Periodically Self‐Pulsating Microcapsule as Programmed Microseparator via ATP‐Regulated Energy Dissipation

Abstract

systems have been known very early; however, in vitro mimicking such "living" systems with adaptive features using "nonliving" molecular building blocks is still a fundamental challenge in chemistry. [5,6] To date, chemists have established a plethora of synthetic self-assembly entities, [7] some of which can undergo reversible shape changes or phase transitions under external stimuli, [8][9][10] but they are not yet comparable to their natural counterparts. The main reason is that synthetic self-assembly systems operate in thermodynamic equilibrium, resulting in timeindependent steady-state structures. In contrast, natural self-assembly requires a continuous supply of energy to keep the assemblies away from equilibrium, resulting in time-dependent dynamic structures. [11] If the energy dissipates, the system will fall apart and revert to ground state. This process is referred to as dissipative self-assembly, [12] which offers impetus for biological motions such as cell deformation and growth (in situ motion without distance change), and cell migration and division (motion with distance change). Hence, implanting this energy-driven assembly in man-made assemblies may create life-like systems, possessing structural adaption and behavioral evolution over time and space. However, such artificial systems formed by dissipative pathway are quite limited thus far. The few reports focused on biocatalytic active gels, [13][14][15] switchable films, [16] and molecule-level reaction networks. [17] Nanoscale nonequilibrium assemblies have received little attention. An insuperable obstacle is how to harmonize sophisticated self-assembly process with continuous energy influx in a time-ordered manner.Herein, we report a "living" giant vesicle system that can perform autonomous and periodic pulsating motion via energy dissipation. The energy source of this pulsation derives from the cellular biochemical fuel, ATP. To achieve the energy-regulated self-assembly, our design concept is based on transient ligandreceptor supramolecular interactions between the ATP fuels and the vesicular membrane components. The system is necessary to satisfy the following conditions: (i) a self-assembling vesicle with specific ATP receptor units can toggle between expansile and contractile state by the association and dissociation of ATP; (ii) the temporary formation of ATP-polymer ligand-receptor complexes can cause the system energy gain Living systems can experience time-dependent dynamic self-assembly for periodic, adaptive behavior via energy dissipation pathway. Creating in vitro mimics is a daunting mission. Here a "living" giant vesicle system that can perform a periodic pulsating motion using adenosine-5'-triphosphate (ATP)-fuelled dissipative self-assembly is described. This dynamic system is built on transient supramolecular interactions between the polymer and cellular energy currency ATP. The vesicles capturing ATPs will deviate away from equilibrium, leading to an energy ascent that drives a continuous vesicular expansion, until a comp...

Pathway Complexity in Fuel-Driven DNA Nanostructures with Autonomous Reconfiguration of Multiple Dynamic Steady States

“…The difficulty in implementing such a concept in synthetic system is related to the need for highest levels of programmability and ability for deterministic autonomous reconfiguration leading to multiple transient dynamic steady-state (DySS) structures, which is a profound challenge in supramolecular chemistry. [24][25][26] On the contrary, DNA shows great potential to program reaction networks and pathways for self-assemblies in a systems chemistry approach. [27][28][29] Herein, we demonstrate pathway complexity in ATP-fueled transient DNA polymerizations from a species pool realizing autonomous and transient multiple DySS structures (Figure 1a,b).…”

Smart Microcapsules with Molecular Polarity‐ and Temperature‐Dependent Permeability

“…[16][17][18] The simplest way to regulate transmembrane transport is the molecular size-selective permeation using membranes with a consistent size of pores. [19][20][21][22][23][24] To create microcapsules with regular pores in the membranes, various approaches have been employed. For example, metal-organic framework [16,17,22,25] or nanoparticles [26,27] are formed on the surface of emulsion drops through interfacial condensation or adsorption, and also a polymeric layer is prepared by a layer-by-layer (LBL) deposition.…”

“…The simplest way to regulate transmembrane transport is the molecular size‐selective permeation using membranes with a consistent size of pores . To create microcapsules with regular pores in the membranes, various approaches have been employed.…”

ATP‐Mediated Transient Behavior of Stomatocyte Nanosystems

“…[1] Fore xample,m olecular motors, [2] micro-and nanoscale sized Janus motors, [3] self-assembled polymeric motors, [4] and movable tubules and rods [5] have been developed. [7] Theintroduction of transient behavior into synthetic molecular or nanoscaled systems has been demonstrated for active materials with unique properties such as dissipative fibres, [8] transient peptide hydrogels,v esicles or microcapsules, [9] temporally programmed "breathing" microgels and polymersomes, [10] and non-equilibrium molecular recognition and colloidal systems. [7] Theintroduction of transient behavior into synthetic molecular or nanoscaled systems has been demonstrated for active materials with unique properties such as dissipative fibres, [8] transient peptide hydrogels,v esicles or microcapsules, [9] temporally programmed "breathing" microgels and polymersomes, [10] and non-equilibrium molecular recognition and colloidal systems.…”