1
Supplementary Information
2
Mechanical transformation of fullerene (C60) to
3
nano-C60 (aqu-nC60) in the presence and absence
4
of light
5
6
Paul A. Indeglia*, Vijay B. Krishna, Angelina Georgieva, and Jean-Claude J. Bonzongo
7
8
Pages:
9
Figures: SI-S1, SI-S2, SI-S3, SI-S4, SI-S5, SI-S6, SI-S7, SI-S8, SI-S9, SI-S10, SI-S11, SI-
10
S12, SI-S13, SI-S14, SI-S15, SI-S16, SI-S17, SI-S18, SI-S19, SI-S20, SI-S21, SI-
11
S22, SI-S23, SI-S24
12
Tables:
28
SI-S1, SI-S2, SI-S3
13
1
14
15
Figure SI-S1. Aliquots of filtered nC60 taken over on alternate days for a 28-day period.
16
Starting from the upper left (t2) to the upper right (t14) and continuing to the lower
17
left (t16), terminating at the lower right (t28), depicting increasing material in
18
dispersed state.
19
2
400
LIGHT
350
DARK
Particle Diameter (nm)
300
250
200
150
100
50
0
0
20
21
22
4
8
12
16
20
24
28
Stirring Time (days)
Figure SI-S2. Number-weighted mean agglomerate size for nC60 samples as a function of time
of unfiltered material (with standard deviation).
23
3
9
Light
Dark
8
7
pH
6
5
4
3
2
0
4
8
12
16
20
24
28
Stirring Time (days)
24
25
Figure SI-S3. pH of unfiltered nC60 stirred for 28 days in dark and light as a function of time (n
26
= 3) (with standard deviation). Unfiltered control samples (n = 1) are shown in
27
light-weighted lines.
28
4
9
Light
Dark
8
7
pH
6
5
4
3
2
0
4
8
12
16
20
24
28
Stirring Time (days)
29
30
31
Figure SI-S4. pH of unfiltered nC60 stirred for 28 days in dark and light as a function of time (n
= 3) (with standard deviation).
32
5
0
Light
Dark
-10
Zeta Potential (mV)
Control
-20
-30
-40
-50
-60
0
4
8
12
16
20
24
28
Stirring Time (days)
33
34
35
Figure SI-S5. Zeta potential () for unfiltered nC60 samples as a function of time (n = 3) (with
standard deviation). Control is shown (n = 3) (with standard deviation).
36
6
0
LIGHT
DARK
Zeta Potential (mV)
-10
-20
-30
-40
-50
-60
0
4
39
12
16
20
24
28
Stirring Time (days)
37
38
8
Figure SI-S6. Zeta potential () for filtered nC60 samples as a function of time (n = 3) (with
standard deviation).
7
1.4
DAY 6
DAY 12
DAY 20
DAY 28
1.2
Absorbance
1
0.8
0.6
0.4
0.2
0
300
400
500
600
700
800
Wavelength (nm)
40
41
42
Figure SI-S7. UV/Vis spectrum of unfiltered nC60 stirred in dark at t6, t12, t20, and t28 (n = 3)
(error bars were omitted for clarity).
43
8
0.14
DAY 6
DAY 12
DAY 20
DAY 28
0.12
Absorbance
0.1
0.08
0.06
0.04
0.02
0
300
400
500
600
700
800
Wavelength (nm)
44
45
46
Figure SI-S8. UV/Vis spectrum of filtered nC60 stirred in dark at t6, t12, t20, and t28 (n = 3) (error
bars were omitted for clarity).
47
9
1.4
DAY 6
DAY 12
DAY 20
DAY 28
1.2
Absorbance
1
0.8
0.6
0.4
0.2
0
300
400
500
600
700
800
Wavelength (nm)
48
49
50
Figure SI-S9. UV/Vis spectrum of unfiltered nC60 stirred in light at t6, t12, t20, and t28 (n = 3)
(error bars were omitted for clarity).
