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For rapid detection of carbaryl pesticides, we developed a simple colorimetric detection method based on azo-coupling reaction. Pretreating carbaryl pesticides with an organic base yielded 1-naphthol, which readily reacted with a diazonium salt with a dramatic color change. Since the resulting azo dye can further change color with the organic base used in the pretreatment, phosphoric acid was added to suppress the confounding colorimetric response. We report that this new colorimetric method can selectively detect carbaryl pesticides from other carbamate pesticides within a minute. Moreover, carbaryl can be detected below 10 parts per million (ppm), which is below its permissible exposure limit (∼15 ppm). Finally, we successfully estimated the concentrations of carbaryl pesticides on fruit samples in the presence of natural interferences.

We developed a continuous roll-to-roll redox-welding and embedding method for the fabrication of electrodes of silver nanowire (AgNWs) networks. The roll-to-roll welding method involved a sequence of oxidation and reduction reactions in an aqueous solution. The redox-welding significantly decreased the sheet resistance of the AgNW film owing to the strong fusion and interlocking at the nanowire junction, while the optical transmittance was maintained. The first oxidation step using HNO3 generated ionized silver (Ag+) which got re-deposited onto the nanowire junctions via an autocatalytic reaction. The oxide layers, which formed on the nanowire surface by both air exposure and the first step of oxidation, were removed by the second reduction step using NaBH4. The redox-welded AgNW electrodes exhibited a sheet resistance of 11.3 Ω sq-1 at the optical transmittance of 90.5% at 550 nm. Furthermore, redox-welding of the AgNWs significantly enhanced their mechanical robustness compared to that of the as-coated AgNWs. The redox-welded AgNWs embedded in a UV curable resin, using a roll-to-roll embedding process, were successfully applied as anode electrodes for large-area and flexible organic light emitting diodes (OLEDs). The device performance is superior to that of a device based on the as-coated AgNW electrode, and is also comparable to that of a device using commercial ITO as the electrode. The redox-welding and embedding processes provide a facile and reliable method for fabricating large-area transparent flexible electrodes for next-generation flexible optoelectronic devices.

For highly efficient water–oil separation, superhydrophobic surfaces were prepared by coating the virus-like silica nanoparticles (VLSNs) on a substrate in scalable manner and subsequent fluoroalkyl silane through the sol–gel process. On the VLSN-coated glass substrate, the contact angle of the water droplet increased from 100.8° (plain silica nanoparticles) to 178.9° in the air as the areal density of coated nanoparticles increased up to 8,170 nanoparticles per µm2. Furthermore, fabric membrane and stainless-steel mesh were coated with VLSNs and subsequently functionalized with fluoroalkyl silane, which was utilized for continuous oil–water separation with a high separation efficiency (>99%), high flux (>2,000 L/m2⋅h) and high washing durability (>500 cycles). Additionally, these superhydrophobic fabrics were applied for removing oil contaminants on water by absorption within ten seconds.

Optically transparent poly(ether sulfone) (PES) nanocomposite films with low coefficients of thermal expansion (CTE) were synthesized for use as flexible display substrates. Boehmite (AlOOH) nanowires ~10 nm in diameter were synthesized and applied as fillers to reduce the CTE of the PES film. PES molecules were slightly sulfonated to enhance their compatibility with AlOOH nanowires via hydrogen bonding. The aspect ratio of the AlOOH nanowires had a significant effect on the CTE of nanocomposite films. At a fixed filler concentration of 15 wt%, the AlOOH nanowires with an aspect ratio of 100 reduced the CTE of the PES film by 73.6 % from 65.5 ppm/°C to 17.3 ppm/°C, while those with an aspect ratio of 20 reduced it only by 28 %. Although such a huge reduction of CTE was provided by AlOOH nanowires, the optical transmittance was still 96 % of the pristine PES film because the refractive indices of PES and AlOOH nanowires were the same. Introduction of AlOOH nanowires also enhanced the thermal and dimensional stabilities of the PES film.

The thermal conductivity (κ) of polymer nanocomposites with boron nitride (BN) nanoplates is critically dependent on the distribution of BN in the polymer matrix. Here, we heavily functionalized BN nanoplates with hydroxyl groups by ultrasonication in solution with boric acid. Then, the hydroxylated BN nanoplates could be homogeneously distributed in an epoxy matrix, which improved the through-plane κ of 2.09 and 1.96 W/m·K at 25 and -90 °C, respectively. Processable composite resin with hydroxylated BN was utilized as an adhesive for a low-temperature superconducting (LTS) coil to enhance its normal zone propagation velocity (NZPV) and cooling rate performance. Consequently, fast heat dissipation through the adhesive between superconductors contributed to a 65.8% of increase in NZPV and a 13.1% improvement in the cooling rate of the device compared with a commercial adhesive.

