ATP as Building Blocks for the Self-Assembly of Excitonic Nanowires

Abstract

Supramolecular nanowires are specifically self-assembled from adenosine 5'-triphosphate (ATP) and dichloro-substituted thiacarbocyanine dyes. Spectral blue-shift and induced circular dichroism with exciton coupling are observed upon mixing the dye and ATP molecules in water. These observations indicate the formation of chiral 1/ATP supramolecular assemblies with excitation energy delocalized in the parallel-oriented (H-aggregated) chromophores. Interestingly, formation of H-aggregates is facilitated most in the presence of ATP and not by other nucleotides (ADP or AMP). In electron microscopy, aqueous 1/ATP mixture gives developed nanowires with a minimum width of ca. 10 nm and lengths of several micrometers. The ATP-directed nanowires exhibit reversible thermal self-assembly accompanied by supramolecular thermochromism. This is the first example of ATP-based supramolecular nanoassemblies, and the use of small biomolecules as building blocks for functional supermolecules provides a new perspective in the design of bio-nanomaterials.

Chiral assembly of achiral pseudoisocyanine with D- and L-phenylalanine

“…In general, chiral self-assembly of achiral cyanine dyes has been focused on using large biopolymers such as proteins [8,25,26] , oligopetides [23] , DNA [27,28] and carboxymethyl amylase [7] as template. However, natural small biomolecules grafting into chromophores through noncovalent interaction to create functional supramolecular systems also show very enticing potential because they have been important targets for bio-and chemo-sensors [6] . Integration of biologically important small molecules and functional organic molecules provides access to supramolecular nanoarchitectures that are capable of converting biomolecular structural information to physicochemical signals [29] .…”

“…Recently, there has been growing interest in the supramolecular assembly of achiral molecules into chiral nanostructures with a controlled helical sense [1][2][3][4] . Among them, chiral J-aggregates of achiral cyanine dyes [5][6][7][8] and porphyrins [9][10][11][12] are particularly interesting because of their potential applications to optoelectronic materials and photosynthesis, as well as the possible explanation for the origin of biomolecular homochirality [13,14] .…”

A dynamic supramolecular polymer with stimuli-responsive handedness for in situ probing of enzymatic ATP hydrolysis

“…Typical designs of helical assemblies consist of optically active monomers, which bias the handedness during the (supramolecular) polymerization process [8][9][10][11][12][13][14][15][16][17][18][19] . In this respect, helicity induction in racemic or achiral assemblies constructed from achiral monomers through non-covalent interactions with the chiral guest molecules is an alternative, synthetic strategy [20][21][22][23][24][25][26] . This host-guest design for helical motifs not only provides new opportunities to investigate mechanistic details of supramolecular chirality, but also offers practical chirotechnological applications.…”

Challenges and breakthroughs in recent research on self-assembly

“…As structures self-assembled from simple molecular units, Kimizuka and coworkers have recently found dynamic nanowire formation through self-assembly of adenosine triphosphate (ATP) and dichloro-substituted thiacarbocyanine dyes (figure 66) [607]. An immediate color change from pink to orange was observed upon addition of ATP to an aqueous solution of the thiacarbocyanine dye.…”