Review Article

Chem Soc Rev

<table><caption>Table 15 Values from Fig. 17: selectivity of different ligands across the Ln³⁺ series</caption><thead><tr><th>Ln³⁺</th><th>EDTA<sup>a</sup></th><th>DTPA<sup>a</sup></th><th>Macropa<sup>b</sup></th><th>Macrotripa<sup>c</sup></th><th>LBT12<sup>d</sup></th><th>LF4<sup>e</sup></th><th>RTX<sup>f</sup></th><th>LanD<sup>g</sup></th><th>LanM<sup>h</sup></th><th>LanM<sup>i</sup></th><th>LanM<sup>j</sup></th><th>LanM<sup>k</sup></th></tr></thead><tbody><tr><td>La<sup>3+</sup></td><td>15.5</td><td>19.5</td><td>15.0</td><td>12.6</td><td>5.5</td><td>4.2</td><td>4.1</td><td>5.7</td><td>11.3</td><td></td><td>10.2</td><td></td></tr><tr><td>Ce<sup>3+</sup></td><td>16.1</td><td>20.5</td><td>15.1</td><td>12.8</td><td>6.0</td><td></td><td></td><td>6.0</td><td></td><td></td><td></td><td></td></tr><tr><td>Pr<sup>3+</sup></td><td>16.3</td><td>21.1</td><td>14.7</td><td>12.7</td><td></td><td></td><td>4.5</td><td>6.3</td><td></td><td>10.2</td><td></td><td>11.0</td></tr><tr><td>Nd<sup>3+</sup></td><td>16.6</td><td>21.6</td><td>14.4</td><td>12.3</td><td>6.6</td><td></td><td>4.5</td><td>6.6</td><td>11.3</td><td></td><td>10.0</td><td>10.7</td></tr><tr><td>Sm<sup>3+</sup></td><td>17.0</td><td>22.3</td><td>13.8</td><td>11.4</td><td></td><td></td><td></td><td>6.5</td><td>11.2</td><td></td><td></td><td>10.6</td></tr><tr><td>Eu<sup>3+</sup></td><td>17.2</td><td>22.4</td><td>13.0</td><td>10.9</td><td>7.2</td><td>4.6</td><td>4.6</td><td>6.5</td><td></td><td></td><td></td><td></td></tr><tr><td>Gd<sup>3+</sup></td><td>17.3</td><td>22.5</td><td>13.0</td><td>10.2</td><td>7.1</td><td>4.6</td><td></td><td>6.2</td><td>11.0</td><td>10.0</td><td></td><td></td></tr><tr><td>Tb<sup>3+</sup></td><td>17.8</td><td>22.7</td><td>11.8</td><td>10.2</td><td>7.2</td><td>4.9</td><td>4.6</td><td></td><td>10.7</td><td></td><td></td><td></td></tr><tr><td>Dy<sup>3+</sup></td><td>18.2</td><td>22.8</td><td>11.7</td><td>10.5</td><td>7.2</td><td></td><td>4.6</td><td></td><td></td><td>9.7</td><td>8.6</td><td>10.8</td></tr><tr><td>Ho<sup>3+</sup></td><td>18.4</td><td>22.8</td><td>10.6</td><td>10.7</td><td></td><td>4.9</td><td></td><td></td><td>10.6</td><td>9.6</td><td></td><td>11.1</td></tr><tr><td>Er<sup>3+</sup></td><td>18.9</td><td>22.7</td><td>10.1</td><td>11.1</td><td>7.1</td><td>5.0</td><td></td><td></td><td></td><td></td><td></td><td>11.9</td></tr><tr><td>Tm<sup>3+</sup></td><td>19.6</td><td>22.7</td><td>9.6</td><td>11.4</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>12.4</td></tr><tr><td>Yb<sup>3+</sup></td><td>19.7</td><td>22.6</td><td>8.9</td><td>11.8</td><td>7.0</td><td>4.4</td><td>4.6</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Lu<sup>3+</sup></td><td>20.0</td><td>22.4</td><td>8.3</td><td>11.9</td><td>6.9</td><td>4.2</td><td>4.6</td><td></td><td></td><td></td><td></td><td></td></tr></tbody></table>

<sup>a</sup> log β<sub>ML</sub> from ref. 173. <sup>b</sup> log β<sub>ML</sub> from ref. 160. <sup>c</sup> log β<sub>MI</sub> from ref. 161. <sup>d</sup> log K<sub>app</sub> in HEPES 10 mM pH 7, NaCl 100 mM, ref. 64. <sup>e</sup> log K<sub>app</sub> in HEPES 10 mM pH 7.5, NaCl 10 mM, ref. 103. <sup>f</sup> log K<sub>app</sub> in bis-Tris 20 mM pH 6, NaCl 25 mM, ref. 129. <sup>g</sup> log K<sub>app</sub> in MOPS 30 mM pH 7, KCl 100 mM, ref. —.

<sup>h</sup> log K<sub>app</sub> for *Mex-LanM* in MOPS 30 mM pH 7.2, KCl 100 mM, measured by CD spectroscopy, ref. 81. <sup>i</sup> log K<sub>app</sub> for *Mex-LanM* in acetate buffer 20 mM pH 5, KCl 100 mM, measured by CD spectroscopy, ref. 155. <sup>j</sup> log K<sub>app</sub> for *Hans-LanM* acetate buffer 20 mM pH 5, KCl 100 mM, measured by CD spectroscopy, ref. 280. <sup>k</sup> log K<sub>app</sub> for *Mex-LanM* KCl/KCH<sub>3</sub>COO<sup>−</sup> buffer 100 mM pH 5.0, measured by UV-vis spectroscopy, ref. 155.

