Details

Autor(en) / Beteiligte

• Fan, Xinlong
• Walther, Andreas

Titel

Autonomous Transient pH Flips Shaped by Layered Compartmentalization of Antagonistic Enzymatic Reactions

Ist Teil von

• Angewandte Chemie (International ed.), 2021-02, Vol.60 (7), p.3619-3624

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2021

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Transient signaling orchestrates complex spatiotemporal behaviour in living organisms via (bio)chemical reaction networks (CRNs). Compartmentalization of signal processing is an important aspect for controlling such networks. However, artificial CRNs mostly focus on homogeneous solutions to program autonomous self‐assembling systems, which limits their accessible behaviour and tuneability. Here, we introduce layered compartments housing antagonistic pH‐modulating enzymes and demonstrate that transient pH signals in a supernatant solution can be programmed based on spatial delays. This overcomes limitations of activity mismatches of antagonistic enzymes in solution and allows to flexibly program acidic and alkaline pH lifecycles beyond the possibilities of homogeneous solutions. Lag time, lifetime, and the pH minima and maxima can be precisely programmed by adjusting spatial and kinetic conditions. We integrate these spatially controlled pH flips with switchable peptides, furnishing time‐programmed self‐assemblies and hydrogel material system. Chemical reaction networks based on antagonistic enzymes can show new behaviour when the enzymes are immobilized into layered compartments to impose spatial diffusive constraints. This allows to overcome mismatches of the enzymatic activities and reduces crosstalk in their pH‐dependent activity when targeting pH‐feedback mechanisms to program self‐assembly lifecycles.