10847_2009_9660_MOESM1_ESM.docElectronic supplementary materials

Novel Phosphorylated calixarenes for the recognition of f-elements

Maria Karavan,a,b Françoise Arnaud-Neu,a Véronique Hubscher-Bruder,a Igor Smirnovb and Vitaly Kalchenkoc

Table S1. Extraction of various metal ions from nitric acid solutions into m-NBTF by wide rim substituted calixarene phosphine oxides. Distribution coefficients D:

Eu3+ (10-5 M), Am3+ (traces), ligand (0.01 M)

UO22+ (10-5 M), ligand (0.001 M)

Ligands / Metal ions / Nitric acid concentration (M)
0.1 / 0.3 / 1 / 3 / 6
1a / Eu3+ / <0.01 / 0.01 / 0.02 / 0.1 / 0.01
Am3+ / <0.01 / 0.01 / 0.01 / 0.04 / 0.01
1b / Eu3+ / 0.2 / 1.3 / 2.4 / 0.06 / 0.01
Am3+ / 0.1 / 0.42 / 1.1 / 0.03 / <0.01
UO22+ / 14.6 / 31.1 / 20.9 / 6.8 / 2.1
1c / Eu3+ / 6.5 / 6.23 / 1.27 / 0.05 / <0.01
Am3+ / 1.9 / 2.15 / 0.49 / 0.02 / <0.01
UO22+ / 23.6 / 17.8 / 12.7 / 4.8 / 1.3
1d / Eu3+ / 0.03 / 0.03 / 0.01 / <0.01 / <0.01
Am3+ / 0.04 / 0.05 / 0.03 / <0.01 / <0.01
1e / Eu3+ / 4.0 / 3.5 / 0.68 / 0.03 / <0.01
Am3+ / 1.5 / 1.3 / 0.27 / 0.01 / <0.01
UO22+ / 39 / 21 / 16.5 / 4.6 / 1.5
2b / Eu3+ / 0.37 / 1.54 / 2.71 / 0.11 / <0.01
Am3+ / 0.11 / 0.49 / 1.06 / 0.04 / <0.01
2e / Eu3+ / 2.68 / 3.44 / 0.70 / 0.02 / <0.01
Am3+ / 0.98 / 1.2 / 0.26 / 0.01 / <0.01
UO22+ / 36.7 / 21.8 / 14.8 / 3.07 / 1.69
3b / Eu3+ / 0.01 / 0.03 / 0.05 / 0.01 / <0.01
Am3+ / <0.01 / 0.02 / 0.03 / 0.01 / <0.01
3e / Eu3+ / 0.6 / 0.4 / 0.15 / 0.01 / <0.01
Am3+ / 0.2 / 0.23 / 0.1 / 0.01 / <0.01
UO22+ / 21 / 16.8 / 12.1 / 8.6 / 4.0
0e (0.04 M) / Eu3+ / 0.01 / 0.023 / 0.01 / <0.01 / <0.01
Am3+ / 0.004 / 0.008 / <0.01 / <0.01 / <0.01
0e (0.06 M) / Eu3+ / 0.01 / 0.025 / 0.016 / 0.015 / <0.01
Am3+ / 0.007 / 0.026 / 0.008 / <0.01 / <0.01
TOPO (0.04M) / Eu3+ / 0.04 / 0.05 / 0.006 / <0.01 / <0.01
Am3+ / 0.04 / 0.04 / 0.01 / <0.01 / <0.01
(0.004 M) / UO22+ / 8.3 / 5.9 / 1.23 / 0.19 / 0.09

Table S2. Extraction of various metal ions from nitric acid solutions into m-NBTF by narrow rim substituted calixarene phosphine oxides : Distribution coefficients D:

Eu3+ (10-5 M), Am3+ (traces), ligand (0.01 M)

UO22+ (10-5 M), ligand (0.001 M)

Ligands / Metal ions / Nitric acid concentration (M)
0.1 / 0.3 / 1 / 3 / 6
5a / Eu3+ / 0.02 / 0.03 / 0.02 / <0.01 / <0.01
Am3+ / 0.01 / 0.03 / 0.01 / <0.01 / <0.01
UO22+ / 0.85 / 0.39 / 0.27 / 0.14 / 0.08
5b / Eu3+ / 0.13 / 0.05 / 0.03 / <0.01 / <0.01
Am3+ / 0.04 / 0.05 / 0.03 / <0.01 / <0.01
UO22+ / 0.63 / 0.54 / 0.2 / 0.2 / 0.18
6b / Eu3+ / 4.3 / 5.6 / 2.6 / 0.32 / 0.03
Am3+ / 7.5 / 7.7 / 3.6 / 0.38 / 0.03
UO22+ / 0.24 / 0.32 / 0.49 / 0.23 / 0.15
7a / Eu3+ / 0.02 / 0.04 / 0.02 / <0.01 / <0.01
Am3+ / 0.01 / 0.02 / 0.01 / <0.01 / <0.01
UO22+ / 7.5 / 3.1 / 1.69 / 1.22 / 0.84

Table S3. Extraction of various metal ions from nitric acid solutions into m-NBTF by wide rim substituted calixarene phosphonates. Distribution coefficients D:

Eu3+ (10-5 M), Am3+ (traces), ligand (0.01 M)

UO22+ (10-5 M), ligand (0.001 M)

