Supplementary data
Title: Mixed lanthanide oxide nanoparticles as dual imaging agent in biomedicine
Authors: Wenlong Xu, Badrul Alam Bony, Cho Rong Kim, Jong Su Baeck, Yongmin
Chang, Ji Eun Bae, Kwon Seok Chae, Tae Jeong Kim, and Gang Ho Lee
(1) HRTEM and HVEM images
HRTEM images of D-glucuronic acid coated ultrasmall Dy1.5Eu0.5O3, Ho1.6Eu0.4O3, and
Ho1.1Tb0.9O3 nanoparticles are provided in Figs. S1A1 to S1C2. A low resolution TEM
image was inserted into one of HRTEM images in all samples and its one area as
indicated with a dotted square was magnified to the HRTEM image. An additional
HVEM image of D-glucuronic acid coated ultrasmall Ho1.1Tb0.9O3 nanoparticles is
provided in Fig. S1C2 with an improved lattice resolution. Particle diameters generally
ranged from 1 to 4 nm in all samples with slightly different average particle diameters
as provided in the text.
1
2
3
4
5
6
Figure S1 Low resolution TEM (as inserted) and HRTEM images of D-glucuronic acid
coated ultrasmall (A1 and A2) Dy1.5Eu0.5O3, (B1 and B2) Ho1.6Eu0.4O3, (C1) Ho1.1Tb0.9O3
nanoparticles, and (C2) a HVEM image of D-glucuronic acid coated ultrasmall
Ho1.1Tb0.9O3 nanoparticles. A dotted square in each low resolution TEM image
corresponded to the area magnified to a HRTEM image.
(2) XRD patterns before (i.e., as-prepared) and after thermal treatment with
TGA
As shown in Figs. S2A to S2C, as-prepared powder samples showed very broad
patterns likely due to ultrasmall particle diameters. However, powder samples after
thermal treatment showed sharp peaks, all corresponding to a highly crystallized
cubic Ln2O3 due to particle size growth during TGA treatment. All XRD peaks after
thermal treatment could be assigned with Miller indices (hkl). They were labelled with
numbers in XRD patterns and assigned with Miller indices in Table S1. The peaks with
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the same (hkl) values were labelled with the same numbers in all XRD patterns.
Lattice constants of TGA treated powder samples are provided in Table S2. They are
all consistent with weighted lattice constants of individual oxides1-4 by compositions
(i.e., x and y values).
Counts (Arb. Units)
(A)
2
Dy1.5Eu0.5O3
10
15
4
after TGA
1
28
35
as-prepared
20
40
60
80
100
2
2
Ho1.6Eu0.4O3
Counts (Arb. Units)
(B)
10
4
15
after TGA
28
1
38
as-prepared
20
40
60
2
8
80
100
Counts (Arb. Units)
(C)
2
Ho1.1Tb0.9O3
10
4
15
after TGA
as-prepared
20
40
60
2
80
100
Figure S2 XRD patterns of D-glucuronic acid coated ultrasmall (A) Dy1.5Eu0.5O3, (B)
Ho1.6Eu0.4O3, and (C) Ho1.1Tb0.9O3 nanoparticles before (i.e., as-prepared) and after
thermal treatment with TGA. All peaks were labelled with numbers and assigned with
Miller indices as provided in Table S1.
Table S1. Peak assignment with Miller index (hkl).
