Reinforced Self-Assembly of Donor–Acceptor π-Conjugated Molecules to DNA Templates by Dipole–Dipole Interactions Together with Complementary Hydrogen Bonding Interactions for Biomimetics

Abstract

One of the most important criteria for the successful DNA-templated polymerization to generate fully synthetic biomimetic polymers is to design the complementary structural monomers, which assemble to the templates strongly and precisely before carrying polymerization. In this study, water-soluble, laterally thymine-substituted donor-acceptor π-conjugated molecules were designed and synthesized to self-assemble with complementary oligoadenines templates, dA(20) and dA(40), into stable and tubular assemblies through noncovalent interactions including π-π stacking, dipole-dipole interactions, and the complementary adenine-thymine (A-T) hydrogen-bonding. UV-vis, fluorescence, circular dichroism (CD), atomic force microscopy (AFM), and transmission electron microscopy (TEM) techniques were used to investigate the formation of highly robust nanofibrous structures. Our results have demonstrated for the first time that the dipole-dipole interactions are stronger and useful to reinforce the assembly of donor-acceptor π-conjugated molecules to DNA templates and the formation of the stable and robust supramolecular nanofibrous complexes together with the complementary hydrogen bonding interactions. This provides an initial step toward DNA-templated polymerization to create fully synthetic DNA-mimetic polymers for biotechnological applications. This study also presents an opportunity to precisely position donor-acceptor type molecules in a controlled manner and tailor-make advanced materials for various biotechnological applications.

Hydrogen-bonding regulated assembly of molecular and macromolecular amphiphiles

“…In a slightly different design, 32 the ssDNA-templated assembly was explored using thymine appended OVP (9) wherein the thymine moiety was made to interact with the oligo-deoxyadenylic acid by a complementary H-bond (A-T base pair) to produce helical fibers. In a related work, 33 Lo and co-workers demonstrated co-assembly of a thymine-substituted donor-acceptor p-conjugated amphiphile (10) with oligoadenine templates producing stable tubular assemblies through various noncovalent interactions including p-p stacking, dipole-dipole interactions, and adeninethymine (A-T) H-bonding. While the forgone discussion showed examples on two-component supramolecular assembly of amphiphiles by complementary H-bonding, Ferniri and coworkers reported 34 an interesting example of a cationic amphiphile (11, Fig.…”

Fluorescence control of chitin and chitosan fabricatedviasurface functionalization using direct oxidative polymerization

“… 8,9 The surface modification of chitin nanocrystals with poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV) via chloridization improved the lipophilicity of chitin nanocrystals. 10 The high capacity absorbance of chitin fibers functionalized with a uranyl-selective amidoxime group used for the extraction of uranium from seawater has been reported. 11 The hydrophobic of the modified chitin surface leads to the highly effective separation of oil from water.…”

Investigation of Supramolecular Nanofibers Formed from Multicomponent Nucleotide‐Appended Bolaamphiphiles and Heteropolymeric DNA as a Template

“…The predetermined sequence of the scaffold DNA and conjugation of metal ligands or chromophores to a single DNA strand allows precise arrangements of hetero‐metal ions or chromophores . Other researchers have constructed well‐defined nanostructures such as micelles, supramolecular helical polymers, and nanofibers, from the homopolymeric DNA‐templated binary self‐assembly of nucleobase‐ and nucleotide‐appended building block molecules. We previously reported the formation of supramolecular helical nanofibers through the binary self‐assembly of homoditopic 1,ω‐nucleotide‐appended bolaamphiphiles with complementary homopolymeric oligonucleotides.…”