. Author manuscript; available in PMC: 2011 May 12.

Published in final edited form as: Chem Rev. 2010 May 12;110(5):2960–3018. doi: 10.1021/cr900284a

TABLE 11.

Exchange rates and bound water lifetimes for Ln³⁺ macrocyclic complexes reviewed in this work.

Complex	k_ex s⁻¹	τ_M	Method	Solvent	Reference
Gd³⁺–1	4.1 × 10⁶	244 ns	¹⁷O NMR	Water	112
Gd³⁺–2	4.8 × 10⁶	208 ns	¹⁷O NMR	Water	112,325
	5.4 × 10⁶ – SAP	185 ns	¹H NMRD/¹⁷O
	500.0 × 10⁶- TSAP	2 ns	NMR/EPR (global analysis)
			¹H NMRD/¹⁷O NMR/EPR (global analysis)
Gd³⁺–3	14.3 × 10⁶	70 ns	¹⁷O NMR	Water	113
Gd³⁺–4	167.0 × 10⁶	6.0 ns	¹⁷O NMR	Water	113
Gd³⁺-5	270.0 × 10⁶	3.7 ns	¹⁷O NMR	Water	114
Gd³⁺-7	31.0 × 10⁶	32 ns	¹⁷O NMR	Water	115
Gd³⁺-8	330.0 × 10⁶	3 ns	¹⁷O NMR	Water	115
Gd³⁺-10	25.0 × 10⁶	40 ns	¹H NMRD/¹⁷O NMR	Water (pH 4.7)	119
	71.4 × 10⁶	14 ns	¹H NMRD/¹⁷O NMR	Water (pH 7)	119
Gd³⁺-13 (RRRR)	8.3 × 10⁶	120 ns	¹⁷O NMR	Water	130
Gd³⁺-13 (SSSS)	66.7 × 10⁶	15 ns	¹⁷O NMR	Water	130
Gd³⁺-15	4.3 × 10⁵	2.3 μs	¹⁷O NMR	Water	326,131
Gd³⁺-15 (310 K)	1.03 × 10⁶	967 ns	¹⁷O NMR	Water	327
Gd³⁺-15	1.2 × 10⁶	810 ns	¹H NMRD	Water	177
Eu³⁺-15	0.66 × 10⁶	1.5 μs	¹⁷O NMR	Water	131
Dy³⁺-15	3.5 × 10⁶	285 ns	¹⁷O NMR	Water	131
Nd³⁺-15	0.53 × 10⁶	1.9 μs	¹⁷O NMR	Water	131
Tb³⁺-15	1.6 × 10⁶	621 ns	¹⁷O NMR	Water	131
Ho³⁺-15	6.0 × 10⁶	167 ns	¹⁷O NMR	Water	131
Pr³⁺-16	22.0 × 10³	45 μs	¹⁷O NMR	CD₃CN	132
	52.6 × 10³	19 μs	¹H NMR		132
Nd³⁺-16	6.0 × 10³	168 μs	¹⁷O NMR	CD₃CN	132
	14.1 × 10³	70 μs	¹H NMR
Sm³⁺-16	1.5 × 10³	653 μs	¹⁷O NMR	CD₃CN	132
	1.8 × 10³	565 μs	¹H NMR
Eu³⁺-16	1.2 × 10³	789 μs	¹H NMR	CD3CN	132,42
Eu³⁺-16	1.2 × 10³	789 μs	17O NMR	CD3CN	132,42
Eu³⁺-16	2.61 × 10³	382 μs	¹H NMR	Water	132,42
Eu³⁺-16	4.76 × 10³	210 μs	CEST-Numerical Solutions	Water	178
Eu³⁺-16	4.4 × 10³	225 μs	¹H NMR	Water	178
Eu³⁺-16	4.04 × 10³	247 μs	Omega Plot	Water	178
Gd³⁺ -16	4.0 × 10³	250 μs	¹⁷O NMR	CD₃CN	153
	5.2 × 10³ (pH 7)	190 μs	T₁ ¹H NMR	Water	153
