2 research outputs found
Macroscopic Self-Assembly Based on Molecular Recognition: Effect of Linkage between Aromatics and the Polyacrylamide Gel Scaffold, Amide versus Ester
The
interactions of polyacrylamide- (pAAm-) based gels possessing
cyclodextrin (CD) residues (CD-gels) with pAAm-based gels modified
with aromatic residues through amide and ester linkages (ArA-gels
and ArE-gels, respectively) were investigated to examine the effect
of linkage (i.e., amide and ester) between aromatic residues and the
pAAm gel scaffold. In the present study, benzyl (Bz), 2-naphthylmethyl
(Np), 9-phenanthrylmethyl (Ph), and 1-pyrenylmethyl (Py) residues
were chosen as a series of aromatic residues. αCD-gel did not
interact notably with the ArA-gels and ArE-gels in water. βCD-gel
interacted with the ArA-gels and ArE-gels possessing smaller aromatic
residues (i.e., Bz and Np residues) in water to form gel assemblies.
γCD-gel showed different tendencies of its interactions with
the ArA-gels and with the ArE-gels; γCD-gel interacted with
the ArA-gels carrying larger aromatic residues (i.e., Ph and Py residues),
while γCD-gel formed stable gel assemblies only with NpE-gel
among the ArE-gels examined. This is because γCD residues in
γCD-gel included favorably dimeric aromatic residues in the
ArA-gels and ArE-gels. Reflection fluorescence spectra for the ArA-gels
and ArE-gels possessing fluorescent aromatic residues (i.e., Np, Ph,
and Py residues) in the presence of 10 mM γCD were indicative
of weak selectivities of γCD toward NpE, PhA, and PyA residues.
Such weak selectivities may be largely enhanced in the macroscopic
observation of interaction of CD-gels with the ArA-gels and ArE-gels
presumably because of multivalency
Temperature-Sensitive Macroscopic Assembly Based on Molecular Recognition
The interaction of polyacrylamideÂ(pAAm)-based gel modified
with
benzyl (Bz) moiety (BzÂ(<i>x</i>)-gel, where <i>x</i> denotes the mol % content of Bz moiety) with a pAAm-based gel possessing
cyclodextrin (CD) moieties (αCD-gel, βCD-gel, and γCD-gel)
was investigated at various temperatures to elucidate the effect of
temperature on the formation of macroscopic assembly. The interaction
of BzÂ(<i>x</i>)-gel with CD-gels was stronger at a lower
temperature, consistent with the binding constants for the model system
of pAAm modified with 1 mol % Bz moiety and native CDs. Bz(15)-gel
interacted only with βCD-gel at a higher temperature