<table><caption>Table 16 Values from Fig. 19: selectivity of small chelators and some peptide/protein scaffolds for Ln³⁺ over Ca²⁺</caption><thead><tr><th>Ln³⁺</th><th>EDTA<sup>a</sup></th><th>DTPA<sup>a</sup></th><th>P3W<sup>b</sup></th><th>EF loop<sup>c</sup></th><th>CaM<sup>d</sup></th><th>Hans-LanM<sup>e</sup></th><th>Mex-LanM<sup>f</sup></th><th>RTX<sup>g</sup></th><th>PqqT<sup>h</sup></th><th>PA<sup>i</sup></th><th>2SCC<sup>j</sup></th></tr></thead><tbody><tr><td>La<sup>3+</sup></td><td>15.5</td><td>19.5</td><td>5.20</td><td></td><td></td><td>10.2</td><td>11.3</td><td>4.1</td><td>6.2</td><td></td><td>6.2</td></tr><tr><td>Ce<sup>3+</sup></td><td>16.1</td><td>20.5</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Pr<sup>3+</sup></td><td>16.3</td><td>21.1</td><td></td><td></td><td></td><td></td><td></td><td>4.5</td><td></td><td></td><td></td></tr><tr><td>Nd<sup>3+</sup></td><td>16.6</td><td>21.6</td><td></td><td></td><td>10.0</td><td></td><td>11.3</td><td>4.5</td><td></td><td></td><td></td></tr><tr><td>Sm<sup>3+</sup></td><td>17.0</td><td>22.3</td><td></td><td></td><td></td><td></td><td>11.2</td><td></td><td></td><td></td><td></td></tr><tr><td>Eu<sup>3+</sup></td><td>17.2</td><td>22.4</td><td>5.2</td><td>6.8</td><td>8.00</td><td></td><td></td><td></td><td>4.6</td><td>6.8</td><td></td></tr><tr><td>Gd<sup>3+</sup></td><td>17.3</td><td>22.5</td><td>5.2</td><td></td><td></td><td></td><td>11.0</td><td></td><td></td><td></td><td></td></tr><tr><td>Tb<sup>3+</sup></td><td>17.8</td><td>22.7</td><td></td><td>6.8</td><td>8.8</td><td></td><td>10.7</td><td>4.6</td><td></td><td>6.3</td><td></td></tr><tr><td>Dy<sup>3+</sup></td><td>18.2</td><td>22.8</td><td></td><td></td><td>8.6</td><td></td><td></td><td>4.6</td><td></td><td></td><td></td></tr><tr><td>Ho<sup>3+</sup></td><td>18.4</td><td>22.8</td><td></td><td></td><td></td><td></td><td>10.6</td><td></td><td></td><td></td><td></td></tr><tr><td>Er<sup>3+</sup></td><td>18.9</td><td>22.7</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Tm<sup>3+</sup></td><td>19.6</td><td>22.7</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Yb<sup>3+</sup></td><td>19.7</td><td>22.6</td><td></td><td></td><td></td><td></td><td></td><td></td><td>4.6</td><td></td><td>6.4</td></tr><tr><td>Lu<sup>3+</sup></td><td>20.0</td><td>22.4</td><td></td><td></td><td></td><td></td><td></td><td></td><td>4.6</td><td></td><td></td></tr><tr><td>Ca<sup>2+</sup></td><td>11.0</td><td>10.7</td><td>4.5</td><td>4.6</td><td>6</td><td>4.2</td><td>3.2</td><td>3.3</td><td>3.8</td><td>3.7</td><td>1.7</td></tr></tbody></table>

<sup>a</sup> log β<sub>ML</sub> from ref. 173. <sup>b</sup> log K<sub>app</sub> in TRIS 5 mM pH 7.8, from ref. 76. <sup>c</sup> log K<sub>app</sub> in HEPES 10 mM pH 7, NaCl 100 mM, from ref. 169. <sup>d</sup> log K<sub>app</sub> in PIPES 25 mM pH 6.8, KCl 100 mM, from ref. 82. <sup>e</sup> log K<sub>app</sub> for *Hans-LanM* acetate buffer 20 mM pH 5, KCl 100 mM, measured by CD spectroscopy, ref. 280. <sup>f</sup> log K<sub>app</sub> for *Mex-LanM* in MOPS 30 mM pH 7.2, KCl 100 mM, measured by CD spectroscopy, ref. 81. <sup>g</sup> log K<sub>app</sub> in bis-Tris 20 mM pH 6, NaCl 25 mM, ref. 129. <sup>h</sup> log K<sub>app</sub> in HEPES 30 mM pH 7, NaCl 100 mM, from ref. 20. <sup>i</sup> log K<sub>app</sub> in HEPES 10 mM pH 7, from ref. 41. <sup>j</sup> log K<sub>app</sub> in Imidazole 30 mM pH 6.9, KCl 50 mM, from ref. 95.

Acknowledgements

The authors acknowledge financial support from the French National Research Agency (ANR) through the ANR-23-CE07-0002 (LnZYME) and ANR-22-CE29-0026 (DREAMY) projects.

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