Supramolecular helical assembly of an achiral cyanine dye in an induced helical amphiphilic poly(phenylacetylene) interior in water.
A water-soluble amphiphilic poly(phenylacetylene) bearing the bulky aza-18-crown-6-ether pendants forms a one-handed helix induced by l- or d-amino acids and chiral amino alcohols through specific host-guest interactions in water. We now report that such an induced helical poly(phenylacetylene) with a controlled helix sense can selectively trap an achiral benzoxazole cyanine dye among various structurally similar cyanine dyes within its hydrophobic helical cavity inside the polymer in acidic water, resulting in the formation of supramolecular helical aggregates, which exhibit an induced circular dichroism (ICD) in the cyanine dye chromophore region. The supramolecular chirality induced in the cyanine aggregates could be further memorized when the template helical polymer lost its optical activity and further inverted into the opposite helicity. Thereafter, thermal racemization of the helical aggregates slowly took place.
Miyagawa
Toyoharu
T
Yashima Super-structured Helix Project, Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency (JST), 101 Creation Core Nagoya, 2266-22 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-0003, Japan.
Yamamoto
Miho
M
Muraki
Reiko
R
Onouchi
Hisanari
H
Yashima
Eiji
E
D000114:Acetylene / Q000031:analogs & derivatives* / Q000737:chemistry; D002232:Carbocyanines / Q000737:chemistry*; D002942:Circular Dichroism; D057927:Hydrophobic and Hydrophilic Interactions; D018625:Microscopy, Atomic Force; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism; D014867:Water
D002232:Carbocyanines; C519145:poly(phenylacetylene); D014867:Water; D000114:Acetylene