dynamers, the addition of alkali metal cations results in a redistribution of the
monomeric components between the members of the set, leading to a marked
modification of the fractions of the four constituents. The effect is largest for
lithium, sodium, and potassium ions, which bind best to the receptor site formed
on helical wrapping of the P3 dynamer chain, favored also by interaction between
the donor and acceptor subunits brought into proximity (Fig. 11). In addition, the
latter feature induces a color change. Considering more specifically the sodium
cation effector, the four dynamers can be arranged in a square network, in which the
couples P1, P2 and P3, P4 are agonists (connected via the diagonals) and are
respectively both repressed and amplified (Fig. 12). Thus, this system displays
adaptation by dynamer redistribution, with component selection as well as agonist
0
5
10
15
20
25
30
35
40
45
50
P1d
P2d
P4d
relative mol% of imine bond
equi.
Li
Na
K
Rb
Cs
Antagonistic
Agonistic
Li
Li
Li
Li
Na
Na
Na
Na
K
K
K
K
P3d
Response to Addition of
a Metal Cation Effector
Rb
Cs
Rb
Cs
Rb
Cs
Rb
Cs
Fig. 11 Adaptation of the set of multifunctional dynamers P1, P2, P3, and P4 (see Fig. 10) by
variation in constitutional distribution in response to the addition of alkali metal cations Li
+ , Na
+ ,
K
+ , Rb
+ , and Cs
+ . The initial relative amounts of the four dynamers are shown in pale colors
(on the left of each set). Large variations in relative amounts are observed on addition of alkali
metal cations. A marked increase in the fraction of the trifunctional dynamer P3, containing the
donor, acceptor, and cation binding fragments, occurs as a result of its ability to bind alkali cations
in a helically folded form (shown in the top middle). The fraction of its agonist P4 is increased
similarly, whereas the fractions of antagonists P1 and P2 are strongly decreased. The changes
occurring in the case of Na
+ are shown in darker colors. P1d, P2d, P3d, and P4d indicate the
repeat units of the four corresponding dynamers
168
J.-M. Lehn
monomeric components between the members of the set, leading to a marked
modification of the fractions of the four constituents. The effect is largest for
lithium, sodium, and potassium ions, which bind best to the receptor site formed
on helical wrapping of the P3 dynamer chain, favored also by interaction between
the donor and acceptor subunits brought into proximity (Fig. 11). In addition, the
latter feature induces a color change. Considering more specifically the sodium
cation effector, the four dynamers can be arranged in a square network, in which the
couples P1, P2 and P3, P4 are agonists (connected via the diagonals) and are
respectively both repressed and amplified (Fig. 12). Thus, this system displays
adaptation by dynamer redistribution, with component selection as well as agonist
0
5
10
15
20
25
30
35
40
45
50
P1d
P2d
P4d
relative mol% of imine bond
equi.
Li
Na
K
Rb
Cs
Antagonistic
Agonistic
Li
Li
Li
Li
Na
Na
Na
Na
K
K
K
K
P3d
Response to Addition of
a Metal Cation Effector
Rb
Cs
Rb
Cs
Rb
Cs
Rb
Cs
Fig. 11 Adaptation of the set of multifunctional dynamers P1, P2, P3, and P4 (see Fig. 10) by
variation in constitutional distribution in response to the addition of alkali metal cations Li
+ , Na
+ ,
K
+ , Rb
+ , and Cs
+ . The initial relative amounts of the four dynamers are shown in pale colors
(on the left of each set). Large variations in relative amounts are observed on addition of alkali
metal cations. A marked increase in the fraction of the trifunctional dynamer P3, containing the
donor, acceptor, and cation binding fragments, occurs as a result of its ability to bind alkali cations
in a helically folded form (shown in the top middle). The fraction of its agonist P4 is increased
similarly, whereas the fractions of antagonists P1 and P2 are strongly decreased. The changes
occurring in the case of Na
+ are shown in darker colors. P1d, P2d, P3d, and P4d indicate the
repeat units of the four corresponding dynamers
168
J.-M. Lehn