pH-feedback systems to program autonomous self-assembly and material lifecycles

Sharma, Charu; Maity, Indrajit; Walther, Andreas

doi:10.1039/d2cc06402b

Cited by 32 publications

(32 citation statements)

References 84 publications

(139 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…ACA fuels were also employed to drive the operation of pH-responsive smart materials. Compared to the widely used clock reactions or pH-feedback systems based on enzymatic reaction networks, the ACA method is based on a one-component fuel and requires simple operative conditions, a key feature for application-oriented uses. Quintard and co-workers pioneered the use of 2 to achieve sol–gel–sol transitions involving a pH-responsive organogelator .…”

Section: Dissipative Systems Driven By Acasmentioning

confidence: 99%

See 1 more Smart Citation

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Stefano

2023

Acc. Chem. Res.

View full text Add to dashboard Cite

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.

show abstract

Section: Dissipative Systems Driven By Acasmentioning

confidence: 99%

“…Eventually, bilayers capable of self-regulation through chemo-mechanical feedback were developed, by coupling 3 -driven actuation with localized ammonia production by means of mechanically activated urea/urease reaction. 36 …”

Section: Dissipative Systems Driven By Acasmentioning

confidence: 99%

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Stefano

2023

Acc. Chem. Res.

View full text Add to dashboard Cite

show abstract

“…In nature, one of the distinctive features of living organisms is that they are under nonequilibrium conditions, which need to be regulated by chemical reaction networks (CRNs). 1,2 The most typical example is the reversible formation of actin filaments 3 and the continuous supply of guanosine triphosphate (GTP) to maintain the formation of microtubule assemblies. 4 Conventional stimuli-responsive gels are potentially switchable upon exposure to external stimuli such as temperature changes, pH alteration, light, and redox conditions, resulting in changes in their structures, properties, and functions.…”

Section: Introductionmentioning

confidence: 99%

“…[5][6][7][8][9][10] However, such gels in equilibrium status lack the autonomous behavior that is essential in nonequilibrium biological systems. 1 A significant difference between equilibrium and nonequilibrium systems is that the latter can realize spontaneous processes from one state to another via chemical fuel consumption or spatiotemporal modulation. 11,12 Recent works have shown the great potential of nonequilibrium gels in a wide range of applications, including information encryption, [13][14][15] drug release, 16 wound dressings, 17 and smart actuators.…”

Section: Introductionmentioning

confidence: 99%

Transient regulation of gel properties by chemical reaction networks

et al. 2023

View full text Add to dashboard Cite

show abstract

“…Synthetic non-equilibrium self-assembling systems can be realized either by designing the structural elements to be energy dissipating themselves, [11][12][13][14][15][16] or by coupling responsive structural elements to energy dissipating environments in which the selfassemblies act as a system load to the active environment. Selected examples include pH feedback systems, 17 ATP degradation in ATP-co-assembling systems, 18,19 DNA strand displacement (DSD) circuits, [20][21][22] Polymerase-Exonuclease-Nickase (PEN) toolbox, 23,24 DNA/RNA genelet circuits, [25][26][27] and gene regulatory networks. 28,29 Colloidal nano-and microparticles are versatile building blocks for the development of functional materials, for instance, for applications in photonics and sensing.…”

Section: Introductionmentioning

confidence: 99%

DNA-based Signaling Networks for Transient Colloidal Co-Assemblies

Sharma

Samanta

Schmidt

et al. 2023

Preprint

View full text Add to dashboard Cite

Programmable chemical circuits inspired by the signaling networks in living cells are a promising approach for the development of adaptive and autonomous self-assembling molecular systems and material functions. Progress has been made at the molecular level, but connecting molecular control circuits to self-assembling larger elements such as colloids that enable real-space studies and access to functional materials is sparse and can suffer from kinetic traps, flocculation, or difficult system integration protocols. Here we report a toehold-mediated DNA strand displacement reaction network capable of autonomously directing two different microgels into transient and self-regulating co-assemblies. The microgels are functionalized with DNA and become elemental components of the network. The flexibility of the circuit design allows the installation of delay phases or accelerators by chaining additional circuit modules upstream or downstream of the core circuit. The design provides an adaptable and robust route to regulate other building blocks for advanced biomimetic functions.

show abstract

pH-feedback systems to program autonomous self-assembly and material lifecycles

Abstract: pH-responsive systems have gained importance for the development of smart materials and for biomedical applications because they can switch between different states by simple acid/base triggers. However, such equilibrium systems...

Cited by 32 publications

References 84 publications

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Transient regulation of gel properties by chemical reaction networks

DNA-based Signaling Networks for Transient Colloidal Co-Assemblies

Contact Info

Product

Resources

About