Nucleotide‐Selective Templated Self‐Assembly of Nanoreactors under Dissipative Conditions

Abstract

Nature adopts complex chemical networks to finely tune biochemical processes.I ndeed, small biomolecules play ak ey role in regulating the flux of metabolic pathways. Chemistry,w hichw as traditionally focused on reactions in simple mixtures,i sd edicating increasing attention to the network reactivity of highly complex synthetic systems,a ble to displayn ew kinetic phenomena. Herein, we show that the addition of monophosphate nucleosides to am ixture of amphiphiles and reagents leads to the selective templated formation of self-assembled structures,w hichc an accelerate ar eaction between two hydrophobic reactants.T he correct matching between nucleotide and the amphiphile head group is fundamental for the selective formation of the assemblies and for the consequent up-regulation of the chemical reaction. Transient stability of the nanoreactors is obtained under dissipative conditions,driven by enzymatic dephosphorylation of the templating nucleotides.T hese results show that small molecules can play akey role in modulating network reactivity, by selectively templating self-assembled structures that are able to up-regulate chemical reaction pathways.

Chemically Fueled Self‐Assembly in Biology and Chemistry

“…The transient formation of ATP‐templated vesicles offers a new possibility to control chemical reactivity in the time domain [109–111] . Vesicles are characterized by an apolar bilayer, which can be used to trap apolar reactants that are poorly soluble in the aqueous medium [112, 113] .…”

Analyzing Catalytic Co‐operativity and Membrane Parameters in a Substrate‐driven Vesicular Assembly Modified by Nucleotides

“…Apart from TEM images, the presence of the aqueous interior in the aggregates was also checked by encapsulation experiment of a water-soluble cationic dye, Rhodamine 6G (Rh6G) and hydrophobic domain was confirmed by using a apolar probe, coumarin 153 (C153). [20][21] The Rh6G encapsulation was confirmed by ultracentrifugation of a mixture of 50 μM surfactant and 100 μM of HPNPP or the nucleotides with 50 nM of Rh6G at 10000 rpm for 1 h (Figure S12-S13, SI). The supernatant was analyzed for quantification of the encapsulated dye by fluorescence.…”

Construction of Supramolecular Systems That Achieve Lifelike Functions

“…When ATP was added to this system, vesicles formed again, but they were gradually converted to micelles. This group also designed and synthesized an amphiphilic molecule with the zinc complex of 1,4,7-triazacyclononane as the hydrophilic part, noting that the zinc complex of 1,4,7,10-tetraazacyclododecane recognizes the phosphate moiety of monophosphate nucleic acids such as AMP [ 89 ]. They also reported transient formation of vesicles from micelles in the presence of monophosphate nucleic acid-hydrolyzing enzymes.…”