Reconfigurable Droplet–Droplet Communication Mediated by Photochemical Marangoni Flows

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air–water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air–water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating

Reconfigurable Droplet–Droplet Communication Mediated by Photochemical Marangoni Flows

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air–water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air–water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating

Reconfigurable Droplet–Droplet Communication Mediated by Photochemical Marangoni Flows

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air–water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air–water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating

Reconfigurable Droplet–Droplet Communication Mediated by Photochemical Marangoni Flows

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air–water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air–water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating

Reconfigurable Droplet–Droplet Communication Mediated by Photochemical Marangoni Flows

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air–water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air–water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating

Reconfigurable Droplet–Droplet Communication Mediated by Photochemical Marangoni Flows

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air–water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air–water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating

Reconfigurable Droplet–Droplet Communication Mediated by Photochemical Marangoni Flows

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air–water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air–water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating

Solvent Clathrate Driven Dynamic Stereomutation of a Supramolecular Polymer with Molecular Pockets

Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3,5-dialkoxy substitution on the imide phenyl groups (<b>CBI-35CH</b>), leading to “molecular pockets” in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of <b>CBI-35CH</b> at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of self-assembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly

Pathway-Controlled Aqueous Supramolecular Polymerization via Solvent-Dependent Chain Conformation Effects

Solute–solvent interactions play a critical role in multiple fields, including biology, materials science, and (physical) organic, polymer, and supramolecular chemistry. Within the growing field of supramolecular polymer science, these interactions have been recognized as an important driving force for (entropically driven) intermolecular association, particularly in aqueous media. However, to date, solute–solvent effects remain poorly understood in the context of complex self-assembly energy landscapes and pathway complexity. Herein, we unravel the role of solute–solvent interactions in controlling chain conformation effects, allowing energy landscape modulation and pathway selection in aqueous supramolecular polymerization. To this end, we have designed a series of oligo(phenylene ethynylene) (OPE)-based bolaamphiphilic Pt(II) complexes OPE2–4 bearing solubilizing triethylene glycol (TEG) chains of equal length on both molecule ends, but a different size of the hydrophobic aromatic scaffold. Strikingly, detailed self-assembly studies in aqueous media disclose a different tendency of the TEG chains to fold back and enwrap the hydrophobic molecular component depending on both the size of the core and the volume fraction of the co-solvent (THF). The relatively small hydrophobic component of OPE2 can be readily shielded by the TEG chains, leading to only one aggregation pathway. In contrast, the decreased capability of the TEG chains to effectively shield larger hydrophobic cores (OPE3 and OPE4) enables different types of solvent quality-dependent conformations (extended, partly back-folded and back-folded), which in turn induce various controllable aggregation pathways with distinct morphologies and mechanisms. Our results shed light on previously underappreciated solvent-dependent chain conformation effects and their role in governing pathway complexity in aqueous media

Kinetic Analysis as a Tool to Distinguish Pathway Complexity in Molecular Assembly: An Unexpected Outcome of Structures in Competition

While the sensitive dependence of the functional characteristics of self-assembled nanofibers on the molecular structure of their building blocks is well-known, the crucial influence of the dynamics of the assembly process is often overlooked. For natural protein-based fibrils, various aggregation mechanisms have been demonstrated, from simple primary nucleation to secondary nucleation and off-pathway aggregation. Similar pathway complexity has recently been described in synthetic supramolecular polymers and has been shown to be intimately linked to their morphology. We outline a general method to investigate the consequences of the presence of multiple assembly pathways, and show how kinetic analysis can be used to distinguish different assembly mechanisms. We illustrate our combined experimental and theoretical approach by studying the aggregation of chiral bipyridine-extended 1,3,5-benzenetricarboxamides (<i>BiPy-<b>1</b></i>) in <i>n</i>-butanol as a model system. Our workflow consists of nonlinear least-squares analysis of steady-state spectroscopic measurements, which cannot provide conclusive mechanistic information but yields the equilibrium constants of the self-assembly process as constraints for subsequent kinetic analysis. Furthermore, kinetic nucleation-elongation models based on one and two competing pathways are used to interpret time-dependent spectroscopic measurements acquired using stop-flow and temperature-jump methods. Thus, we reveal that the sharp transition observed in the aggregation process of <i>BiPy-<b>1</b></i> cannot be explained by a single cooperative pathway, but can be described by a competitive two-pathway mechanism. This work provides a general tool for analyzing supramolecular polymerizations and establishing energetic landscapes, leading to mechanistic insights that at first sight may seem unexpected and counterintuitive