Y³⁺-16	16.9 × 10³	58.9 μs	¹⁷O NMR	CD₃CN	132
Er³⁺-16	56.5 × 10³	17.7 μs	¹⁷O NMR	CD₃CN	132
Dy³⁺-16	47.6 × 10³	21 μs	¹⁷O NMR	Water	328
	25.5 × 10³	39 μs		CH₃CN	152
Gd³⁺-17	5.2 × 10⁴	19 μs	¹⁷O NMR	Water	125
Eu³⁺-17	8.3 × 10³ (SAP)	120 μs	¹H/¹⁷O NMR	CD₃CN	126
	327.0 × 10³ (TSAP)	3 μs
Eu³⁺-17	9.4 × 10³ (SAP)	106 μs	¹H NMR	CD₃CN	126,128
	474 × 10³ (TSAP)	2.1 μs
Eu³⁺-18	8.2 × 10³ (SAP)	122 μs	¹H NMR	CD₃CN	128
	59.7 × 10³ (TSAP)	16.7 μs
Eu³⁺-19	3.6 × 10³	278 μs	¹H NMR	CD₃CN	143
Yb³⁺-19	1.9 × 10⁶	526 μs	¹H NMR	CD₃CN	143
Gd³⁺-20	0.769 × 10³	1.3 μs	¹⁷O NMR	Water	5
Gd³⁺-21	0.161 × 10³	6.2 μs	¹⁷O NMR	Water	5
Gd³⁺-22	39.2 × 10³	26 ns	¹⁷O NMR	Water (pH 7.2)	153
Dy³⁺-22	47.6 × 10³	21 ns	¹⁷O NMR	Water	329
Gd³⁺-23	1.9 × 10⁶	526 ns	¹⁷O NMR	Water	136
Gd³⁺-24	1.3 × 10⁶	769 ns	¹⁷O NMR	Water	136
Gd³⁺-24 (310 K)	5.6 × 10⁶	179 ns	¹⁷O NMR	Water	330
Gd³⁺-25	0.98 × 10⁶	1.02 μs	¹⁷O NMR	Water	174
Gd³⁺-26	0.6 × 10⁶	1.67 μs	¹⁷O NMR	Water	174
Gd³⁺-27	0.21 × 10⁶	4.7 μs	¹H NMRD	Water	176
Gd³⁺-27 (310 K)	1.54 × 10⁶	648 ns	¹⁷O NMR	Water	330
Gd³⁺-28 (310 K)	1.2 × 10⁶	841 ns	¹⁷O NMR	Water	330
Gd³⁺-29 (310 K)	1.1 × 10⁶	901 ns	¹⁷O NMR	Water (pH 6)	330
	8.7 × 10⁶	115 ns	¹⁷O NMR	Water (pH 9.7)	330
Gd³⁺-30 (310 K)	0.04 × 10⁶	2521 ns	¹⁷O NMR	Water	330
Gd³⁺-31 (310 K)	0.035 × 10⁶	2882 ns	¹⁷O NMR	Water	330
Gd³⁺-32 (310 K)	0.7 × 10⁶	1.4 μs	¹H NMRD	Water	176
Gd³⁺-33 (310 K)	0.2 × 10⁶	4.0 μs	¹H NMRD	Water	176
Gd³⁺-34	0.42 × 10⁶	2.4 μs	¹H NMRD	Water	176
Gd³⁺-34 (310 K)	0.71 × 10⁶	1.4 μs	¹H NMRD	Water	176
Gd³⁺-35	6.3 × 10⁶	159 ns	¹⁷O NMR	Water	137
Eu³⁺-36	11.2 × 10³	890 μs	¹H NMR	CD₃CN	128
Gd³⁺-37 (NO₂)	7.4 × 10⁶	135 ns	¹⁷O NMR	Water	144
Gd³⁺-37 (NH₂)	17.6 × 10⁶	57 ns	¹⁷O NMR	Water	144
Eu³⁺-38 (CH₃)	3.2 × 10³	310 μs	CEST - Numerical solutions	Water/CH₃CN	145
Eu³⁺-38 (OCH₃)	5.1 × 10³	198 μs	CEST - Numerical solutions	Water/CH₃CN	145
Eu³⁺-38 (H)	3.7 × 10³	269 μs	CEST - Numerical solutions	Water/CH₃CN	145
