Photocatalytic Regulation of an Autocatalytic Wave of Spatially Propagating Enzymatic Reactions

Abstract

Bioinspiration is an attractive way to develop new robust chemistry. In biological cell, chemical reactions form complex networks (e.g. signaling and metabolic) that communicate with each other and control cell division, growth, and interaction with environment. Thus, combining multiple chemical subsystems into a single network is an attractive way to design a chemical system with new functions. In this paper, we combined two chemical networks: i) a photocatalytic oxidation/ reduction on TiO2 particles, and ii) an autocatalytic formation of enzyme trypsin (Tr) from its precursor trypsinogen (Tg). Moreover, we put the combined network in hydrogel media, where all reactions are coupled to diffusion, to achieve a photocatalytic regulation of an autocatalytic wave. We showed that TiO2 particles affected the fluorescence quenching of Tr, but, without irradiation, had no effect on the autocatalytic formation of Tr. With irradiation, however, a cascade of photocatalytic reactions causes media acidification that suppress the autocatalytic formation of Tr and propagation of the autocatalytic wave.

Nanoparticles in Polyelectrolyte Multilayer Layer-by-Layer (LbL) Films and Capsules—Key Enabling Components of Hybrid Coatings

“…Photocatalytic reduction [107] of noble metal particles on titania core [95] leads to dual-wavelength responsiveness: in the UV to near-IR regions of electromagnetic spectrum. It is possible to regulate photocatalytically (auto-catalytic) waves of enzymatic reactions [108], switch biofilm fluorescence [109], build a platform for a chemical logic device [110], and perform sustainable diagnostics [111][112][113]. The trend in the field of encapsulated systems is to combine different functions in one capsule matrix.…”

Coupling pH-Regulated Multilayers with Inorganic Surfaces for Bionic Devices and Infochemistry

“…The approach described herein can be used in many applications where targeted and delayed switching and light upconversion are required. Such complex materials are very important for complex chemical network integration with biological networks such as enzymatic networks, 38 bacterial quorum sensing, 89 and synthetic biology, 90 suggesting them to be one working reaction network.…”

“…91 Stimuli-responsive biointerfaces open perspectives to smart materials for tissue engineering. Thus, the formation of trypsin from its precursor trypsinogen was chosen as an example of the pH-sensitive autocatalytic enzymatic reaction and was studied on the TiO 2 / PSS/PEI hybrid and TiO 2 surface as a control 38 (Figure 8). The results indicated that the acidification of the media near pristine TiO 2 was the most possible explanation of trypsin suppressed formation in comparison to the hybrid system.…”

“…(c) Photograph of (left) the reactor pointing to the glass flask spatially separated from the surface to decrease the effect of the temperature increase and (right) reaction monitoring over time, with the autocatalytic increase in fluorescence in test cuvettes. Adapted from ref , Wiley.…”

“…Here we present a strategy for both mentioned characteristics: (i) a controllable, sustainable pH concentration gradient in solution produced photochemically, electrochemically, or biochemically and controlled by multilayers as well as (ii) possible logic-operated materials. The synergy between components in such materials is important for the future green and sustainable way of controlling cells and tissue growth, communication with bacterial colonies, and the acceleration of autocatalytic processes in solution and even developing a platform of transmembrane channels in bionic devices with a size-tuning bioinspired response.…”