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85178346126
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note
-
Clustering or cooperative binding thermodynamically represents the increased stabilization associated with intercalative binding in the presence of another intercalator bound at the nearest neighbor site compared to the stabilization in the absence of the nearest neighbor. Noncooperative binding indicates equal stabilization in the absence and presence of a nearest neighbor. Anticooperative binding indicates a destabilization in the presence of a nearest neighbor compared to that in its absence. Structurally, cooperative binding might allow possible contact between the favored nearest neighbors. Anticooperativity, while leading to correlated binding, that is the complexes statistically avoiding one another on the helix, would result in an increased separation between complexes compared to random occupation.
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Other theoretical models may better describe our results, however. See: (b) Felts, A. K.; Pollard, W. T.; Friesner, R. A. J. Phys. Chem. 1995, 99, 2929.
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85178385112
-
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note
-
2 is not observed, due to its greater solvent accessibility as the terminal base.
-
-
-
-
59
-
-
85178384115
-
-
note
-
This is also readily apparent in the region of the TMe to aromatic cross-peaks (Supporting Information).
-
-
-
-
60
-
-
85178380610
-
-
note
-
The cross-peaks between TMe groups and aromatic H6 and H8 protons are also informative about the structure of the decamer with two metallointercalators (Supporting Information).
-
-
-
-
62
-
-
85178373845
-
-
note
-
This nearest neighbor exclusion leads us to define cooperative binding as a two base pair separation between intercalating ligands, and noncooperative binding as three or greater base pair separation.
-
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74
-
-
85178339557
-
-
note
-
For the major population with a 4 bp separation between complexes, the closest distances between protons on the ancillary ligands range from 13 to 14 Å. For the minor population at a 3 bp separation, the closest distances between protons on the ancillary ligands range from 7 to 8 Å.
-
-
-
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