Eu³⁺-38 (F)	6.9 × 10³	144 μs	CEST - Numerical solutions	Water/CH₃CN	145
Eu³⁺-38 (COO^tBu)	2.8 × 10³	352 μs	CEST - Numerical solutions	Water/CH₃CN	145
Eu³⁺-38 (CN)	3.0 ×10³	324 μs	CEST - Numerical solutions	Water/CH₃CN	145
Eu³⁺-43	2.7 × 10⁴	37 μs	CEST - Numerical solutions	Water	138
Eu³⁺-44	1.0 × 10⁵	10 μs	CEST - Numerical solutions	Water	138
Eu³⁺-45	5.9 × 10⁴	17 μs	CEST - Numerical solutions	Water	138
Eu³⁺-46	>1 × 10⁶	< 1 μs	CEST - Numerical solutions	Water	138
Eu³⁺-47	9.61 × 10³	104 μs	CEST - Numerical solutions	Water	138
Eu³⁺-48	4.8 × 10³	210 μs	CEST - Numerical solutions	Water	138
Gd³⁺-50	0.787 × 10³	1.27 μs	T₁ ¹H NMR	Water	153
Tb³⁺-51	2.3 × 10⁵	4 μs	¹H NMR	Water	154
Nd³⁺-51 (312 K)	4.9 × 10⁴	20 μs	¹H NMR	Water	154
Pr³⁺-51 (312 K)	2.1 × 10⁵	4.8 μs	¹H NMR	Water	154
Eu³⁺ -51	3.8 × 10³	262 μs	¹H NMR	Water (pH 7)	153
	6.3 × 10³	160 μs	CEST - Numerical solutions	Water	178
	6.4 × 10³	156 μs	CEST - Omega plot	Water	178
Eu³⁺-51 (312 K)	5.8 × 10⁴	17 μs	1H NMR	Water	154
Eu³⁺-54	5.0 × 10³	200 μs	CEST - Numerical solutions	Water	173
Eu³⁺-55	12.3 × 10³	81 μs	CEST - Numerical solutions	Water	173
Eu³⁺-56	18.2 × 10³	55 μs	CEST- Numerical solutions	Water	173
Eu³⁺-57	3.7 × 10³	271 μs	CEST - Numerical solutions	Water	194
Eu³⁺-58	45.0 × 10³	22 μs	CEST - Numerical solutions	Water	197
Eu³⁺-58 + Glucose	23.2 × 10³	43 μs	CEST - Numerical solutions	Water	197
Eu³⁺-64	10.0 × 10³	100 μs	CEST - Numerical solutions	Water	232
Gd³⁺-76	14.7 × 10⁶	68 ns	¹⁷O NMR	Water	127
Eu³⁺-90	4.5 × 10³	221 μs	CEST - Numerical solutions	Water	241
Eu³⁺-91	6.9 × 10³	144 μs	CEST - Numerical solutions	Water	241
Eu³⁺-94	1.5 × 10³	687 μs	CEST - Numerical solutions	Water	270
Gd³⁺-96	1.24 × 10³	805 μs	T₁ (¹H)	Water	153,331
Eu³⁺-96	0.743 × 10³	1346 μs	1H NMR	CD₃CN	153,331
Gd³⁺-107	0.5 × 10⁶ (SAP)	200 ns	¹⁷O NMR	Water	127
	22.0 × 10⁶ (TSAP)	45 ns
Gd³⁺-108	0.7 × 10⁶ (SAP)	1.35 μs	¹⁷O NMR	Water	263
	71 × 10⁶ (TSAP)	14 ns