Ligands / Metal ions / Nitric acid concentration (M)
0.1 / 0.3 / 1 / 3 / 6
8a / Eu3+ / 0.86 / 0.50 / 0.20 / 0.08 / 0.01
Am3+ / 1.02 / 0.55 / 0.22 / 0.07 / 0.01
8b / Eu3+ / 0.23 / 0.17 / 0.14 / 0.17 / 0.06
Am3+ / 0.3 / 0.24 / 0.24 / 0.27 / 0.06
8c / Eu3+ / >1000 / 350 / 25 / 4.7 / 0.61
Am3+ / >500 / 300 / 30 / 4.6 / 0.47
8d / Eu3+ / 0.78 / 0.54 / 0.42 / 0.27 / 0.02
Am3+ / 1.05 / 0.77 / 0.56 / 0.33 / 0.02
8e / Eu3+ / 0.01 / 0.01 / 0.06 / 0.18 / 0.06
Am3+ / 0.01 / 0.02 / 0.11 / 0.27 / 0.05
9c (0.02 M) / Eu3+ / <0.01 / 0.002 / 0.007 / 0.014 / 0.015
Am3+ / <0.01 / 0.004 / 0.007 / 0.019 / 0.017
9e (0.02 M) / Eu3+ / <0.01 / 0.01 / 0.005 / 0.013 / 0.019
Am3+ / <0.01 / 0.01 / 0.01 / 0.02 / 0.018

Figure S1. UV-spectra corresponding to the titration of 1c (CL = 2.25´10-4 M) by La(NO3)3 in methanol (0 ≤ R = CM/CL ≤ 23).

Figure S2. Microcalorimetric titration of 2.5 ml calixarene 1c (1.07×10-3 M) by addition of 17×15mL of 0.0208 M Eu(NO3)3 in methanol, at 25°C. The lower graph corresponds to the dilution of the salt in methanol.

Figure S3. Microcalorimetric titration of 2.5 ml calixarene 1c (1.356×10-3 M) by addition of 17×15mL of 0.0293 M UO2(NO3)2 in methanol, at 25°C. The lower graph corresponds to the dilution of the salt in methanol.

a)  direct titration
b)  reverse titration
Figure S4. Microcalorimetric titrations corresponding to the complexation of Eu(NO3)3 with 1c in acetonitrile, at 25°C.
a) Direct titration of 2.5 ml of ligand (1.04×10-3 M) by addition of 17×15mL of 0.0287 M Eu(NO3)3;
The lower graph corresponds to the dilution of the salt in acetonitrile.
b) Reverse titration of 2.5 ml of 2.33×10-4 M Eu(NO3)3 by addition of 17×15mL of ligand (5.09×10-3 M). The lower graphs correspond to the dilution of the ligand in acetonitrile.
a)  direct titration
b)  reverse titration
Figure S5. Microcalorimetric titrations corresponding to the complexation of UO2(NO3)2 with 1c in acetonitrile, at 25°C.
a) Direct titration of 2.5 ml of ligand (1.04×10-3 M) by addition of 17×15mL of 0.029 M UO2(NO3)2;
The lower graph corresponds to the dilution of the salt in acetonitrile.
b) Reverse titration of 2.5 ml of 2.32×10-4 M UO2(NO3)2 by addition of 17×15mL of ligand (5.09×10-3 M). The lower graphs correspond to the dilution of the ligand in acetonitrile.

Figure S6. Microcalorimetric titration of 2.5 ml calixarene 5b (0.002 M) by addition of 17×15mL of 0.032 M Eu(NO3)3 in methanol, at 25°C. The lower graph corresponds to the dilution of the salt in methanol.

(a) : 1:1 / (b): 1:1 + 1:2

Figure S7. Experimental (x) and calculated (line) corrected heat (Qc) vs. the volume of titrant added assuming the formation of 1:1 species (a) or 1:1 and 1:2 (b) for the microcalorimetric titration of 2.5 ml 5b (2.043×10-3 M) by addition of 17×15mL of 0.0341 M Eu(NO3)3 in methanol, at 25°C.

Figure S8. Microcalorimetric titration of 2.5 ml calixarene 6b (0.748×10-3 M) by addition of 17×15mL of 0.0201 M UO2(NO3)2 in acetonitrile, at 25°C. The lower graph corresponds to the dilution of the salt in acetonitrile.

Figure S9. Microcalorimetric titration of 2.5 mL of ligand 8c (1.022×10-3 M) by 17×15 mL of 0.0315 M Eu(NO3)3 in methanol, at 25 °C. The lower curve corresponds to the dilution of the salt in methanol.
Figure S10. Microcalorimetric titration of 2.5 mL of calixarene 8e (1.055×10-3 M) by 17×15 mL of 0.0494 M UO2(NO3)2 in methanol at 25 °C. The lower curve corresponds to the dilution of the salt in methanol.
Figure S11. Microcalorimetric titration of 2.5 mL of ligand 8c (7.19×10-4 M) by 17×15 mL of 0.0203 M Eu(NO3)3 in acetonitrile, at 25 °C. The lower curve corresponds to the dilution of the salt in acetonitrile.
Figure S12. Microcalorimetric titration of 2.5 mL of calixarene 8e (7.19×10-4 M) by 17×15 mL of 0.02 M UO2(NO3)2, in acetonitrile at 25 °C. The lower curve corresponds to the dilution of the salt in acetonitrile.

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