51
10
0.14
DAY 6
DAY 12
DAY 20
DAY 28
0.12
Absorbance
0.1
0.08
0.06
0.04
0.02
0
300
400
500
600
700
800
Wavelength (nm)
52
53
54
Figure SI-S10. UV/Vis spectrum of filtered nC60 stirred in light at t6, t12, t20, and t28 (n = 3)
(error bars were omitted for clarity).
55
11
1.4
1.2
1
Absorbance
LIGHT
0.8
0.6
DARK
0.4
0.2
0
0
56
57
58
4
8
12
16
20
24
28
Stirring Time (days)
Figure SI-S11. UV peak at  = 360 nm for unfiltered nC60 as a function of time and photocondition (n = 3) (error bars were omitted for clarity).
59
12
0.2
0.18
LIGHT
0.16
Absorbance
0.14
0.12
0.1
0.08
0.06
0.04
DARK
0.02
0
0
60
61
62
4
8
12
16
20
24
28
Stirring Time (days)
Figure SI-S12. UV peak at  = 360 nm for filtered nC60 as a function of time and photocondition (n = 3) (error bars were omitted for clarity).
63
13
4.0
LIGHT
DARK
3.5
A 360 nm / A 525 nm
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0
4
8
12
16
20
24
28
Stirring Time (days)
64
65
Figure SI-S13. Ratio of UV ( = 360 nm) to visible ( = 525 nm) peaks (R) for unfiltered nC60
66
as a function of time and photo-condition (n = 3) (error bars were omitted for
67
clarity).
68
14
4.0
LIGHT
DARK
3.5
A 360 nm / A 525 nm
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0
4
8
12
16
20
24
28
Stirring Time (days)
69
70
71
Figure SI-S14. Ratio of UV ( = 360 nm) to visible ( = 525 nm) peaks (R) for filtered nC60 as
72
a function of time and photo-condition (n = 3) (error bars were omitted for
73
clarity).
74
15
GROUND
STATE
C
C
OH OH
HYDROXYL
C
C
O
EPOXIDE
C
C
O
ETHER
C
C
OIONIC
OXYGEN
C
C
O
HEMIKETAL
CARBONYL +
HYDROXYL
OH
75
O
OH
C
C
C
C
O
OH
O
OH
C
C
C
C
O
CARBOXYLIC
ACID
HO
C
OH
C
76
77
Figure SI-S15. Surface groups potentially associated with water-stirred fullerene (aqu-nC60).
16
1066
1183
0.14
940
0.12
0.06
803
2919
0.08
1669
1538
1428
1384
0.10
3175
KM
Kubelka-Munk
0.16
0.04
A
0.02
4000
4000
3000
2000
3000
1000
2000
1000
Wavenumbers (cm-1)-1
Wavelength
(cm )
1062
78
1185
0.07
945
0.06
0.05
0.02
B
805
0.01
4000
4000
3000
2000
3000
2000
1000
1000
Wavenumbers (cm-1)-1
Wavelength
(cm )
79
80
1429
1384
2364
2963
0.03
1670
0.04
3172
KM
Kubelka-Munk
0.08
Figure SI-S16. FTIR spectra for 7-day dark and light water-stirred fullerene (aqu-nC60)
81
samples. A) 7-day dark water-stirred fullerene sample. B) 7-day light water-
82
stirred fullerene sample.
83
17
1384
0.012
0.010
1129
0.014
1063
979
850
1453
KM
Kubelka-Munk
0.016
0.008
1679
2920
0.004
3466
0.006
0.002
A
0.000
4000
4000
3000
3000
2000
2000
1000 1000
1129
1384
0.014
0.010
1636
0.012
943
1460
0.016
2920
KM
Kubelka-Munk
3431
0.020
0.018
1001
Wavenumbers (cm-1)-1
Wavelength
(cm )
84
2364
0.008
0.006
0.004
B
85
86
0.002
0.000
4000
4000
3000
2000
3000
2000
1000
1000
Wavenumbers (cm-1)-1
Wavelength
(cm )
Figure SI-S17. FTIR spectra for 14-day dark and light water-stirred fullerene (aqu-nC60)
87
samples. A) 14-day dark water-stirred fullerene sample. B) 14-day light
88
water-stirred fullerene sample.
