Structural fine-tuning of (-donor-spacer-acceptor-spacer-)n type foldamers. Effect of spacer segment length, temperature, and metal-ion complexation on the folding process

Macromolecules

Volumn 38, Issue 3, 2005, Pages 676-686

  Ghosh, Suhrit ^a   Ramakrishnan, S ^a  

^a INDIAN INSTITUTE OF SCIENCE   (India)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL COMPOUNDS; CONFORMATIONS; ETHYLENE; OLIGOMERS; POLYMERS; SPECTRUM ANALYSIS; SYNTHESIS (CHEMICAL); THERMAL EFFECTS;

DONORS; HETEROATOMS; SOLVOPHOBIC EFFECTS; SUPRAMOLECULES;

COMPLEXATION;

EID: 13444288305     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma0478759     Document Type: Article

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66. The polymer PDA - 3OE, with a tri(oxyethylene) spacer, was also prepared but was found to have very poor solubility, and hence its solution properties could not be examined.
67. All the spectral data are available in the Supporting Information.
68. 3), as evidenced from the light scattering detector signal. Ultrasonication of the solutions prior to injection reduces the high molecular tail but does not completely remove it.
69. 30 we had shown that the spectral changes seen in the nascent polymer PDA - 6OE were very similar to those seen in the high molecular weight fractionated samples. Similarly, representative studies using fractionated samples of the other two polymers were also done, which helped reaffirm the earlier observations.
70. Polyimides from pyromellitic dianhydride and simple amine terminated oligo(oxyethylene)s were prepared as controls and these were white in color.
71. For all the complete spectra refer to the Supporting Information.
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73. + ion (see Figure S13 in Supporting Information) provides further evidence in support of the hypothesis that while the NMR chemical shifts are sensitive to the presence of sandwiched structures and reflects the formation of extended stacked structures in the polymer, the CT absorbance fails to detect this stacking. Since in the DA model only simple pairing can occur but not extended stacking, one sees a smaller change in the δ values compared to that seen in the polymer, while the variations in the CT absorbance in both systems are almost parallel.
74. The higher the stability of the fully folded state when compared to the unfolded one, the greater would be the temperature-dependence of the equilibrium constant; i.e., one would expect the equilibrium to shift more toward the fully folded form as one reduces the temperature.
75. The solvent effect was examined using methanol/chloroform mixtures as it exhibited a larger effect on folding, while an aprotic solvent mixture, such as acetonitrile/chlorofonn mixture, is more suitable for metal-ion titration studies.
76. 4 and NaSCN, and no significant difference was noticed.
77. The spectral changes of PDA - 5OE and PDA - 6OE with increasing concentrations of various alkali-metal ions are provided in the Supporting Information. The variation of the spectral features in the aliphatic region in these spectra provides further direct evidence for the fact that the complexation indeed occurs with the OE spacer. The nonuniform changes in the aliphatic region (some of the peaks move upfield while others move downfield) of the spectra confirms that the variation in the chemical shift is not induced by changes in the dielectric (or ionic strength) of the medium but is a direct reflection of complexation. Formation of the CT complex between the donor and acceptor units could bring some of the methylene protons, particularly those close to the aromatic rings, under the influence of the aromatic ring current, and therefore further influencing their chemical shifts. Similar changes have been seen in the case of podands by Vogue et al. See ref 26a.
78. In PDA - 5OE, the changes seen in the 6 values of the acceptor protons in the presence of Li and Na are almost the same while changes in their UV-visible spectra are distinctly different. This is possibly because of differences in the geometries of the CT complexes formed upon complexation with Na and Li. The effect of differences in geometry appears to be more significant on the ACT, but not on acceptor proton chemical shifts. This is confirmed from the model compound (DAD - 5OE) studies, wherein the changes seen in the chemical shifts of the acceptor proton under similar conditions are roughly similar for both Na and Li (see Figure 10), although they exhibit distinct differences in their ACT.
79. We assume, of course, that the DAD and ADA model compounds readily form sandwiched structures in the presence of alkali-metal ions. This assumption is supported by the large difference in the NMR spectral variations between these models and the corresponding DA analogue.
80. Similar changes in the proton NMR spectra of naphthalene donor containing adeamers were reported by Iverson and coworkers, and were ascribed to differences in the geometries of the D-A complexes. See ref 22c.
81. When the donor is sandwiched both the aromatic rings of the naphthalene unit it experiences similar changes and remains undifferentiated.
82. Dynamic light scattering studies on a representative polymer, PDA - 6OE, revealed that a dramatic narrowing of the size distribution occurred in the presence of an excess of K ion, possibly reflecting the breaking of aggregated structures, which was also seen in the GPC chromatograms. However, a quantitative estimate of extent of stacking could not be obtained.