Gold Nanoparticle-Decorated Polymer Particles for High-Optical-Density Immunoassay Probes.

To realize a highly sensitive immunoassay, high-optical-density probes conjugated with antibodies for target antigens are needed to increase the detectability of antigen-antibody complex formation. In this work, gold nanoparticle (NP)-decorated polymer (GNDP) particles were successfully prepared by mixing positively charged polymer particles and negatively charged Au NPs. GNDP particles decorated with NPs of 20 nm in size had higher optical density than the original Au NPs and GNDPs decorated with smaller Au NPs. Using GNDP particles as a probe, a highly sensitive immunoassay for influenza H1N1 hemagglutinin was realized with a minimum detectable concentration of 32.5 pg/mL. These results indicate that GNDP particles have high potential as an immunoassay probe that can be used in practical immunoassay systems for detecting a wide variety of antigens.

Effect of the Poly(ethylene glycol) Diacrylate (PEGDA) Molecular Weight on Ionic Conductivities in Solvent-Free Photo-Cross-Linked Solid Polymer Electrolytes.

To obtain safe, high-performance Li-ion batteries, the development of electrolytes with high impact resistance and high ionic conductivity is important. Ionic conductivity at room temperature has been improved by using poly(ethylene glycol) (PEG) diacrylate (PEGDA) to form three-dimensional (3D) networks and solvated ionic liquids. However, the effects of the molecular weight of PEGDA on ionic conductivities and the relationship between ionic conductivities and network structures of cross-linked polymer electrolytes have not been discussed in detail. In this study, the dependence of the ionic conductivity of photo-cross-linked PEG solid electrolytes on the molecular weight of the PEGDA was evaluated. X-ray scattering (XRS) gave detailed information about the dimensions of 3D networks formed by the photo-cross-linking of PEGDA, and the effects of the network structures on the ionic conductivities were discussed.

Involvement of ionic interactions in self-assembly and resultant rodlet formation of class I hydrophobin RolA from Aspergillus oryzae.

Hydrophobins are small amphiphilic proteins that are conserved in filamentous fungi. They localized on the conidial surface to make it hydrophobic, which contributes to conidial dispersal in the air, and helps fungi to infect plants and mammals and degrade polymers. Hydrophobins self-assemble and undergo structural transition from the amorphous state to the rodlet (rod-like multimeric structure) state. However, it remains unclear whether the amorphous or rodlet state is biologically functional and what external factors regulate state transition. In this study, we analyzed the self-assembly of hydrophobin RolA of Aspergillus oryzae in detail and identified factors regulating this process. Using atomic force microscopy, we observed RolA rodlet formation over time, and determined "rodlet elongation rate" and "rodlet formation frequency." Changes in these kinetic parameters in response to pH and salt concentration suggest that RolA rodlet formation is regulated by the strength of ionic interactions between RolA molecules.

Adsorption Kinetics and Self-Assembled Structures of Aspergillus oryzae Hydrophobin RolA on Hydrophobic and Charged Solid Surfaces.

Hydrophobins are small secreted amphipathic proteins ubiquitous among filamentous fungi. Hydrophobin RolA produced by Aspergillus oryzae attaches to solid surfaces, recruits polyesterase CutL1, and thus promotes hydrolysis of polyesters. Because the N-terminal region of RolA is involved in the interaction with CutL1, the orientation of RolA on the solid surface is important. However, the kinetic properties of RolA adsorption to solid surfaces with various chemical properties remain unclear, and RolA structures assembled after the attachment to surfaces are unknown. Using a quartz crystal microbalance (QCM), we analyzed the kinetic properties of RolA adsorption to the surfaces of QCM electrodes that had been chemically modified to become hydrophobic or charged. We also observed the assembled RolA structures on the surfaces by atomic force microscopy and performed molecular dynamics (MD) simulations of RolA adsorption to self-assembled monolayer (SAM)-modified surfaces. The RolA-surface interaction was considerably affected by the zeta potential of RolA, which was affected by pH. The interactions of RolA with the surface seemed to be involved in the self-assembly of RolA. Three types of self-assembled structures of RolA were observed: spherical, rod-like, and mesh-like. The kinetics of RolA adsorption and the structures formed depended on the amount of RolA adsorbed, chemical properties of the electrode surface, and the pH of the buffer. Adsorption of RolA to solid surfaces seemed to depend mainly on its hydrophobic interaction with the surfaces; this was supported by MD simulations, which suggested that hydrophobic Cys-Cys loops of RolA attached to all SAM-modified surfaces at all pH values. IMPORTANCE The adsorption kinetics of hydrophobins to solid surfaces and self-assembled structures formed by hydrophobin molecules have been studied mostly independently. In this report, we combined the kinetic analysis of hydrophobin RolA adsorption onto solid surfaces and observation of RolA self-assembly on these surfaces. Since RolA, whose isoelectric point is close to pH 4.0, showed higher affinity to the solid surfaces at pH 4.0 than at pH 7.0 or 10.0, the affinity of RolA to these surfaces depends mainly on hydrophobic interactions. Our combined analyses suggest that not only the adsorbed amount of RolA but also the chemical properties of the solid surfaces and the zeta potential of RolA affect the self-assembled RolA structures formed on these surfaces.

