title: Structures and Surface Properties of "Cyclic" Polyoxyethylene Alkyl Ethers: Unusual Behavior of Cyclic Surfactants in Water.
abstract: The cyclization of amphiphiles has emerged as an attractive strategy for inducing remarkable properties in these materials without changing their chemical composition. In this study, we successfully synthesized three cyclic polyoxyethylene dodecyl ethers (c-POEC12's) with different ring sizes and explored the effects of their topology on their surface and self-assembly properties related to their function, comparing them with those of their linear counterparts (l-POEC12's). The surface activity of the c-POEC12's remained almost constant despite the change in their hydrophobic and hydrophilic balance (HLB) value, while that of the l-POEC12's decreased with an increase in the HLB value as general surfactants. In contrast to the normal micelles seen in the case of the l-POEC12's (3.4-9.7 nm), the cyclization of the POEC12's resulted in the formation of large spherical structures 72.8-256.8 nm in size. It also led to a dramatic decrease of 28 °C in the cloud point temperature. Furthermore, the cyclization of the POEC12's markedly suppressed the rate of protease hydrolysis caused by the surfactants. The initial rate of reduction of a detergent enzyme from Bacillus licheniformis was increased by more than 40% in the case of c-POE600C12 and c-POE1000C12, even though they exhibited surface activities almost equal to or higher than those of their linear counterparts. These results suggest that cyclization induces unusual aqueous behaviors in POEC12, making the surfactant milder with respect to detergent enzymes while ensuring it exhibits increased surface activity.
authors.affiliation: Faculty of Science and Technology, Tokyo University of Science , 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Hirose
authors.affiliation: Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST) , Central 5-2, 1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Taira
authors.affiliation: Faculty of Science and Technology, Tokyo University of Science , 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
authors.forename: Kenichi
authors.initials: K
authors.lastname: Sakai
authors.affiliation: Faculty of Science and Technology, Tokyo University of Science , 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
authors.forename: Hideki
authors.initials: H
authors.lastname: Sakai
authors.affiliation: Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST) , Central 5-2, 1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.
authors.forename: Akira
authors.initials: A
authors.lastname: Endo
authors.affiliation: Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST) , Central 5-2, 1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.
authors.forename: Tomohiro
authors.initials: T
authors.lastname: Imura