Suzana Natour, Suheir Omar and Raed Abu-Reziq*

Supporting Information

Catalysis with Solid Lipid Particles

Suzana Natour, Suheir Omar and Raed Abu-Reziq*

Institute of Chemistry, Casali Center of Applied Chemistry, Center for Nanoscience and Nanotechnology, the Hebrew University of Jerusalem, Israel.

Table S1.Compositions for preparation of catalytic SLPs.a

Formula / Aqueous phase / Oil phase
TDW (g) / Surfactant (g) / Wax (g) / TEOS (g)
1 / 38 / CTAB-1g / Parrafin wax-10g / 10
2 / 38 / CTAB-1g / Parrafin wax -10g / 5
3 / 50 / Brij 78-1.6g / Parrafin wax -10g / 2.5
4 / 50 / Brij 78-1g / Parrafin wax -10g / 10
5 / 47 / Brij 78-3.6g / Parrafin wax -10g / 4
6 / 50 / DC 5329- 1g / Parrafin wax -10g / 10
7 / 32 / G.-KDMP – 2g / Parrafin wax -10g / 2
8b / 32 / G.-KDMP – 2g / Parrafin wax -10g / 2
9 / 20 / Bu-PVP 5%- 19g / Parrafin wax -10g / 4
10b / 20 / Bu-PVP 5%- 19g / Parrafin wax -10g / 4
11 / 20 / Bu-PVP 5%- 19g / Parrafin wax -10g / 6
12 / 20 / Bu-PVP 5%- 19g / Parrafin wax -10g / 10
13 / 50 / Tween 80- 1.6g / Parrafin wax -10g / 2.5
14 / 38 / G.-KDMP-2g / AMS-C30-9g / 4
15 / 38 / DC 5329- 2g / AMS-C30-9g / 4
16 / 20 / Bu-PVP 5%- 19g / AMS-C30-9g / 4
a 1g of PEI-C18 was added to the oil phase in all formulas. After hot emulsification, pH was set to 10 by NaOH 1M. bpH 7.3, no NaOHwas added.

Fig. S1 SEM micrographs of catalytic SLPs prepared by using different surfactants and waxes. a) Brij 78 (Formula 3), b) Brij 78 (Formula 4), c) Brij 78 (Formula 5), d) Genamin KDMP (Formula 14), e) Genamin KDMP (Formula 7)and f) Tween 80 (Formula 13).

Characterization Data of the Knoevenagel Condensation Products

Table 1

2-benzylidenemalononitrile (Entry1)

1H NMR (400MHz, CDCl3): δ 7.90 (d, J =8.5 Hz, 2H), 7.78 (s, 1H), 7.63 (t, J=7.6 Hz, 1H), 7.61 (t, J= 7.6 Hz, 2H) ppm. 13C NMR (100MHz, CDCl3): δ 160.2, 134.7, 130.7, 129.6, 113.8, 112.7, 109.4 ppm.

2-(4-chlorobenzylidene)malononitrile (Entry 4)

1H NMR (400MHz, CDCl3): δ 7.86 (d, J =8.5 Hz, 2H), 7.73 (s, 1H), 7.52 (d, J=8.6 Hz, 2H) ppm. 13C NMR (100MHz, CDCl3): δ 158.6, 141.1, 131.9, 130, 129.3, 113.6, 112.4, 83.1 ppm.

2-(4-cyanobenzylidene)malononitrile (Entry 5)

1H NMR (400MHz, CDCl3): δ 7.98 (d, J =8.4 Hz, 2H), 7.84 (s, 1H), 7.82 (d, J=2.4 Hz, 2H) ppm. 13C NMR (100MHz, CDCl3): δ 157.6, 134.3, 133.1, 130.7, 117.4, 112.8, 111.7, 109.1, 86.7 ppm.

2-(4-nitrobenzylidene)malononitrile (Entry 6)

1H NMR (400MHz,CDCl3): δ 8.38 (d, J =8.8 Hz, 2H), 7.84 (d, J=9.2 Hz, 2H), 7.88 (s, 1H) ppm. 13C NMR (100MHz, CDCl3): δ 156.9, 150.9, 135.8, 131.3, 124.6, 112.6, 111.6, 87.5 ppm.

