title: Columnar structures from asymmetrically tapered biphenylamide.
abstract: An asymmetrically tapered N,N'-tris[[(2-dodecylaminocarbonyl)ethyl]methyl]-4-biphenylamide (asym-C(12)PhA, where n is the number of carbon atoms in the alkyl chains, n = 12) was newly designed and synthesized. In this asymmetrically tapered asym-C(12)PhA biphenylamide, H-bondable hydrophilic amide moieties are located at between a rigid hydrophobic biphenyl rod and three flexible hydrophobic alkyl chains. Computer energy minimization indicated that three-dimensional (3D) geometry of asym-C(12)PhA biphenylamide looks like a cone with dimensions of 3.01 nm in height and 1.44 nm in bottom radius. Phase transitions and supra-molecular structures were identified utilizing the combined techniques of differential scanning calorimetry, 1D wide-angle X-ray diffraction (1D WAXD), Fourier-transform infrared spectroscopy, and solid-state (13)C nuclear magnetic resonance analyses. The asym-C(12)PhA self-assembled into a highly ordered columnar mesophase just below the isotropization temperature and then transformed to 3D columnar crystalline phase (Phi(Cr)) on further cooling. Selected area electron diffractions in transmission electron microscopy (TEM) along with 1D WAXD and cross-polarized optical microscopy suggested that discotic building blocks were constructed by rotating 120 degrees of three asym-C(12)PhA with respect to neighboring ones and the tmb (top-middle-bottom) stacked discotic building blocks further self-organized into columns. These columns are laterally intercalated to form the Phi(Cr) phase. On the basis of the TEM image and polyethylene surface decoration technology, it was identified that the self-assembled asym-C(12)PhA fibers with approximately 1 mum in diameter and several millimeters in length were braids of tiny single crystals.
authors.affiliation: Polymer Materials Fusion Research Center and Department of Polymer-Nano Science and Technology, Chonbuk National University, Jeonju 561-756, Korea.
authors.forename: Soo-Jin
authors.initials: SJ
authors.lastname: Park
authors.forename: Seok-Ho
authors.initials: SH
authors.lastname: Hwang
authors.forename: Namil
authors.initials: N
authors.lastname: Kim
authors.forename: Shiao-Wei
authors.initials: SW
authors.lastname: Kuo
authors.forename: Hak Yong
authors.initials: HY
authors.lastname: Kim
authors.forename: Seul-Ki
authors.initials: SK
authors.lastname: Park
authors.forename: Young-Jin
authors.initials: YJ
authors.lastname: Kim
authors.forename: Changwoon
authors.initials: C
authors.lastname: Nah
authors.forename: Joong Hee
authors.initials: JH
authors.lastname: Lee
authors.forename: Kwang-Un
authors.initials: KU
authors.lastname: Jeong