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
Aqueous phase
Formula
a
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
1g of PEI-C18 was added to the oil phase in all formulas. After hot emulsification, pH was
set to 10 by NaOH 1M. b pH 7.3, no NaOH was 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 (Entry 1)
1
H 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)
1
H 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.
C NMR (100MHz, CDCl3): δ 158.6, 141.1, 131.9, 130, 129.3, 113.6, 112.4, 83.1 ppm.
13
2-(4-cyanobenzylidene)malononitrile (Entry 5)
1
H 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)
1
H 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.
C NMR (100MHz, CDCl3): δ 156.9, 150.9, 135.8, 131.3, 124.6, 112.6, 111.6, 87.5 ppm.
13
2-(2-nitrobenzylidene)malononitrile (Entry 7)
1
H 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)
1
H 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)
1
H 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.
40.1 ppm.
13
C NMR (100MHz, CDCl3): δ 158.1, 154.3, 133.5, 119.2, 116, 115.4, 111.9, 71.5,
2-(4-methoxybenzylidene)malononitrile (Entry 10)
1
H 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.
13
C 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 (Entry 1)
1
H 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.
13
C NMR (100MHz, CDCl3): δ 163.5, 155.3, 133.4, 131, 129.3, 115.4, 102.5, 53.4
ppm.
2-benzoyl-3-phenylacrylonitrile (Entry 2)
1
H 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.
13
C 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).
1
H NMR (400MHz, CDCl3): δ 5.27 (-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.
13
C 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-CH2CH=CH-CH2-(CH2)4-CH2-CH2-CH3], 36.5 [PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2(CH2)4-CH2-CH2-CH3],
CH2-CH3],
29.24-29.69
31.8
[PEI-NHCO-CH2-CH2-(CH2)4-CH2-CH=CH-CH2-(CH2)4-CH2-
[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 [PEINHCO-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-CH2CH=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.
1.208
1.177
1.071
0.942
0.900
0.882
0.860
0.840
0.804
0.788
0.771
0.742
0.631
0.614
1.5
1.5
3.000
18.460
2.028
2.0
3.000
1.941
3.504
1.522
1.422
11.416
2.5
18.460
2.0
1.764
3.0
2.028
2.5
1.920
1.906
2.374
3.5
3.504
2.080
0.207
4.0
2.241
2.626
2.554
2.486
4.5
1.941
3.0
2.779
0.000
5.0
11.416
3.5
3.045
3.236
3.180
3.556
5.5
2.374
0.207
2.779
2.626
2.554
2.486
2.241
2.080
1.920
1.906
1.764
1.522
1.422
1.208
1.177
1.071
0.942
0.900
0.882
0.860
0.840
0.804
0.788
0.771
0.742
0.631
3.236
3.180
3.045
3.556
5.285
5.273
5.241
5.044
1H
5.902
5.869
5.836
NMR Spectra of PEI-C18
NMR
1.0
0.5
1.0
ppm
ppm
170
40
39
140
38
37
36
35
120
34
110
33
100
32
90
31
80
30
70
29
28
60
27
50
26
22.605
22.580
22.496
22.255
130
32.544
31.829
31.708
31.680
31.438
29.694
29.654
29.604
29.542
29.457
29.242
28.903
28.767
27.889
27.156
26.842
26.521
25.877
25.559
34.316
150
36.576
160
37.557
39.098
77.476
77.363
77.158
76.840
54.341
53.439
49.260
48.913
47.663
39.098
37.557
36.576
34.316
32.544
31.829
31.708
31.680
31.438
29.694
29.654
29.604
29.542
29.457
29.242
130.302
130.121
129.901
129.597
127.998
127.798
173.515
13C
NMR
40
25
30
24
20
23
ppm
ppm
IR spectrum of PEI-OA