Bifunctional rare metal-free electrocatalysts synthesized entirely from biomass resources.

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are important processes for various energy devices, including polymer electrolyte fuel cells, rechargeable metal-air batteries, and water electrolyzers. We herein report the preparation of a rare metal-free and highly efficient ORR/OER electrocatalyst by calcination of a mixture of blood meal and ascidian-derived cellulose nanofibers. The obtained carbon alloys showed high ORR/OER performances and proved to be promising electrocatalysts. The carbon alloys synthesized entirely from biomass resources not only lead to a new electrocatalyst fabrication process but also contribute to CO2 reduction and the realization of a good life-cycle assessment value in fabrication of a sustainable energy device.

Bio-inspired Incrustation Interfacial Polymerization of Dopamine and Cross-linking with Gelatin toward Robust, Biodegradable Three-Dimensional Hydrogels.

In nature, laccase enzymatically catalyzes the reaction of phenolic compounds with oxygen to produce hardened surfaces known as cuticles on insects and plants. Inspired by this natural process, the present work investigated a robust, biodegradable hydrogel synthesized from dopamine and gelatin. This gel is obtained by the oxidation of dopamine dissolved in water, after which the resulting quinone compound automatically undergoes self-polymerization. The oxidized dopamine subsequently undergoes Schiff base and Michael addition reactions with gelatin, such that the exposed gelatin surface cross-links to generate a continuous hardened hydrogel film. Because gelatin transitions between sol and gel states with changes in temperature, two- and three-dimensional structures could be obtained from the gel state. This bio-inspired interfacial cross-linking reaction provides a simple means of forming complex morphologies and represents a promising technique for bio-applications.

Underwater Bubble and Oil Repellency of Biomimetic Pincushion and Plastron-Like Honeycomb Films.

Underwater highly bubble and oil-repellent surfaces were prepared based on honeycomb- and pincushion-structured films prepared by breath figure technique and post modifications including UV-ozone treatment and peeling the top layer. Furthermore, bubble generation from the plastron-like honeycomb gas chamber by attaching oil droplet onto the surface of honeycomb films was first observed. Both controlling gas bubbles and oil droplets underwater are important issues in the field of microfluidics since they are useful and may solve the maleficence to liquid transportation in narrow microchannels.

Site-Selective Wettability Control of Honeycomb Films by UV-O3-Assisted Sol-Gel Coating.

Wettability control of porous materials is significant in lateral flow immunoassay, microfluidic systems, microdroplet manipulation, and so on. In this report, formation of metal oxide layers on self-organized polymer honeycomb films to control surface wettability by simple sol-gel coating and UV-O3 treatment was demonstrated. By the combination of bottom-up and top-down processes, silica thin layers can be formed by retaining their original three-dimensional honeycomb structures. Furthermore, photopatterning of metal oxides on honeycomb films can be achieved by UV irradiation through photomasks. Site-selective wettability control of honeycomb films was realized by patterning silica layers on the surface of the film.

Hierarchical Nano/Micro Moth Eyelike Polymer Film Using Solid/Liquid Interfacial Reaction at Room Temperature.

A simple pathway for the fabrication of real moth eyelike patterned (MEP) polymer film with a double-layered nano/microhierarchical structure is demonstrated through a solid/liquid interfacial reaction at atmospheric conditions. A convex-structured polyvinyl alcohol (PVA) film containing CdCl2 was first fabricated using a self-organized honeycomb-patterned porous film as a template. The CdCl2/PVA convex film was immersed into Na2S/ethanol solution to facilitate the reaction between CdCl2 and Na2S at the solid/liquid interface, which led to the functionalization of CdS nanoparticles in the convex-structured PVA film. The tunable introduction of interfacial reaction resulted in the formation of a CdS moth eyelike nanoarray on the top surface of the PVA convex microarray, which mimicked the real moth eye (PVA-CdS MEP). PVA-CdS MEP film with a double moth eyelike structure showed improved antireflective property in comparison with flat and convex-structured PVA films. The PVA-CdS MEP film showed photoresponse under simulated solar light radiation and flexible duration after 500 cycles of folding.

