Nano‐ and Microstructure Fabrication by Using a Three‐Component System

Abstract

Two-component amphiphiles based on hydrogen-bonded complexes between terephthaloylbisalanine (H(2)TBA) and dodecylamine (DA) are able to self-assemble into nano- and microsized superstructures in an aqueous solvent. It is possible to modulate the morphology of these self-assembled superstructures by modifying the composition of the complexes, which can be achieved by changing the molar ratio of the two components or by changing the chirality of H(2)TBA. For example, right-handed microhelical ribbon structures were formed with L-TBA(1.0)DA(2.0), whereas in the case of rac-TBA(1.0)DA(2.0), flat ribbonlike structures were observed. Although L-TBA(1.0)DA(1.0) exhibited entangled fibrous structures, rac-TBA(1.0)DA(1.0) exhibited wire structures. Different ratios of H(2)TBA and DA were self-assembled into fiber-, wire-, and tubulelike superstructures, as well as monoclinic, columnar, and lamellar aggregation patterns. The self-assembled superstructures of TBA(x)DA(y) were significantly changed by adding metal ions. Transition metal (Cd(II), Co(II), and Zn(II)) complexes with L-TBA(x)DA(y) self-assembled into rod-, tubule-, wire-, and platelike superstructures. Metal-ion complexes with rac-TBA(x)DA(y) exhibited different superstructures. Our work suggests that it is possible to fabricate a wide variety of nano- and microsized superstructures by using two- and three-component amphiphiles.

Handedness Inversion of Chiral 3‐Aminophenol Formaldehyde Resin Nanotubes Mediated by Metal Coordination

“…[28] At this time,due to the present of partially deprotonated carboxyl groups,3 -AP would tend to be adsorbed near the surface of the nanoribbons. [35] Nevertheless,a fter the introduction of Mn 2+ to the coassembly system, the carboxyl groups in the L-PhgC 16 were further deprotonated, resulting in increased electrostatic resistance between adjacent amphiphilic molecules.Simultaneously,the coordination between the Mn 2+ ,c arboxyl and amide groups (green region in Figure 6c)r ather than original hydrogen bond between amide units dominated the stacking mode of the coassemblies,leading to the formation of Mn 2+ -mediated right-handed supramolecular twisted nanoribbons.T he coordinated carboxylate groups pointed out from the edges of these nanoribbons.A fter the subsequent addition of formaldehyde,t he resin oligomers were formed and preferentially adsorbed on the edges and surfaces of the nanoribbons (Figure 6d). [36] Ther eaction rate was so fast that the metastable twisted APF could be formed within 30 seconds.…”

Bio-inspired supramolecular self-assembly towards soft nanomaterials

“…The constructive supramolecular self-assembly of glycolipids into soft nanostructures has also been explored by several groups such as O’Brien [48–49], Nolte [50], Lee [51–52], Ho [53–56], Cintas [57], and Hong [58]. Besides, Shinkai group studied the combinatorial library of atypical sugar-integrated amphihphiles which exhibit unique organic gelling capabilities with different three-dimensional network [59–64].…”

Self-Assembling Functionalized Amino Acids into Unusual Shapes

“…Using smaller biobased molecules is a rather interesting motif because of a potentially easier synthesis and less complicated assembly. Derivatives of lysine 8 , alanine 18 , glycine, 19 aspartic acid, 19 and phenylalanine 20 have been reported in the synthesis of structures. The largest drawback to most of these approaches is the deviation from the aqueous standard conditions at which nature operates.…”

“…Jang et al synthesized fibers, wires, ribbon-like structures, tubules and plate-like structures using a three component system of terephthaloylbisalanine, dodecylamine, and a metal complex of zinc, cadmium, or copper. 18 The materials described in this were formed from one component systems of substituted amino acids in aqueous solution.…”