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Consistent with our own self-assembly model (ref 29) and in analogy to the model proposed by Boden et al. (ref 40), the terms tapes, ribbons, and fibrils are explicitly used to describe single β-sheets, stacked dimers of β-sheets, as well as higher aggregates via stacking of β-sheets, respectively.
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Consistent with our own self-assembly model (ref 29) and in analogy to the model proposed by Boden et al. (ref 40), the terms tapes, ribbons, and fibrils are explicitly used to describe single β-sheets, stacked dimers of β-sheets, as well as higher aggregates via stacking of β-sheets, respectively.
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A few reports concerning the CD activity of poly(diacetylene)s have been published previously (refs 36, 37, 44-47, With the exception of the investigations by Ando et al. and Hanks et al, refs 36 and 37, however, only poorly defined CD signatures were observed that were typically not interpretable and probably resulted from a circular intensity differential scattering (cids) contribution of large, ill-defined superstructures. This conclusion is, for example, illustrated by the results reported by Liu et al, ref 47, who observed CD activity in LB films of achiral poly(diacetylene)s; the CD activity was irreproducible and depended, e.g, on the subphase; TEM images showed supposedly helical superstructures with a pitch on the order of the wavelength of the absorbed light. For more information on cids, see Bustamante, C. Tinoco, I, Jr, Maestre, M. F. Proc. Natl. Acad. Sci. U.S.A. 1983, 80, 3568
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A few reports concerning the CD activity of poly(diacetylene)s have been published previously (refs 36, 37, 44-47). With the exception of the investigations by Ando et al. and Hanks et al. (refs 36 and 37), however, only poorly defined CD signatures were observed that were typically not interpretable and probably resulted from a circular intensity differential scattering (cids) contribution of large, ill-defined superstructures. This conclusion is, for example, illustrated by the results reported by Liu et al. (ref 47), who observed CD activity in LB films of achiral poly(diacetylene)s; the CD activity was irreproducible and depended, e.g., on the subphase; TEM images showed supposedly helical superstructures with a pitch on the order of the wavelength of the absorbed light. For more information on cids, see Bustamante, C. Tinoco, I., Jr.; Maestre, M. F. Proc. Natl. Acad. Sci. U.S.A. 1983, 80, 3568.
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49
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The color changes may look similar to previously published examples (refs 32-35) at first sight, but there are important differences. Solutions of P1 or P2 in chlorinated solvents maintained their blue-purple color, and only the addition of strong hydrogen bond breaking agents induced the color changes. The transition from the blue to the yellow form clearly proceeded in two consecutive steps, with the red form as an actual intermediate. A similar supposedly two-step transition was recently described by Dautel, Moreau et al. (ref 28), but the reported UV spectra showed mixtures of different species and were, hence, difficult to interpret.
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The color changes may look similar to previously published examples (refs 32-35) at first sight, but there are important differences. Solutions of P1 or P2 in chlorinated solvents maintained their blue-purple color, and only the addition of strong hydrogen bond breaking agents induced the color changes. The transition from the blue to the yellow form clearly proceeded in two consecutive steps, with the red form as an actual intermediate. A similar supposedly two-step transition was recently described by Dautel, Moreau et al. (ref 28), but the reported UV spectra showed mixtures of different species and were, hence, difficult to interpret.
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Giesa et al. have conclusively shown that this explanation falls short anyway; UV absorption maxima above about 550 nm probably result from interactions of poly(diacetylene) chromophores in the crystalline or aggregated state; see Giesa, R. R. Schulz, C. Polym. Int. 1994, 33, 43.
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Giesa et al. have conclusively shown that this explanation falls short anyway; UV absorption maxima above about 550 nm probably result from interactions of poly(diacetylene) chromophores in the crystalline or aggregated state; see Giesa, R. R. Schulz, C. Polym. Int. 1994, 33, 43.
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