Fuel-Driven Dissipative Self-Assembly of a Supra-Amphiphile in Batch Reactor

Dissipative self-assembly is an intriguing but challenging research topic in chemistry, materials science, physics, and biology because most functional self-assembly in nature, such as the organization and operation of cells, is actually an out-of-equilibrium system driven by energy dissipation. In this article, we successfully fabricated an I₂-responsive supra-amphiphile by a PEGylated poly­(amino acid) and realize its dissipative self-assembly in batch reactor by coupling it with the redox reaction between NaIO₃ and thiourea, in which I₂ is an intermediate product. The formation and dissipative self-assembly of the supra-amphiphile can be repeatedly initiated by adding the mixture of NaIO₃ and thiourea, which herein acts as “chemical fuel”, while the lifetime of the transient nanostructures formed by the dissipative self-assembly is easily tuned by altering thiourea concentration in the “chemical fuel”. Furthermore, as an application demo, the dissipative self-assembly of the supra-amphiphile is examined to control dispersion of multiwalled carbon nanotubes in water, exhibiting a good performance of organic pollutant removal

The Structure of Self-Assembled Multilayers with Polyoxometalate Nanoclusters

Using electrostatic layer-by-layer self-assembly (ELSA), the formation of multilayers with polyelectrolytes and nanoscopic polyoxometalate (POM) clusters of different sizes and charges is investigated. The multilayers are characterized by UV−vis absorption spectroscopy, optical ellipsometry, cyclic voltammetry, and atomic force microscopy. In all cases, it is possible to find experimental conditions to achieve irreversible adsorption and regular multilayer deposition. Most importantly, the surface coverage is directly related to the total charge of the POM anion and can be controlled from submonolayer to multilayer coverage by adjusting the ionic strength of the dipping solutions. Imaging the interfaces after POM deposition by atomic force microscopy reveals a granular surface texture with nanometer-sized features. The average interfacial roughness amounts to approximately 1 nm. Cyclic voltammetry indicates that the electrochemical properties of the POM clusters are fully maintained in the polyelectrolyte matrix, which opens a route toward practical applications such as sensors or heterogeneous catalysts. Moreover, the permeability toward electrochemically active probe molecules can be tailored through the multilayer architecture and deposition conditions. Finally, we note that despite the low total charge and comparably small size of the discrete POM anions, the multilayers are remarkably stable. This work provides basic guidelines for the assembly of POM-containing ELSA multilayers and provides detailed insight into characteristic surface coverage, permeability, and electrochemical properties

Novel Acid-Driven Bioinspired Self-Resettable Bilayer Hydrogel Actuator Mimicking Natural Muscles

Soft robots have great potential applications in manufacturing, disaster rescue, medical treatment, etc. Artificial muscle is one of the most important components of a soft robot. In previous years, hydrogel actuators that can be controllably deformed by the stimuli of external signals have been developed as good candidates for muscle-like materials. In this article, we successfully prepared a chemical fuel-driven self-resettable bilayer hydrogel actuator mimicking natural muscles with the aid of a new negative feedback reaction network. The actuator can temporarily deform upon the addition of H+ (chemical fuel). Subsequently, H+ accelerated the reaction between BrO3– and Fe(CN)64–, which consume H+. It resulted in the spontaneous recovery of the pH as well as the shape of the actuator. Such an actuator exhibits a great similarity with natural muscles in actuation mechanisms and automaticity in the manipulation compared to the widely reported stimuli-responsive hydrogel actuators. This illustrates that fuel-driven self-resettable hydrogel is a promising dynamic material for mimicking the functions of living creatures

Toward Understanding of Transfer Mechanism between Electrochemiluminescent Dyes and Luminescent Quantum Dots

Electrochemiluminescence resonance energy transfer (ECL-RET) based on dye–quantum dot (QD) hybrids, is a very powerful tool for chemical sensing and probing many important biological processes. In this work, we have investigated both electrochemiluminescence (ECL) and photoluminescence (PL) properties of the hybrid system, in which tris­(2,2′-bipyridyl)­ruthenium­(II) ([Ru­(bpy)₃]²⁺)/2-(dibutylamino)­ethanol (DBAE) and QD are employed as the ECL donor and acceptor, respectively. Unexpectedly, we find that ECL of the [Ru­(bpy)₃]²⁺/DBAE system can be efficiently quenched by various types of QDs. In addition, ECL quenching in the [Ru­(bpy)₃]²⁺/DBAE system is independent of the core size and the surface charge of QDs, indicating that the quenching effect does not originate from resonance energy transfer between the [Ru­(bpy)₃]²⁺/DBAE system and QDs. Photoluminescence properties of the hybrid system under electrochemical control and electron spin resonance (ESR) measurements further reveal that a charge transfer between QDs and the radical-state DBAE is responsible for ECL quenching in the [Ru­(bpy)₃]²⁺/DBAE system. Contrary to previously published information, we propose that electron transfer, rather than energy transfer, dominates in the hybrid system under electrochemical control. We further demonstrate that such electron transfer could be switched to energy transfer by controlling the distance between [Ru­(bpy)₃]²⁺/DBAE ECL and QDs. The energy/electron transfer process between [Ru­(bpy)₃]²⁺/DBAE ECL and QDs is implemented to develop a novel platform for immune sensing

Polyoxometalate-Based Electro- and Photochromic Dual-Mode Devices

Molecular or supramolecular systems capable of electro- and photostimulated color changes are still rare. We present a device design based on an electrostatic complex of a nanoscopic polyoxometalate cluster and a polyelectrolyte. The coating reversibly changes color from transparent to blue by photo- and/or electroinduced stimulation. The choice of the components results in perfect transparency over the entire visible range, a large optical response, reversible operation, and excellent stability

