Reversible double-helix-random-coil transition process of bis{hexa(ethynylhelicene)}s.
Two compounds with two hexa(ethynylhelicene) parts connected by a flexible hexadecamethylene and a rigid butadiyne linker were synthesized. The 1H NMR spectroscopic and CD analyses and vapor-pressure osmometry (VPO) of these two compounds revealed intramolecular double-helix formation. Upon heating a 5-microM solution in toluene, the double-helix structure unfolded to form a random coil, and on cooling it folded again into a double helix. The thermodynamic stabilities of both structures were dependent on temperature, and the structural change in both compounds is due to the large enthalpies and entropies under equilibrium. The rate constants of their unfolding were obtained by assuming a pseudo-first-order reaction; the compound with a rigid linker unfolded slower than that with a flexible linker. The former has a larger activation energy, and its double-helix and random-coil conformers were separated by chromatography. The rate of folding was also faster for the flexible-linker compound with larger activation energy. The rate constants for the folding of both compounds slightly decreased with increasing temperature, which was ascribed to the presence of exothermic pre-equilibrium and rate-determining steps. The folding was markedly accelerated with increasing random-coil concentration, which suggests the involvement of self-catalysis. A mechanism of folding was proposed. The involvement of different mechanisms of folding and unfolding was suggested by the kinetic studies, and it was confirmed by the presence of hysteresis in the melting profiles. The difference in linker structure also affected the thermal-switching profiles of the double-helix-random-coil structural changes.
Sugiura
Hiroki
H
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aoba 6-3, Sendai 980-8578, Japan.
Amemiya
Ryo
R
Yamaguchi
Masahiko
M
D002942:Circular Dichroism; D005030:Ethylenes / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D011083:Polycyclic Compounds / Q000737:chemistry*; D013816:Thermodynamics
D005030:Ethylenes; D011083:Polycyclic Compounds; C031660:helicenes; C036216:ethylene