Analysis of the self-assembly process of Aspergillus oryzae hydrophobin RolA by Langmuir-Blodgett method.

Hydrophobins are small, amphipathic proteins secreted by filamentous fungi. Hydrophobin RolA, which is produced by Aspergillus oryzae, attaches to solid surfaces, recruits the polyesterase CutL1, and consequently promotes hydrolysis of polyesters. Because this interaction requires the N-terminal, positively charged residue of RolA to be exposed on the solid surface, the orientation of RolA on the solid surface is important for recruitment. However, the process by which RolA forms the self-assembled structure at the interface remains unclear. Using the Langmuir-Blodgett technique, we analyzed the process by which RolA forms a self-assembled structure at the air-water interface and observed the structures on the hydrophobic or hydrophilic SiO2 substrates via atomic force microscopy. We found that RolA formed self-assembled films in two steps during phase transitions. We observed different assembled structures of RolA on hydrophilic and hydrophobic SiO2 substrates.

A Fluorescence Indicator at Extreme Low pH Region Based on Dissolution of Zn Tetra-2,3-Pyridoporphyradine (TPP) Nanocrystal Suspension.

Conventional organic pH indicators are widely used for chemical synthesis and analysis based on change of π conjugation length depending on pH values. However, there are a few organic pH indicators for strong acid conditions, because organic compounds are usually decomposed at extreme low pH. Tetra-2,3-pyridoporphyradine (TPP) has high chemical stability and crystallinity, and its nano-crystal is widely used as stable pigments. ZnTPP exhibits red fluorescence, but ZnTPP crystals don't exhibit fluorescence due to concentration quenching. In this paper, we show a UV-assisted synthesis of ZnTPP nano-crystals and application for fluorescence pH indicator at extreme low pH condition by quaternization of ZnTPP nano-crystals. ZnTPP crystals were successfully synthesized and then dispersed into 1 to 10 M HCl aq. UV-Vis and fluorescence spectroscopy revealed that absorption and fluorescence change were observed depending on HCl concentrations at extreme low pH conditions due to quarternization of ZnTPP and dissolution of ZnTPP nano-crystals. These results indicate that ZnTPP nano-crystals can be used for fluorescence pH indicators at extreme low pH.

Reversible Shape Transformation of Ultrathin Polydopamine-Stabilized Droplet.

Here we report on the flattening of water droplets using an ultrathin membrane of autopolymerized polydopamine at the air/water interface. This has only been previously reported with the use of synthetic or extracted peptides, two-dimensional designed synthetic peptide thin films with thicknesses of several tens of nanometers. However, in the previous study, the shape of the water droplet was changed irreversibly and the phenomenon was observed only at the air/water interface. In the present study, an ultrathin polydopamine membrane-stabilized droplet induced the flattening of a water droplet at the air/liquid and liquid/liquid interfaces because a polydopamine membrane was spontaneously formed at these interfaces. Furthermore, a reversible transformation of the droplet to flat and dome shape droplets were discovered at the liquid/liquid interface. These are a completely new system because the polydopamine membrane is dynamically synthesized at the interface and the formation speed of the polydopamine membrane overcomes the flattening time scale. These results will provide new insight into physical control of the interfacial shapes of droplets.

Biomimetic Bubble-Repellent Tubes: Microdimple Arrays Enhance Repellency of Bubbles Inside of Tubes.

The adhesion of bubbles underwater remains the greatest cause of malfunctions in applications such as microfluidics, medical devices, and heat exchangers. Recently, the combination of oxidization and peeling the top layer of self-organized honeycomb films with an adhesive tape resulted in the formation of an ultra-bubble-repellent and pillared polymer surface structure. However, the fabrication of honeycomb films on the inner surface of tubes and the formation of structured hydrophilic textures by peeling the top layer of honeycomb films still remain problematic. In this report, a simple fabrication technique for producing a honeycomb-patterned polymer film on the interior of a tube by dip-coating a polymer solution and blowing humid air in the tube is described. Furthermore, an ultra-bubble-repellent dimple-arrayed structure was fabricated by applying ultrasonication to the honeycomb structure formed on the interior surface of the tubes.

One step fabrication of mesh-reinforced hierarchic perforated microporous honeycomb films with tunable filtering property.

