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3-OMe are shown in Figure S3, which support the interaction models schematically illustrated in Figure 3, parts B and C, respectively.
-
3-OMe are shown in Figure S3, which support the interaction models schematically illustrated in Figure 3, parts B and C, respectively.
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65
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35548992798
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The ICD intensities of the polymers with (L-Ala)3 decreased in the order of poly-3 > poly-2 > poly-1 as the case with (L-Ala) 3-OMe, while completely opposite with N-Ac-(L-Ala)3-OMe. This can be explained in view of the contribution of the interaction models illustrated in Figure 3. N-Ac-(L-Ala)3-OMe may mainly interact with the polymers through the intermolecular hydrogen bonding as illustrated in Figure 3C because of the absence of attractive ionic interactions. If this is the case, the preferred-handed helicity induction may occur more efficiently in poly-1 and poly-2 rather than poly-3 because the N-Ac-(L-Ala)3-OMe can be located at position closer to the polymer backbones of poly-1 and poly-2 having a smaller size of the glycine residues
-
3-OMe can be located at position closer to the polymer backbones of poly-1 and poly-2 having a smaller size of the glycine residues.
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The hydrogen bonding between the N-H of the pendants of polymers and the carbonyl groups of the oligopeptides and/or the dipole-dipole interaction between the carbonyl groups of the pendants of polymers and oligopeptides may also contribute to the helicity induction to some extent because apparent ICDs are observed in the presence of N-Ac-(L-Ala-Me)3-OMe
-
3-OMe.
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67
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35548989309
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The changes in the 1H NMR spectra during the complexation of poly-3 with N-Ac-(L-Ala)3-OMe also support the hydrogen-bond formation. In the presence of an increasing amount of N-Ac-(L-Ala) 3-OMe, the resonance of the N-H proton of poly-3 showed a small but significant downfield shift (0.023 ppm, Figure S4).4,6 Moreover, the magnitude of the ICDs in the poly-3-N-Ac-(L-Ala)3-OMe and poly-3-(L-Ala)3 complexes were influenced by the pH (Figure S5) and the salt (NaCl) concentration (Figure S6, which also supports the importance of the polar interaction rather than a hydrophobic one in the helicity induction in water.21b However, the ICD intensity of poly-3 with N-Ac-(L-Ala)3-OMe, N-Ac-(L-Ala)3-OMe, poly-3, 20) in water at 0 °C gradually decreased by adding increasing of methanol and almost disappeared in the presence of 75 of methanol see Figure S7, suggesting that th
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3-OMe]/[poly-3] = 20) in water at 0 °C gradually decreased by adding increasing volumes of methanol and almost disappeared in the presence of 75 vol % of methanol (see Figure S7), suggesting that the hydrophobic interactions between me polymers and oligopeptides likely contribute to the helicity induction in the polymers.
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