The Structure of Self-Assembled Multilayers with Polyoxometalate Nanoclusters

Using electrostatic layer-by-layer self-assembly (ELSA), the formation of multilayers with polyelectrolytes and nanoscopic polyoxometalate (POM) clusters of different sizes and charges is investigated. The multilayers are characterized by UV−vis absorption spectroscopy, optical ellipsometry, cyclic voltammetry, and atomic force microscopy. In all cases, it is possible to find experimental conditions to achieve irreversible adsorption and regular multilayer deposition. Most importantly, the surface coverage is directly related to the total charge of the POM anion and can be controlled from submonolayer to multilayer coverage by adjusting the ionic strength of the dipping solutions. Imaging the interfaces after POM deposition by atomic force microscopy reveals a granular surface texture with nanometer-sized features. The average interfacial roughness amounts to approximately 1 nm. Cyclic voltammetry indicates that the electrochemical properties of the POM clusters are fully maintained in the polyelectrolyte matrix, which opens a route toward practical applications such as sensors or heterogeneous catalysts. Moreover, the permeability toward electrochemically active probe molecules can be tailored through the multilayer architecture and deposition conditions. Finally, we note that despite the low total charge and comparably small size of the discrete POM anions, the multilayers are remarkably stable. This work provides basic guidelines for the assembly of POM-containing ELSA multilayers and provides detailed insight into characteristic surface coverage, permeability, and electrochemical properties

Preparation, Structures, and Electrochemistry of a New Polyoxometalate-Based Organic/Inorganic Film on Carbon Surfaces

The preparation, structure, and electrochemical and electrocatalytical properties of a new polyoxometalate-based organic/inorganic film, composed of cetyl pyridinum 11-molybdovanadoarsenate (CPMVA) molecules, have been studied. Cyclic potential scanning in acetone solution led to a stable CPMVA film formed on a highly oriented pyrolytic graphite (HOPG) surface. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used for characterizing the structure and properties of the CPMVA film. These studies indicated that self-aggregated clusters were formed on a freshly cleaved HOPG surface, while a self-organized monolayer was formed on the precathodized HOPG electrode. The CPMVA film exhibited reversible redox kinetics both in acidic aqueous and in acetone solution, which showed that it could be used as a catalyst even in organic phase. The CPMVA film remained stable even at pH >7.0, and the pH dependence of the film was much smaller than that of its inorganic film (H4AsMo11VO40) in aqueous solution. The CPMVA film showed strong electrocatalysis on the reduction of bromate, and the catalytic currents were proportional to the square of the concentration of bromate. The new kind of polyoxometalate with good stability may have extensive promise in catalysis

Enantioselective Circular Dichroism Sensing of Cysteine and Glutathione with Gold Nanorods

Enantioselective analysis of biological thiols, including cysteine (Cys) and glutathione (GSH), is extremely important because of their unique role in bioentities. Here we demonstrated that the end-to-end assemblies of plasmonic gold nanorods with chiral Cys or GSH can be used as a distinctive chiroptical sensor for reliable determination of the absolute configuration of Cys and GSH at the visible light region. The end-to-end assemblies of Au nanorods induced by Cys or GSH exhibit strong circular dichroism (CD) signals in the region of 500–850 nm, which is attributed to chiral current inside Au nanorods induced by the mixed biothiols. The CD intensity of the assemblies shows good linearity with the amount of Cys and GSH. The limit of detection for Cys and GSH using end-to-end assemblies is at micromolar concentrations. In addition, the sensing system exhibits good selectively toward Cys and GSH in the presence of other amino acids

Novel Acid-Driven Bioinspired Self-Resettable Bilayer Hydrogel Actuator Mimicking Natural Muscles

Soft robots have great potential applications in manufacturing, disaster rescue, medical treatment, etc. Artificial muscle is one of the most important components of a soft robot. In previous years, hydrogel actuators that can be controllably deformed by the stimuli of external signals have been developed as good candidates for muscle-like materials. In this article, we successfully prepared a chemical fuel-driven self-resettable bilayer hydrogel actuator mimicking natural muscles with the aid of a new negative feedback reaction network. The actuator can temporarily deform upon the addition of H+ (chemical fuel). Subsequently, H+ accelerated the reaction between BrO3– and Fe(CN)64–, which consume H+. It resulted in the spontaneous recovery of the pH as well as the shape of the actuator. Such an actuator exhibits a great similarity with natural muscles in actuation mechanisms and automaticity in the manipulation compared to the widely reported stimuli-responsive hydrogel actuators. This illustrates that fuel-driven self-resettable hydrogel is a promising dynamic material for mimicking the functions of living creatures

Novel Acid-Driven Bioinspired Self-Resettable Bilayer Hydrogel Actuator Mimicking Natural Muscles

Soft robots have great potential applications in manufacturing, disaster rescue, medical treatment, etc. Artificial muscle is one of the most important components of a soft robot. In previous years, hydrogel actuators that can be controllably deformed by the stimuli of external signals have been developed as good candidates for muscle-like materials. In this article, we successfully prepared a chemical fuel-driven self-resettable bilayer hydrogel actuator mimicking natural muscles with the aid of a new negative feedback reaction network. The actuator can temporarily deform upon the addition of H+ (chemical fuel). Subsequently, H+ accelerated the reaction between BrO3– and Fe(CN)64–, which consume H+. It resulted in the spontaneous recovery of the pH as well as the shape of the actuator. Such an actuator exhibits a great similarity with natural muscles in actuation mechanisms and automaticity in the manipulation compared to the widely reported stimuli-responsive hydrogel actuators. This illustrates that fuel-driven self-resettable hydrogel is a promising dynamic material for mimicking the functions of living creatures