18
1034
11883
0.006
0.005
1431
1384
0.004
2364
0.002
1689
1577
0.003
2920
KM
Kubelka-Munk
0.007
0.001
A
4000
4000
3000
3000
2000
2000
1000 1000
Wavenumbers (cm-1)-1
Wavelength (cm )
1050
89
1089
1428
1383
2364
0.015
1636
0.020
2963
0.010
0.005
1183
0.025
880
2973
0.030
3317
KM
Kubelka-Munk
0.035
B
4000
4000
3000
2000
1000
1000
Wavenumbers (cm-1)-1
Wavelength
(cm )
90
91
2000
3000
Figure SI-S18. FTIR spectra for 28-day dark and light water-stirred fullerene (aqu-nC60)
92
samples. A) 7-day dark water-stirred fullerene sample. B) 7-day light water-
93
stirred fullerene sample.
19
10000
9000
X2 = 13.6
R2 = 0.998
nC60 - 7D
C60Ox(OH)y, x + y = 21
8000
Experimental Data
Counts per Second
7000
Curve Fitted Data
6000
Non-oxygenated Carbon
5000
Mono-oxygenated
Carbon
4000
3000
Di-oxygenated
Carbon
2000
1000
A
0
292
290
288
286
284
282
280
278
Binding Energy (eV)
94
4500
4000
3500
Counts per Second
X2 = 13.9
R2 = 0.995
nC60 - 7L
C60Ox(OH)y, x + y = 25
Experimental Data
3000
Curve Fitted Data
2500
Non-oxygenated Carbon
2000
Mono-oxygenated
Carbon
1500
1000
Di-oxygenated
Carbon
500
B
0
292
290
288
286
284
282
280
278
Binding Energy (eV)
95
96
Figure SI-S19. XPS spectra for 7-day dark and light water-stirred fullerene (aqu-nC60) samples.
97
A) 7-day dark water-stirred fullerene sample. B) 7-day light water-stirred
98
fullerene sample.
20
12000
nC60 - 14D
C60Ox(OH)y, x + y = 28
X2 = 38.4
R2 = 0.998
10000
Counts per Second
Experimental Data
8000
Curve Fitted Data
Non-oxygenated Carbon
6000
Mono-oxygenated
Carbon
4000
Di-oxygenated
Carbon
2000
A
0
292
290
288
286
284
282
280
278
Binding Energy (eV)
99
14000
nC60 - 14L
C60Ox(OH)y, x + y = 29
X2 = 4.33
R2 = 0.999
12000
Experimental Data
Counts per Second
10000
Curve Fitted Data
8000
Non-oxygenated Carbon
6000
Mono-oxygenated Carbon
4000
Di-oxygenated
Carbon
2000
B
0
292
290
288
286
284
282
280
278
Binding Energy (eV)
100
101
Figure SI-S20. XPS spectra for 14-day dark and light water-stirred fullerene (aqu-nC60)
102
samples. A) 14-day dark water-stirred fullerene sample. B) 14-day light
103
water-stirred fullerene sample.
104
21
10000
9000
X2 = 33.5
R2 = 0.996
nC60 - 28D
C60Ox(OH)y, x + y = 28
8000
Experimental Data
Counts per Second
7000
Curve Fitted Data
6000
Non-oxygenated Carbon
5000
4000
Mono-oxygenated Carbon
3000
2000
Di-oxygenated
Carbon
1000
A
0
292
290
288
286
284
282
280
278
Binding Energy (eV)
105
14000
X2 = 33.4
R2 = 0.993
nC60 - 28L
C60Ox(OH)y, x + y = 33
12000
Experimental Data
Counts per Second
10000
Curve Fitted Data
8000
Non-oxygenated Carbon
Mono-oxygenated Carbon
6000
4000
Di-oxygenated
Carbon
2000
B
0
292
290
288
286
284
282
280
278
Binding Energy (eV)
106
107
Figure SI-S21. XPS spectra for 28-day dark and light water-stirred fullerene (aqu-nC60)
108
samples. A) 28-day dark water-stirred fullerene sample. B) 28-day light
109
water-stirred fullerene sample.
