Chemical Tools for the Temporal Control of Water Solution pH and Applications in Dissipative Systems

Frateloreto, Federico; Sappino, Carla; Stefano, Stefano Di

doi:10.1002/ejoc.202200407

Cited by 22 publications

(16 citation statements)

References 123 publications

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“…The design of complex, dissipative systems requires robustness, programmability, and recognition specificity of the chemical units used. DNA often meets these requirements, leading to a range of functional systems where chemical fuelspH modulators, redox agents, DNA/RNA, ATP, and other small moleculeshave been used to drive DNA structure assembly and function.…”

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confidence: 99%

Modulating the Lifetime of DNA Motifs Using Visible Light and Small Molecules

2023

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Here we regulate the formation of dissipative assemblies built from DNA using a merocyanine photoacid that responds to visible light. The operation of our system and the relative distribution of species within it are controlled by irradiation time, initial pH value, and the concentration of a small-molecule binder that inhibits the reaction cycle. This approach is modular, does not require DNA modification, and can be used for several DNA sequences and lengths. Our system design allows for waste-free control of dissipative DNA nanotechnology, toward the generation of nonequilibrium, life-like nanodevices.

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confidence: 99%

Modulating the Lifetime of DNA Motifs Using Visible Light and Small Molecules

2023

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“…A recent report by Badjic and co-workers 35 shows that tribromoacetic acid 3, can be employed to control over time the assembly of a nanosized cage (Figure 10). The small imine based cage 35 is the triply condensed product of the reaction between the basket-shaped tris-aldehyde 36 and tris-amine 37.…”

Section: Molecular Cagesmentioning

confidence: 99%

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Stefano

2023

Acc. Chem. Res.

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Conspectus The achievement of artificial systems capable of being maintained in out-of-equilibrium states featuring functional properties is a main goal of current chemical research. Absorption of electromagnetic radiation or consumption of a chemical species (a “chemical fuel”) are the two strategies typically employed to reach such out-of-equilibrium states, which have to persist as long as one of the above stimuli is present. For this reason such systems are often referred to as “dissipative systems”. In the simplest scheme, the dissipative system is initially found in a resting, equilibrium state. The addition of a chemical fuel causes the system to shift to an out-of-equilibrium state. When the fuel is exhausted, the system reverts to the initial, equilibrium state. Thus, from a mechanistic standpoint, the dissipative system turns out to be a catalyst for the fuel consumption. It has to be noted that, although very simple, this scheme implies the chance to temporally control the dissipative system. In principle, modulating the nature and/or the amount of the chemical fuel added, one can have full control of the time spent by the system in the out-of-equilibrium state. In 2016, we found that 2-cyano-2-phenylpropanoic acid (1a), whose decarboxylation proceeds smoothly under mild basic conditions, could be used as a chemical fuel to drive the back and forth motion of a catenane-based molecular switch. The acid donates a proton to the catenane that passes from the neutral state A to the transient protonated state B. Decarboxylation of the resulting carboxylate (1acb), generates a carbanion, which, being a strong base, retakes the proton from the protonated catenane that, consequently, returns to the initial state A. The larger the amount of the added fuel, the longer the time spent by the catenane in the transient, out-of-equilibrium state. Since then, acid 1a and other activated carboxylic acids (ACAs) have been used to drive the operation of a large number of dissipative systems based on the acid–base reaction, from molecular machines to host–guest systems, from catalysts to smart materials, and so on. This Account illustrates such systems with the purpose to show the wide applicability of ACAs as chemical fuels. This generality is due to the simplicity of the idea underlying the operation principle of ACAs, which always translates into simple experimental requirements.

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“…Here, we describe a two‐component system formed from two dipeptides. A number of ways have been described to control pH changes in aqueous systems [6] . Here, coupling with the well‐established urease‐urea [7] and methyl formate combination that drives the pH up and then down, [8] these dipeptides form self‐assembled structures which can be controlled directly by the pH.…”

Section: Figurementioning

confidence: 99%

“…A number of ways have been described to control pH changes in aqueous systems. [6] Here, coupling with the well-established urease-urea [7] and methyl formate combination that drives the pH up and then down, [8] these dipeptides form self-assembled structures which can be controlled directly by the pH. This approach allows us to directly control what structures will be formed in such a complex, multicomponent system.…”

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confidence: 99%

Controlled Annealing in Adaptive Multicomponent Gels

et al. 2022

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We use a pH-driven annealing process to convert between co-assembled and self-sorted networks in multicomponent gels. The initially formed gels at low pH are co-assembled, with the two components coexisting within the same self-assembled structures. We use an enzymatic approach to increase the pH, resulting in a gel-to-sol transition, followed by a hydrolysis to lower the pH once again. As the pH decreases, a self-sorted network is formed by a two-stage gelation process determined by the pK a of each component. This approach can be expanded to layered systems to generate many varied systems by changing composition and rates of pH change, adapting their microstructure and so allowing access to a far greater range of morphologies and complexity than can be achieved in single component systems.

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Chemical Tools for the Temporal Control of Water Solution pH and Applications in Dissipative Systems

Cited by 22 publications

References 123 publications

Modulating the Lifetime of DNA Motifs Using Visible Light and Small Molecules

Modulating the Lifetime of DNA Motifs Using Visible Light and Small Molecules

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Controlled Annealing in Adaptive Multicomponent Gels

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