Journal of the American Chemical Society
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2
removes OPs from water. Apparently, the “slopes” of
the three “saturation” curves corresponding to the opera-
tion of 1−3 are different, to suggest that their relative
with both spatial and temporal control. Accordingly, we
are examining the scope and mechanistic details of our
photochemical procedure for completing rapid and stim-
uli-responsive sequestration of nerve agents, pesticides
and other toxic compounds with amino-acid functional-
ized baskets in both living systems and the environment.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
“
capacity” to remove OPs could be in order 3>2>1. That
is to say, basket 3 (with the greatest slope) should, alleg-
edly, reach its maximum working capacity (i.e. 100%
removal of OPs) within a narrow range of K’s! On the
other hand, basket 1 is less efficient requiring a greater
range but also higher K values for reaching its full po-
tential. It therefore appears that hydrophobic groups at
the rim of 3 (Figure 4E) amplify the guest precipitation
during the phase transition.
ASSOCIATED CONTENT
Supporting Information
Additional experimental details and protocols. The Sup-
porting Information is available free of charge on the ACS
Publications website.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
B)
(
A)
Basket 1
Basket 2
AUTHOR INFORMATION
0
0
.6
.5
0.6
0.5
0.4
0.3
0.2
0.1
24%
55%
Corresponding Author
7
0.4
0.3
0.2
42%
7
8
9
8
0%
8%
8
9
ACKNOWLEDGMENT
8
4%
0.1
9
This work was financially supported with funds obtained
from National Science Foundation under CHE-1606404.
1
00
300
500
700
900
100 200 300 400 500 600 700 800
Time (min)
(C)
(
D)
Basket 3
0
0
.6
.5
90
80
Basket 1
1
3%
REFERENCES
7
8
9
7
0
0.4
0.3
44%
60
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5
0
0
4
6
6%
7
8
9
0
.2
.1
30
Basket 2
Basket 3
2
0
0
10
(
3) Nachon, F.; Brazzolotto, X.; Trovaslet, M.; Masson, P. Chem.Biol.
50 100 150 200 250 300 350 400
Time (min)
0
0.25 0.5 0.75
1
1.25 1.5 1.75
10
(M-1
2
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(E)
(
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R Group Size
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(
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(
troscopy at 298 K; for longer monitoring times, see Figures
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solution of 1−3 as a function of the corresponding stability
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In summary, molecular baskets with three carbox-
ylates at their rim and OP molecules occupying their
inner space undergo photoinduced decarboxylations and
precipitation to remove OPs from solution. The degree
of sequestration is proportional to the stability of bas-
ket⊂OP complex and the nature (hydrophobicity) of
functional groups at the rim of baskets. Since OPs used
in our study are akin in size and shape to G-type nerve
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(
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