Sweet Surfactants: Packing Parameter-Invariant Amphiphiles as Emulsifiers and Capping Agents for Morphology Control of Inorganic Particles

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1 Electronic Supplementary Material (ESI) for Soft Matter. This journal is The Royal Society of Chemistry 2018 I/ [a.u.] I/ [a.u.] Sweet Surfactants: Packing Parameter-Invariant Amphiphiles as Emulsifiers and Capping Agents for Morphology Control of Inorganic Particles Michael Voggel, a Rebecca M. Meinusch, a Vanessa Siewert, a Marius Kunkel, a Valentin Wittmann a * and Sebastian Polarz a * Electronic Supporting Information Fig. ESI-1. (a) SAXS patterns of ManaCn surfactants. ManaC uns 12 ManaC 12 ManaC 10 ManaC q/ [nm -1 ] (b) SAXS patterns of ManbCn surfactants. ManbC uns 12 ManbC 12 ManbC q/ [nm -1 ]

2 I/ [a.u.] I/ [a.u.] (c) SAXS patterns of GalaCn surfactants. GalaC uns 12 GalaC 12 GalaC q/ [nm -1 ] (d) SAXS patterns of GalbCn surfactants. GalbC uns 12 GalbC 12 GalbC 10 GalbC q/ [nm -1 ]

3 Fig. ESI-2. ITC data. (a) Integrated ITC data of GalaC CAC: ± 3.0 mm (b) Integrated ITC data of GalaC CAC: ± 0.54 mm

4 (c) Integrated ITC data of GalbC CAC: ± 9 mm (d) Integrated ITC data of GalaC CAC: 0.80 ± 6 mm

5 (e) Integrated ITC data of GalaC uns CAC: 1.02 ± 4 mm (f) Integrated ITC data of GalbC uns CAC: 1.12 ± 8 mm

6 (g) Integrated ITC data of ManaC CAC: ± 1.3 mm (h) Integrated ITC data of ManaC CAC: ± 0.10 mm

7 (i) Integrated ITC data of ManbC CAC: ± 0.52 mm (j) Integrated ITC data of ManaC CAC: 0.78 ± 3 mm

8 (k) Integrated ITC data of ManbC CAC: 1.52 ± 4 mm (l) Integrated ITC data of ManaC uns CAC: 0.33 ± 1 mm

9 (m) Integrated ITC data of ManbC uns CAC: 0.20 ± 2 mm (n) Integrated ITC data of MalbC CAC: ± 2.0 mm

10 (o) Integrated ITC data of MalbC CAC: ± 0.46 mm (p) Integrated ITC data of MalbC CAC: 2.67 ± 1 mm

11 (q) Integrated ITC data of MalaC CAC: 0.70 ± 2 mm (r) Integrated ITC data of MalbC CAC: 0.16 ± 1 mm

12 (s) Integrated ITC data of GlcbC CAC: ± 4.9 mm (t) Integrated ITC data of GlcbC CAC: ± 0.52 mm

13 (u) Thermodynamic data of demicellation determined via ITC GalaC6 ManaOC6 GlcaC6 MalbC6 cmc [x10-4 ] ± ± ± ± 0.36 ln cmc ± ± ± ± 1 ΔG demic [kj mol -1 ] ± ± ± ± 2 ΔH demic [kj mol -1 ] ± ± ± ± 0.40 TΔS demic [kj mol -1 ] ± ± ± ± 0.42 ΔS demic [J K -1 mol -1 ] ± ± ± ± 1.42 GalaC8 GalbC8 ManaC8 ManbC8 GlcbC8 MalbC8 cmc [x10-4 ] 4.93 ± ± ± ± ± ± 2 ln cmc ± ± ± ± ± ± 1 ΔG demic [kj mol -1 ] ± ± ± ± ± ± 1 ΔH demic [kj mol -1 ] ± ± ± ± ± ± 5 TΔS demic [kj mol -1 ] ± ± ± ± ± ± 6 ΔS demic [J K -1 mol -1 ] ± ± ± ± ± ± 0.22 ManaC10 ManbC10 GalaC10 MalbC10 cmc [x10-4 ] 0.14 ± ± ± ± 1 ln cmc ± ± ± ± 1 ΔG demic [kj mol -1 ] ± ± ± ± 1 ΔH demic [kj mol -1 ] ± ± ± ± 4 TΔS demic [kj mol -1 ] ± ± ± ± 4 ΔS demic [J K -1 mol -1 ] ± ± ± ± 0.14

14 MalaC12 MalbC12 cmc [x10-4 ] 0.13 ± 1 3 ± 1 ln cmc ± ± 3 ΔG demic [kj mol -1 ] ± ± 8 ΔH demic [kj mol -1 ] ± ± 0.14 TΔS demic [kj mol -1 ] ± ± 0.22 ΔS demic [J K -1 mol -1 ] ± ± 0.75 GalaC uns 12 GalbC uns 12 ManaC uns 12 ManbC uns 12 cmc [x10-4 ] 0.18 ± ± 2 6 ± 1 4 ± 1 ln cmc ± ± ± ± 0.11 ΔG demic [kj mol -1 ] ± ± ± ± 0.27 ΔH demic [kj mol -1 ] ± ± ± ± 0.27 TΔS demic [kj mol -1 ] ± ± ± ± 0.38 ΔS demic [J K -1 mol -1 ] ± ± ± ± 1.29

15 av. surface tension / [mn/m] Fig. ESI-3. Tensiometry data. (a) Concentration dependent surface tension of an aqueous solution of GalbC E-6 1E-5 1E concentration / [mm] (b) Concentration dependent surface tension of an aqueous solution of GalbC uns E-7 1E-6 1E-5 1E concentration / [mm] av. surface tension / [mn/m]55

16 av. surface tension / [mn/m] av. surface tension / [mn/m] av. surface tension / [mn/m] (c) Concentration dependent surface tension of a saturated aqueous solution of GalaC dilution / [xsaturated] (d) Concentration dependent surface tension of a saturated aqueous solution of GalbC dilution / [xsaturated] (e) Concentration dependent surface tension of a saturated aqueous solution of ManaC dilution / [xsaturated]

17 av. surface tension / [mn/m] av. surface tension / [mn/m] (f) Concentration dependent surface tension of a saturated aqueous solution of GlcbC dilution / [xsaturated] (g) Concentration dependent surface tension of a saturated aqueous solution of XylbC dilution / [xsaturated]

18 Fig. ESI-4. HLB values.

19 Fig. ESI-5. TEM micrographs. (a) ZnO nanoparticles synthesized in the presence of MalbC12

22 (b) ZnO nanoparticles synthesized in the presence of GalaC12 (including angle analysis)

Chemistry 123: Physical and Organic Chemistry Topic 2: Thermochemistry S H 2 = S H 2 R ln P H2 P NH

Chemistry 123: Physical and Organic Chemistry Topic 2: Thermochemistry S H 2 = S H 2 R ln P H2 P NH N (g) + 3 H (g) NH 3 (g) S N = S H = S NH 3 = S N R ln P N S H R ln P H S NH 3 R ln P NH3 ΔS rxn = (S Rln P NH 3 NH3 ) (S N Rln P N ) 3 (S H Rln P H ) ΔS rxn = S S NH 3 N 3S H + Rln P P 3 N H ΔS rxn =