期刊
CHEMICAL SCIENCE
卷 7, 期 6, 页码 3574-3580出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc04959h
关键词
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资金
- JSPS KAKENHI [25860003, 15K18825]
- Uehara Foundation
- Tohoku University Frontier Research Institute for Interdisciplinary Sciences (FRIS)
- Grants-in-Aid for Scientific Research [25860003, 15K18825] Funding Source: KAKEN
An ethynylhelicene oligomer [(M)-D-4]-C-12-TEG with six tri(ethylene glycol) (TEG) groups at the termini was synthesized, and double-helix formation was studied using CD, UV-Vis, vapor pressure osmometry, dynamic light scattering, and H-1 NMR. [(M)-D-4]-C-12-TEG reversibly changed its structure between a double helix and a random coil in response to heating and cooling in aromatic solvents, non-aromatic polar organic solvents, and aqueous solvent mixtures of acetone/water/triethylamine. Notably, [(M)-D-4]-C-12-TEG in acetone/water/triethylamine (1/2/1) formed a double helix upon heating and disaggregated into random coils upon cooling. The double helix/random coil ratio sharply changed in response to temperature changes. This is an unprecedented inverse thermoresponse, which is opposite to the ordinary thermoresponse in molecular dimeric aggregate formation. This phenomenon was explained by the dehydration of the terminal TEG groups and the formation of condensed triethylamine domains upon heating.
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