With a diffusion-assisted post-crosslinking method, polymer microspheres containing epoxy groups are crosslinked with ethylenediamine (EDA), gradually diffusing and reacting in the particles via amine/epoxy ring-opening reactions as confirmed by FT-IR and DSC results. Using a microcompression test, we find that the mechanical property (deformability under different applied force, breaking points, and recoverability) of the crosslinked microspheres is varied when different amounts of EDA are used in the system, resulting from different crosslinking density of the particles. An additional feature of the EDA treatment is to generate amine groups on the surface of the microspheres, enabling us to produce hybrid microspheres. We exploit them as immobilization sites for gold nanoparticles, forming gold-coated crosslinked microspheres. We also introduce a sequential functionalization method to fabricate crosslinked microspheres with selective functional groups on the surface. This approach can be a facile method to produce functional microspheres with controlled mechanical and surface properties.

We report a simple and robust strategy to prepare pH-responsive biphasic Janus particles composed of polystyrene/poly(2-vinylpyridine) (PS/P2VP) homopolymers that are able to control the reversible formation, breakage, and switching of Pickering emulsions depending on their geometry- and pH-dependent hydrophilic–lipophilic balance. The chemical stability of these PS/P2VP Janus particles was tuned through the incorporation of cross-linkable benzophenone units along the backbone of the homopolymers. By employing these stabilized particles as emulsifiers for toluene and water, a facile transformation of emulsion types (i.e., from toluene-in-water to water-in-toluene emulsions) was achieved by adjusting the pH of the aqueous phase. More importantly, this pH-dependent switching behavior and associated stability of the emulsions could be actively controlled by adjusting the relative size ratio of PS to P2VP. When the PS volume fraction (ϕPS) was between 0.33 and 0.67, a wide range tuning of emulsion phase inclu...

Patches on the surfaces of colloidal particles provide directional information that enables the self-assembly of the particles into higher-order structures. Although computational tools can make quantitative predictions and can generate design rules that link the patch motif of a particle to its internal microstructure and to the emergent properties of the self-assembled materials, the experimental realization of model systems of particles with surface patches (or 'patchy' particles) remains a challenge. Synthetic patchy colloidal particles are often poor geometric approximations of the digital building blocks used in simulations and can only rarely be manufactured in sufficiently high yields to be routinely used as experimental model systems. Here we introduce a method, which we refer to as colloidal fusion, for fabricating functional patchy particles in a tunable and scalable manner. Using coordination dynamics and wetting forces, we engineer hybrid liquid-solid clusters that evolve into particles with a range of patchy surface morphologies on addition of a plasticizer. We are able to predict and control the evolutionary pathway by considering surface-energy minimization, leading to two main branches of product: first, spherical particles with liquid surface patches, capable of forming curable bonds with neighbouring particles to assemble robust supracolloidal structures; and second, particles with a faceted liquid compartment, which can be cured and purified to yield colloidal polyhedra. These findings outline a scalable strategy for the synthesis of patchy particles, first by designing their surface patterns by computer simulation, and then by recreating them in the laboratory with high fidelity.

We present a near-field mapping of electric fields from the individual superspherical and ultrasmooth gold nanoparticles (AuNPs) and artificially assembled AuNP nanostructures by measuring the reconfiguration of an azobenzene-containing polymer(azo-polymer) film. Various configurations of AuNPs and the azo-polymer were studied with atomic force microscopy measurements and calculations. The interference was systematically studied with AuNP dimers of various gap distances and different embedding depth in the polymer film. Finally, we successfully demonstrated the interference of standing waves in artificially assembled plasmonic metasurface.

Colloids with patches, which refer physically or chemically distinct domains at their surface, have broaden the range of complex superstructures that can be achieved by self-assembly. Similarly, patches are recently introduced on micelles which are called “soft patchy micelles”. Due to soft interaction potential between patches on micelles, it holds great potential to form unique soft superstructures at nanoscale. In this review, we first describe a recent development in the synthesis of soft patchy micelles. Diblock amphiphilic copolymers are encapsulated into uniform emulsion which are then aggregated and reformed into patchy micelles with surfactants at interface. Alternatively, triblock amphiphilic copolymers are assembled into uniform spherical patchy micelles via stepwise micellization process. For cylindrical or platelet micelles, block copolymers with crystallizable core-forming blocks are introduced for monodisperse cylindrical or platelet patchy micelles by sequential growth of core blocks. Finally, we discuss how those soft patchy micelles are assembled into two or three-dimensional superstructures by hydrophobic-hydrophobic interaction, electrostatic attraction or coordination between patches, showing potentials of micellar structure as a soft designer micelles.

