Light-Driven Proton Transfer for Cyclic and Temporal Switching of Enzymatic Nanoreactors.

Temporal activation of biological processes by visible light and subsequent return to an inactive state in the absence of light is an essential characteristic of photoreceptor cells. Inspired by these phenomena, light-responsive materials are very attractive due to the high spatiotemporal control of light irradiation, with light being able to precisely orchestrate processes repeatedly over many cycles. Herein, it is reported that light-driven proton transfer triggered by a merocyanine-based photoacid can be used to modulate the permeability of pH-responsive polymersomes through cyclic, temporally controlled protonation and deprotonation of the polymersome membrane. The membranes can undergo repeated light-driven swelling-contraction cycles without losing functional effectiveness. When applied to enzyme loaded-nanoreactors, this membrane responsiveness is used for the reversible control of enzymatic reactions. This combination of the merocyanine-based photoacid and pH-switchable nanoreactors results in rapidly responding and versatile supramolecular systems successfully used to switch enzymatic reactions ON and OFF on demand.

Critical Assessment of the Application of Multidetection SEC and AF4 for the Separation of Single-Chain Nanoparticles.

The intramolecular chain collapse of linear precursors with systematic variation of molar mass and ligation group density (5, 15, and 30 mol %) into single-chain nanoparticles (SCNPs) was studied by two different separation approaches. The efficiency of size exclusion chromatography with quadruple detection (SEC-D4) was compared to asymmetrical field flow fractionation hyphenated to quintuple detection (AF4-D5) in organic solvent. The application of the unique combination of advanced detection to different separation principles opens up the opportunity to critically evaluate the determination of molar masses and different types of radii for an in-depth understanding of the structural properties affected by the internal folding process. This is achieved by a detailed comparison of assets, drawbacks, and limitations of these approaches based on the systematical screening of different chain lengths and sizes of the precursors and the SCNPs. Furthermore, an alternative strategy for quantitative determination of intramolecular ligation density by a combination of AF4 and UV detection is introduced.