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60
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38149089075
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2: C, 61.08; H, 5.64; N, 7.12. Found: C, 60.87; H, 5.75; N, 7.09.
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2: C, 61.08; H, 5.64; N, 7.12. Found: C, 60.87; H, 5.75; N, 7.09.
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61
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38149076777
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in values in Table 1, the fraction of dimer is estimated to be less than 1.2 % in our experimental conditions for fluorescence measurements.
-
in values in Table 1, the fraction of dimer is estimated to be less than 1.2 % in our experimental conditions for fluorescence measurements.
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62
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Park, J.W.1
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38149005141
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2,obs values with large uncertainty.
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2,obs values with large uncertainty.
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65
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0031546366
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66
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38149086377
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Eq 16 was derived under the assumption of complete dethreading of the [2]pseudorotaxane isomers. When [T]o ≪ [α-CD] o ≪ [OcNH3+]o, the equilibrium concentration of α-CD, α-CD]eq, is approximated as [α-CD]o/([OcNH3+]o· KS, where KS is the binding constant of OcNH3+ with α-CD. As KS, 2400 M-1,34 [α-CD]eq in the presence of 0.1 M OcNH3+ are 1.8 × 10-5 M when [α-CD]o, 4.3 mM and 3.8 × 10-6 M when [α-CD]o, 0.9 mM. The rethreading reaction rate could contribute to the observed dethreading rate constants. The pseudo-first order rethreading rate constants, k(rethreading, k1f,app, k 2f,app)·[α
-
2r, of 1/α-CD of which uncertainty is comparable to k(rethreading). This supports the reliability of the present method for the determination of dethreading rate constants.
-
-
-
-
67
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38149079155
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-
The fractions of a thread molecule remaining as P1 and P II [2]pseudorotaxane isomers at equilibrium (fI and fII) are given by fI, K 1,app [α-CD]eq/(1, Kapp[α- CD]eq) and fII, KII,app [α-CD]eq/ 1+Kapp[α-CD]eq, By using the calculated [α-CD]eq values35 in the presence of 0.1 M OcNH3+ and the equilibrium constant data in Table 2, the fI and fII values of 1/α-CD [2]pseudorotaxanes are estimated as 0.007 and 0.10, respectively, when [α-CD]o, 0.9 mM, and 0.024 and 0.34, respectively, when [α-CD]o, 4.3 mM. Similarly, the fI and fII values for 2/α-CD are estimated as 0.0016 and 0.021
-
+. This is a reason why a longer threading time is used for 1 before initiation of the dethreading reaction.
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