Dissipative Self-Assembly of Dynamic Multicompartmentalized Microsystems with Light-Responsive Behaviors

Abstract

Natural living cells are compartmentalized chemical systems that operate far from thermodynamic equilibrium and use energy and fuel from the environment to carry out their functions. Mimicking some aspects of natural living systems by including an artificial pathway for energy dissipation, we demonstrate the autonomous generation and self-assembly of active polymeric microsystems through polymerization-induced self-assembly, driven by chemical fuel. These selforganized synthetic systems exhibit a dynamic change in their multicompartmental structures when exposed to light.

PISA: construction of self-organized and self-assembled functional vesicular structures

“…Remarkably, besides generating functional vesicles with applications to many areas of science and technology, PISA has the potential to solve in a single shot the metabolism-first, information-first and "boot-up" process in the origin of life. 40,41 To explore the application of PISA for producing synthetic functional vesicles, this review is structured as follows: during this introduction we have discussed, in a qualitative way, some of the non-equilibrium aspects of PISA. To make the review somewhat self-contained, in section 2 we will briefly discuss the principles behind PISA, followed by section 3 where we will briefly touch on some relevant methods for producing vesicles by PISA.…”

“…Belousov-Zhabotinsky (BZ) redox oscillatory reactions have also been employed to initiate RAFT-PISA at room temperature, by the polymerization of butyl acrylate and acrylonitrile monomers from PEG-based mCTAs in the aqueous BZ reaction media. 26,27,41 3.2. Oxygen-tolerant systems for producing vesicles by PISA As RAFT polymerizations rely on propagating radical species, most RAFT-based PISA protocols which use initiator molecules as radical sources are sensitive to oxygen and require thorough deoxygenation through nitrogen/argon displacement or multiple freeze-pump-thaw cycles.…”

“…7A). 41 Ru(bpy) 3 2+ is a redox catalyst for the BZ reaction that can also act as a photoredox catalyst for PET-RAFT polymerization, when activated by blue light. 78 The multicompartment giant vesicles were characterized using fluorescence microscopy, cryo-TEM and cryo-SEM ( Fig.…”

“…This maintained a far-from-equilibrium state which produced the dynamic nature of the multicompartment vesicles. 41 Inside cells, compartments are known to merge together for the transmission of genetic or chemical information, through non-equilibrium processes. The BZ reaction media within the lumen of the protocells can manage information, as careful configuration can allow BZ to act as a chemical Turing machine capable of processing information carried by chemistry.…”

Four‐Dimensional Deoxyribonucleic Acid–Gold Nanoparticle Assemblies

“…In the past few years, this strategy has led to a broad spectrum of materials, including transient self-healing hydrogels [8] and colloidal assemblies, [9] temporary nanoreactors and catalysts, [10] dissipative membrane channels, [11] transient molecular cargo-loading devices, [12] among others. [13] Although the dissipative clustering of gold nanoparticles (AuNPs) has been reported, [14] more sophisticated and welldefined out-of-equilibrium nanostructures with programmability of the time domain and richer physiochemical properties remain challenging. [15] To achieve such four-dimensional (4D) assemblies of the important class of DNA-Au nanostructures, we herein present the implementation of a dissipative assembly principle in respect to DNA-fueled gold nanoobjects (Au-nanoparticles (AuNPs) and gold nanorods (AuNRs)), leading to the dissipative clustering of AuNPs accompanied by the evolution of surface plasmonic resonance properties.…”