Highly ordered porous films whose pore size ranges from submicron to micron scale have always been an extensive area of research due to their broad range of application to photonic crystals, cell culturing scaffolds, filtration and separation membranes, just to name a few. However, the fragile nature of such a functional porous film has hindered its implementation to advanced uses. Inspired by the hierarchic structure in nature which offers both robustness and functionality, we created in a single fabrication step a mesh-reinforced hierarchic perforated honeycomb film with highly ordered micron pores using the breath figure method. By using the elastomer 1,2-polybutadiene as the material for the film in the combination of the mesh grid, the pore size of the obtained film can be tuned upon stretching. Tubular structures made from the mesh-reinforced hierarchic perforated porous honeycomb film with tunable pore size have been demonstrated.

3D Lattice Structure Control of Ordered Macroporous Material by Self-Assembly of Liquid Droplets.

Microfluidic devices, which can continuously fabricate single emulsion with monodispersed droplets having a pore diameter of more than 100 µm in large numbers, can be applied to manufacture ordered macroporous films. 3D ordered macroporous films with a diameter of more than 100 µm can be fabricated using ordered arrays of the monodispersed droplets as templates of the macropores, which are self-assembled in the space between two parallel flat glass plates. As the gap between the glass plates increases, the number of the layer increases. Furthermore, in the case with two or more layers, the lattice structure of the macroporous films also changes due to the confinement effects.

Proton Conductivities of Lamellae-Forming Bioinspired Block Copolymer Thin Films Containing Silver Nanoparticles.

Size-controlled metal nanoparticles (NPs) were spontaneously formed when the amphiphilic diblock copolymers consisting of poly(vinyl catechol) and polystyrene (PVCa-b-PSt) were used as reductants and templates for NPs. In the present study, the proton conductivity of well-aligned lamellae structured PVCa-b-PSt films with Ag NPs was evaluated. We found that the proton conductivity of PVCa-b-PSt film was increased 10-fold by the addition of Ag NPs into the proton conduction channels filled with catechol moieties. In addition, the effect of humidity and the origin of proton conductivity enhancement was investigated.

Frustrated phases under three-dimensional confinement simulated by a set of coupled Cahn-Hilliard equations.

We numerically study a set of coupled Cahn-Hilliard equations as a means to find morphologies of diblock copolymers in three-dimensional spherical confinement. This approach allows us to find a variety of energy minimizers including rings, tennis balls, Janus balls and multipods among several others. Phase diagrams of confined morphologies are presented. We modify the size of the interface between microphases to control the number of holes in multipod morphologies. Comparison to experimental observation by transmission electron microtomography of multipods in polystyrene-polyisoprene diblock copolymers is also presented.

Correction: Frustrated phases under three-dimensional confinement simulated by a set of coupled Cahn-Hilliard equations.

Correction for 'Frustrated phases under three-dimensional confinement simulated by a set of coupled Cahn-Hilliard equations' by Edgar Avalos et al., Soft Matter, 2016, 12, 5905-5914.

Biomimetic ultra-bubble-repellent surfaces based on a self-organized honeycomb film.

The adhesion of bubbles underwater remains the greatest cause of malfunctions in applications such as microfluidics, medical devices and heat exchangers. There is therefore an emerging need for ultra-bubble-repellent surfaces. Inspired by fish scales, which show high bubble repellency due to their hydrophilic nature and surface microstructures, we propose a novel method for preparing ultra-bubble-repellent surfaces by the hydrophilic treatment of self-organized microstructures. When in contact with air bubbles underwater, the artificial hydrophilic microstructured surfaces had a higher contact angle and a lower adhesion force than a flat surface. The mechanism leading to these properties is also investigated. Our method for the fabrication of ultra-bubble-repellent, hydrophilic, microstructured surfaces is simple and cost-effective, opening the way for its application in artificial devices, such as the inner surfaces of tubes, medical devices, and heat exchangers.

Frustrated phases: polymeric self-assemblies in a 3D confinement.

This paper reviews recent progress concerning polymeric self-assemblies in confined spaces, including phase-separated structures of polymer blends and block copolymers. Although a wide variety of polymer self-assemblies have been studied in terms of conventional parameters, such as blend ratio, interaction of constituent polymers, block ratio, and molecular weight, a series of unique structures appear when the systems are self-assembled under confined conditions. Due to the limited space for phase separation, the polymers in the confinement are frustrated, and the resulting morphologies are distinctly different from those formed in free space. We give an overview of experimental and theoretical studies of the frustrated morphologies. We begin by defining confinement with respect to dimensionality and surface properties, and then introduce methods for producing various shapes and sizes of three-dimensional confinement. Finally, we present morphological and application-oriented studies and discuss the prospects for this research area.