Supplementary Material (ESI) for Journal of Materials Chemistry

This journal is (c) The Royal Society of Chemistry 2010

Polyaniline-Coated Single-Walled Carbon Nanotubes: Synthesis,

Characterization and Impact on Primary Immune Cells

Shoshana Ben-Valid,a Hélène Dumortier,b,* Marion Décossas,b Ruthy Sfez, a Moreno Meneghetti,c

Alberto Bianco b and Shlomo Yitzchaika,*

a
Institute of Chemistry and the Nanoscience and Nanotechnology Center, The Hebrew University of

Jerusalem, Jerusalem 91904, Israel

b
CNRS, Institut de Biologie Moléculaire et Cellulaire, UPR9021 Immunologie et Chimie

Thérapeutiques 67000 Strasbourg, France

c
Department of Chemical Sciences, University of Padova, 35131 Padova, Italy

Electronic Supporting Information

1
 Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2010

O
C
Unpurified Purified

Si

C Fe
Mg Al
O Ga
Ni

Figure S1. EDX spectra of unpurified and purified SWCNTs. The main peak in the EDX of the raw
SWCNTs is the oxygen originating from metal-oxides where the main peak in the purified SWCNTs is
carbon as expected. This analysis shows that most of the metals were removed in this cleaning
protocol.

Figure S2. TEM images of SWCNTs before (left) and after (right) purification.

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 Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2010

100 SWCNT Pure

SWCNT Crude

80
Precent (%)

60

40

20

Y=9.61
0 Y=1.24%

200 400 600 800

Temperature (oC)

Figure S3. TGA profile of SWCNTs before (dotted line) and after purification (black line). The TGA
profile show quantitatively that the weight percent of metals decreases from 9.61 % to 1.24 % by this
purification protocol. The TGA was determined in air from 50 to 875oC and the temperature was
increased at a rate of 10oC/min.

SWCNT Purified
SWCNT Raw Material 1566.8
1566.87927

1.8
1166.7
1166.72241 Carbonyl peak
Intensity

1.7
1100.1
1100.19031
1384.6
1384.63916
1722.1
1722.12085
1579.4
1579.41431

826.3
826.34802

1.6

500 1000 1500

Wavenumber cm-1

Figure S4. FTIR spectra before (grey) and after (black) purification of SWCNTs. The characteristic
signals of SWCNTs in the IR region are at about 1100 cm-1 and 1579 cm-1. The difference between the
spectra of the raw SWCNTs and the clean material was found at 1712 cm-1 and 1722 cm-1. These signals
come from the carbonyl of carboxylic acid generated at the open ends of the purified SWCNTs.

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 Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2010

80000
unpurified
purified

60000
Raman intensity

40000

20000

0
1000 1500 2000
-1
Frequency (cm )

Figure S5. RAMAN spectra before (red) and after (blue) purification of SWCNTs. The peak area ratio
of the D/G band in the raw SWCNTs and SWCNTs after purification is 0.37±0.08 (n=15) and 0.46±0.05
(n=15), respectively. The RAMAN spectrum shows a higher ratio between the D/G bands after
cleaning, results which mean that the SWCNT structure is damaged during the cleaning procedure.

O
Na
Mg Al Si S

Figure S6. SEM and EDX images of SWCNTs coated with SDS. The SEM image show that the
diameter of the SWCNTs increases from 6.4 to 8.5 nm when they were treated with SDS. The EDX
spectra show the sodium peak and a low intensity sulfur signal which originate from SDS.

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 Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2010

100 SWCNT-COOH
SDS pure
SWCNT/SDS
80

60
Percent (%)

40

Y=24.16%
20

Y=5.75%
0 Y=1.24%
200 400 600 800
o
Temp. ( C)

Figure S7. TGA profile of pure SDS (dashed line), SWCNTs coated with SDS (dotted line) and pure
SWCNT (black line). The TGA was performed in air from 40 to 900oC and the temperature was
increased at a rate of 10oC/min. The ratio between SDS and SWCNTs was determined from the residue
left at 900oC in each of the three above species. We have solved the following two equations
1.24X+24.16Y=5.75, X+Y=1 to calculate the 100Y which is the % of SDS in the hybrid corresponding
to 19.67.

Figure S8. TEM images of SWCNT/SDS/PANI hybrids.

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 Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2010

N O
Na
S

Figure S9. SEM (left) and EDX (right) images of the composite SWCNT/SDS/PANI. The SEM image
of SWCNTs coated with PANI shows that the diameter increase to 42.1±3.8 nm (n=45). This value is
indicative of bundles with a different number of SWCNTs. As expected EDX profile shows PANI’s
nitrogen which is absent in the EDX of SWCNT/SDS hybrid. The sodium signal decreased dramatically
in comparison to the sodium peak in Figure S6 meaning that most of the sodium was exchanged by
anilinium during the synthesis.

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 Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2010
S 2p SWCNT/SDS/PANI
N 1s SWCNT/SDS/PANI
80
80

Name Pos Area Area

70
70
(%) Name Pos Area Area
N 1s 398.6 121.7 7.88 60 (%)
60 S 2p 3/2 168.7 88.9 66.67
N 1s 400.238 1424.4 92.12
50 S 2p 1/2 169.88 44.4 33.33
50
CPS

CPS
40
40

30
30
20
20

10 10

0 0
404 402 400 398 396 174 172 170 168 166
Binding Energy (eV) Binding Energy (eV)

700
N a 1s
600

500

400
CPS

300

200

100

0
1078 1076 10 7 4 1072 1070 1068 1 06 6
B in ding E n ergy (eV )

Figure S10. XPS spectra of the hybrid SWCNT/SDS/PANI. The spectra show that the hybrid contains
sulfur which comes from SDS, quaternary and tertiary nitrogen from PANI and does not contain Na
which is exchanged by the anilinium during the synthesis.

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 Supplementary Material (ESI) for Journal of Materials Chemistry
This journal is (c) The Royal Society of Chemistry 2010

Figure S11. Optical microscopy images of macrophages incubated with the different SWCNT. Cells
were fixed, embedded into Epon, cut into 500 nm-thick sections and stained with toluidine blue. The
nanotubes are clearly visible inside the phagosomes. They are more aggregated in the case of the
uncoated SWCNT. Upon SWCNT internalization, the cells change their morphology in comparison to
control cells (A). Scale bar corresponds to 20 µm.
Intensity (a.u.)

500 1000 1500 2000 2500 3000

-1
Raman shift (cm )

Figure S12. Raman spectrum excited at 633 nm of a macrophage in the absence of the nanotubes.