EDX spectrum obtained by one of the five points. (c) Profile of the present amount of various elements along a line passing through a vesicle.
a b Supplementary Figure S11 Analysis of the SAXS measurement. (a) Porod and (b) Kratky plot from SAXS diffraction pattern of an aqueous vesicle solution. The slope of the Porod plot logi vs. logq is -3.5 which lies in the range fitting to spherical aggregates. The pattern of the Kratky plot q 2 I vs. q exhibits one maximum in the low-q region which is typically for aggregates with spherical shape.
Supplementary Figure S12 Determination of the radius of gyration. The slope of the low-q Guinier plot from SAXS diffraction pattern of an aqueous vesicle solution is equal to -R G 2 /3. The calculated radius of gyration is 8.31 nm.
a b c Supplementary Figure S13 Metachromatic effect of MB. (a) UV/Vis spectra of aqueous solutions of MB loaded vesicles (black line), of MB and the Keggin ion [PW 12 O 40 ] 3- (red line), and pure MB (blue line). (b) TEM image (scalebar 200nm) and (c) DLS of MB loaded vesicles. The entrapped MB has no influence on the morphology, only the size and the polydispersity of the vesicles increase (b, c). If there is a symmetrical MLM the POM head groups will also be present at the inner surface and a short-wavelength shift of the MB absorption will occur. In contrast, there is no blue shift of the MB absorption observable indicating the presence of the POMs on the outer surface (a). However, the intensity of the MB monomer signal (668 nm) decreases and
the intensity of the dimer signal (617 nm) increases. This is caused by the confinement effect of the inner water phase which promotes the MB dimer formation. As a reference, the MB absorption was investigated in the presence of the negatively charged Keggin ion [PW 12 O 40 ] 3- (a) and without any additives (a). The dye exhibits a strong metachromatic effect leading to an absorption maximum at 610 nm with a shoulder on the shortwavelength side.
Supplementary Figure S14 Different fluorescence emissions of calcein dependent on the location of the dye. Emission spectra of conventional calcein solution (circles), calcein solution confined to POMBOLA MLM vesicles (squares) and after treatment with a ph = 7.4 buffer (triangles).