2-(2-nitrobenzylidene)malononitrile (Entry 7)

1H NMR (400MHz, CDCl3): δ 8.44 (s, 1H), 8.35 (d, J=8 Hz, 1H), 7.87 (d, J=7.2 Hz, 1H), 7.8 (m, 2H) ppm. 13C NMR (100MHz, CDCl3): δ 158.8, 146.8, 134.9, 133.4, 130.4, 125.8, 112.2, 110.9, 88.5 ppm.

2-(4-methylbenzylidene)malononitrile (Entry 8)

1H NMR (400MHz, CDCl3): δ 7.81 (d, J=8.4 Hz, 2H), 7.72 (s, 1H), 7.33 (d, J=7.6 Hz, 2H), 2.45 (s, 3H) ppm. 13C NMR (100MHz, CDCl3): δ 160, 146.4, 131.4, 130.4, 128.4, 113.9, 112.9, 83.8, 29.6 ppm.

2-(4-(dimethylamino)benzylidene)malononitrile (Entry 9)

1H NMR (400MHz, CDCl3): δ 7.8 (d, J=9.2 Hz, 2H), 7.45 (s, 1H), 6.7 (d, J=8.8 Hz, 2H), 3.08 (s, 6H) ppm. 13C NMR (100MHz, CDCl3): δ 158.1, 154.3, 133.5, 119.2, 116, 115.4, 111.9, 71.5, 40.1 ppm.

2-(4-methoxybenzylidene)malononitrile (Entry 10)

1H NMR (400MHz, CDCl3): δ 7.9 (d, J=9.1 Hz, 2H), 7.65 (s, 1H), 7.01 (d, J=8.9 Hz, 2H), 3.91 (s, 3H) ppm. 13C NMR (100MHz, CDCl3): δ 164.8, 158.9, 133.5, 124, 115.1, 78.4, 55.8 ppm.

Table 2

Methyl 2-cyano-3-phenylacrylate(Entry1)

1H NMR (400MHz, CDCl3): δ 8.24 (s, 1H), 7.96(d, J=7.8 Hz, 2H), 7.46-7.59 (m, 3H), 3.79 (s, 3H) ppm. 13C NMR (100MHz, CDCl3): δ 163.5, 155.3, 133.4, 131, 129.3, 115.4, 102.5, 53.4 ppm.

2-benzoyl-3-phenylacrylonitrile (Entry2)

1H NMR (400MHz, CDCl3): δ 8.05(s, 1H), 8.02 (d, J=8.6Hz, 2H), 7.88-7.91 (m, 2H), 7.5-7.65 (m, 6H) ppm. 13C NMR (100MHz, CDCl3): δ 189.1, 155.6, 135.7, 133.4, 131.8, 131.1, 129.3, 128.7, 116.8, 110.2 ppm.

Polyethyleneimine modified with oleic acid (PEI-C18).

1H NMR (400MHz, CDCl3): δ5.27 (-CH=CH-, 2H), 3.2 (-NH), 2.2-2.77 (-PEI), 2.08 (-CH2C=O), 1.91 ( J=5.56, 4H CH2-C=C-CH2) , 1.522 (2H, CH2CH2C=O), 1.1921 ( 20H –CH2-), 0.78 ( -CH3) ppm. 13C NMR (100MHz, CDCl3): δ173.15 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 130.3 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 47.7 and 48.9-49.25 and 53.4-54.34 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 36.5 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 31.8 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 29.24-29.69 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 27.1 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 25.8 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 22.5 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 14 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-CH2-CH3]. FT-IR (cm-1): 3444, 3294, 3085, 2930, 2855, 1646, 1554, 1466, 1375, 1294, 1123. Elemental Anal.: C, 72.12; H, 12.34; N, 12.2.

NMR Spectra of PEI-C18

1H NMR

13C NMR

IR spectrum of PEI-OA