22
40
Number of Surface Groups
MONO + DI = TOTAL
35
TOTAL - Light
30
TOTAL - Dark
MONO - Light
25
MONO - Dark
20
15
10
DI - Dark
DI - Light
5
0
0
4
8
12
16
20
24
28
Stirring Time (days)
110
111
Figure SI-S22. Kinetics of surface group formation for aqu-nC60 stirred in dark and light for 28
112
days. (MONO = Mono-oxygenated surface groups; DI = Di-oxygenated surface
113
groups)
114
23
1183
0.20
0.15
0.10
1539
2329
KM
Kubelka-Munk
1429
0.25
0.05
A
4000
4000
3000
3000
2000
2000
10001000
-1
Wavenumbers(cm
(cm-1)
Wavelength
)
115
0.20
1539
0.10
2329
0.15
3434
KM
Kubelka-Munk
0.25
1183
1429
0.30
0.05
B
4000
4000
3000
3000
2000
2000
Wavenumbers (cm-1)-1
1000
1000
Wavelength (cm )
116
117
Figure SI-S23. FTIR spectra of by-products for 14-day light and 28-day light water-stirred
118
fullerene (aqu-nC60) samples. A) 14-day light water-stirred fullerene sample.
119
B) 28-day light water-stirred fullerene sample.
24
2500
WASTE - nC60 - 14L
C60Ox(OH)y, x + y = 1
X2 = 12.7
R2 = 0.999
2000
Counts per Second
Experimental Data
1500
Curve Fitted Data
1000
Non-oxygenated Carbon
500
Mono-oxygenated
Carbon
A
0
292
290
288
286
284
282
280
278
Binding Energy (eV)
120
1800
WASTE - nC60 - 28L
C60Ox(OH)y, x + y = 9
X2 = 24.2
R2 = 0.992
1600
1400
Experimental Data
Counts per Second
1200
Curve Fitted Data
1000
Non-oxygenated Carbon
800
600
400
Mono-oxygenated
Carbon
200
B
0
292
121
122
290
288
286
284
282
280
278
Binding Energy (eV)
Figure SI-S24. XPS spectra of by-products for 14-day light (top) and 28-day light (bottom)
123
water-stirred fullerene (aqu-nC60) samples. A) 14-day light water-stirred
124
fullerene sample. B) 28-day light water-stirred fullerene sample.
125
25
126
Table SI-S1. Mean agglomerate size for nC60 determined through DLS and TEM
TEM
96.6
c
%
23.5%
n C60-14L
158.4
117.6
25.8%
n C60-28D
142.3
117.0
17.8%
n C60-28L
125.8
108.2
14.0%
a
127
d
Fullerene Species DLS
n C60-14D
126.2
b, c
128
DLS = dynamic light scattering
129
TEM = transmission electron microscopy
130
% = [(DLS-TEM) / DLS] x 100
131
a
132
nC60-14D, nC60-14L, nC60-28D, and nC60-28L indicate nC60 stirred for 14 days in dark, 14 days in light, 28 days in
dark, and 28 days in light, respectively.
133
b
DLS measurements based on number-weighted statistics.
134
c
All sizes in nm.
135
d
Percent difference (%) defined between TEM/DLS.
136
26
137
Table SI-S2. Quantification of nC60 oxygenated carbon states as determined via XPS
Fullerene Species
138
139
Mono-oxygenated
Di-oxygenated
nC60 -7D
10
11
nC60 -7L
17
8
nC60 -14D
21
7
nC60 -14L
23
6
nC60 -28D
22
7
nC60 -28L
27
XPS = X-ray photoelectron spectroscopy
6
140
27
141
142
Table SI-S3. Exponential parameters for nC60 surface derivatization kinetics for water-stirred
fullerene (aqu-nC60)
Surface Group Type
Total
n C60 -dark-stirred
143
a
b
3.64
16.49
n C60 -light-stirred
Mono-oxygenated
n C60 -dark-stirred
4.23
19.50
2.59
11.11
n C60 -dark-stirred
Di-Oxygenated
n C60 -dark-stirred
3.18
14.12
1.05
5.38
n C60 -dark-stirred
0.09
4.29
28