Peak
hkl
2θ
number
Dy1.5Eu0.5O3
Ho1.6Eu0.4O3
nanoparticle
nanoparticle
1
211
20.34
20.43
2
222
28.88
28.97
3
123
31.20
31.38
4
400
33.51
33.65
5
411
35.56
35.79
6
420
37.79
7
332
39.45
39.78
8
134
43.07
43.32
9
521
46.42
46.74
10
440
48.08
48.30
11
433
49.65
49.87
12
532
52.73
53.00
13
026
54.12
54.57
14
145
55.60
55.98
15
622
57.08
57.40
16
136
58.34
58.83
17
444
59.86
60.26
18
543
61.16
61.54
19
633
63.75
64.25
20
642
65.16
21
156
69.06
69.50
22
800
70.26
70.78
9
Ho1.1Tb0.9O3
nanoparticle
28.97
33.65
48.17
57.26
-
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
811
820
653
822
831
662
840
833
655
158
763
844
853
860
268
1022
71.56
74.07
76.48
77.69
80.08
81.49
83.70
86.03
88.35
89.56
90.86
91.97
94.29
96.80
71.93
73.34
74.49
75.77
76.90
78.18
80.74
84.29
86.72
89.14
90.27
91.40
92.68
95.12
97.38
-
Table S2. Cell constant (a) of mixed lanthanide oxide nanoparticles after thermal
treatment with TGA.
Nanoparticle
a (Å)
Dy1.5Eu0.5O3
10.71
Ho1.6Eu0.4O3
10.65
Ho1.1Tb0.9O3
10.67
(3) 3 tesla T2 MR images in a mouse
As shown in Figs. S3A and S3B, 3 tesla T2 MR images were obtained before and one
hour after injection of aqueous sample solutions of D-glucuronic acid coated ultrasmall
Dy1.5Eu0.5O3 and Ho1.6Eu0.4O3 nanoparticles to a mouse tail vein. Negative contrast
enhancements after injection were clearly observed in mouse livers, confirming that
these ultrasmall lanthanide oxide nanoparticles functioned as T2 MRI contrast agents.
Figure S3 Coronal views of 3 tesla T2 MR images in mouse livers (indicated with
arrows) before and one hour after injection of aqueous sample solutions of Dglucuronic acid coated ultrasmall (A) Dy1.5Eu0.5O3 and (B) Ho1.6Eu0.4O3 nanoparticles.
Darker images were observed after injection due to negative contrast enhancements
by nanoparticles.
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(4) Fluorescent confocal images in DU145 cells
Fluorescent confocal images in DU145 cells treated with aqueous sample solutions of
D-glucuronic acid coated ultrasmall Dy1.5Eu0.5O3, Ho1.6Eu0.4O3, and Ho1.1Tb0.9O3
nanoparticles are provided in Figs. S4A to S4C, respectively. Top images are
fluorescent confocal images at λex = 405 nm. The pale blue color is from DAPI stained
in cell nuclei. Bottom images are those at ex = 488 nm. The red color in Figs. S4A
and S4B is from ultrasmall Dy1.5Eu0.5O3 and Ho1.5Eu0.5O3 nanoparticles in DU145 cells,
while the green color in Fig. S4C, from ultrasmall Ho1.1Tb0.9O3 nanoparticles in DU145
cells. Here, the red color in Fig. S4A is slightly brighter than that in Fig. S4B because
the former nanoparticles have a slightly higher Eu content in mixed nanoparticles than
the latter nanoparticles. These results clearly demonstrate that these ultrasmall mixed
lanthanide oxide nanoparticles are excellent FI agents.
Figure S4 Fluorescent confocal images at λex = 405 nm (top images) and 488 nm
(bottom images) in DU145 cells treated with aqueous sample solutions of Dglucuronic acid coated ultrasmall (A) Dy1.5Eu0.5O3, (B) Ho1.6Eu0.4O3, and (C)
Ho1.1Tb0.9O3 nanoparticles.
References
1. Eu2O3, 1977 JCPDS-International Centre for Diffraction Data, card no. 43-1008, a =
10.86 Å.
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2. Tb2O3, 1977 JCPDS-International Centre for Diffraction Data, card no. 43-1032, a =
10.73 Å.
3. Dy2O3, 1977 JCPDS-International Centre for Diffraction Data, card no. 43-1006, a =
10.66 Å.
4. Ho2O3, 1977 JCPDS-International Centre for Diffraction Data, card no. 43-1018, a =
10.60 Å.
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