Self-assembly is a powerful approach for constructing colloidal crystals, where spheres, rods or faceted particles can build up a myriad of structures. Nevertheless, many complex or low-coordination architectures, such as diamond, pyrochlore and other sought-after lattices, have eluded self-assembly. Here we introduce a new design principle based on preassembled components of the desired superstructure and programmed nearest-neighbour DNA-mediated interactions, which allows the formation of otherwise unattainable structures. We demonstrate the approach using preassembled colloidal tetrahedra and spheres, obtaining a class of colloidal superstructures, including cubic and tetragonal colloidal crystals, with no known atomic analogues, as well as percolating low-coordination diamond and pyrochlore sublattices never assembled before. Complex colloidal crystal structures can be obtained by a combination of preassembled units and DNA-mediated interactions. This enables, for instance, the generation of a MgCu2 structure with interpenetrating diamond and pyrochlore sublattices.

Polymeric thin films coated on non-wettable substrates undergo film-instabilities, which are usually manifested as surface deformation in the form of dewetting or wrinkling. The former takes place in fluidic films, whereas the latter occurs in solid films. Therefore, there have rarely been reports of systems involving simultaneous deformations of dewetting and wrinkling. In this study, we propose polymeric thin films of liquid crystalline (LC) mesogens prepared on a non-wettable Si substrate and apply a treatment of plasma irradiation to form a thin polymerized layer at the surface. The resulting compressive stress generated in the surface region drives the formation of wrinkles, while at the same time, dipolar attraction between LC molecules induces competitive cohesive dewetting. Intriguing surface structures were obtained whereby dewetting-like hole arrays are nested inside the randomly propagated wrinkles. The structural features are readily controlled by the degree of surface cross-linking, hydrophilicity of the substrates, and the LC film thickness. In particular, dewetting of LC mesogens is observed to be restricted to occur at the trough regions of wrinkles, exhibiting the typical behavior of geometrically confined dewetting. Finally, wrinkling-dewetting mixed structures are separated from the substrate in the form of free standing films to demonstrate the potential applicability as membranes.

Silica nanoparticles can be used as an adhesive for hydrogels or biological tissues due to their physical adsorption to polymer chains. Recently, we found that mesoporous nanoparticles were able to enhance the adhesion energy between hydrogels compared with non-porous nanoparticles because of the higher outer surface area of mesoporous silica nanoparticles. However, even in the case that the outer surface areas of mesoporous silica nanoparticles are similar, mesoporous nanoparticles with larger pore diameters showed significantly higher nanoparticle-mediated adhesion energy between hydrogels with a swelling ratio of 400%. Here, we have changed the swelling ratio of hydrogels in the preparation step so that the blob size in the polymer network changed accordingly. In experimental data, we found that the optimum pore size of mesoporous nanoparticles increased as the blob size increased for higher swelling ratio, which is ascribed to the larger blob size of polymer networks in hydrogels.

Janus colloids with one attractive patch on an otherwise repulsive particle surface serve as model systems to explore structure formation of particles with chemically heterogeneous surfaces such as proteins. While there are numerous computer studies, there are few experimental realizations due to a lack of means to produce such colloids with a well-controlled variable Janus balance. Here, we report a simple scalable method to precisely vary the Janus balance over a wide range and selectively functionalize one patch with DNA. We observe, via experiment and simulation, the dynamic formation of diverse superstructures: colloidal micelles, chains, or bilayers, depending on the Janus balance. Flexible dimer chains form through cooperative polymerization while trimer chains form by a two-stage process, first by cooperative polymerization into disordered aggregates followed by condensation into more ordered stiff trimer chains. Introducing substrate binding through depletion catalyzes dimer chains to form nonequilibrium rings that otherwise do not form., Janus colloids with an attractive patch on the surface are model systems to explore structure formation but experimental realizations of such particles are rare. Here, the authors report a scalable method to precisely vary the Janus balance over a wide range and observe the formation of various structures including fibers, bilayers, and nonequilibrium rings catalyzed by substrate binding.

Injecting human mesenchymal stem cells (hMSCs) at wound sites is known to have a therapeutic effect, however, hMSCs have several limitations, such as low viability and poor engraftment after injection, as well as a potential risk of oncogenesis. The use of a conditioned medium (CM) was suggested as an alternative method for treating various wounds instead of direct hMSC administration. In addition to not having the adverse effects associated with hMSCs, a CM can be easily mass produced and can be stored for long-term, thereby making it useful for clinical applications. In general, a CM is collected from hMSCs with low passage number, whereas, the hMSCs with high passage number are usually discarded because of their low therapeutic efficacy as a result of reduced angiogenic factor secretion. Herein, we used a CM collected from high passage number (passage 12, P12) hMSCs treated with gold-iron nanoparticles (AuFe NPs). Our AuFe NPs were designed to release the iron ion intracellularly via endocytosis. Endosomes with low pH can dissolve iron from AuFe NPs, and thus, the intracellularly released iron ions up-regulate the hypoxia-inducible factor 1&alpha, and vascular endothelial growth factor (VEGF) expression. Through this mechanism, AuFe NPs improve the amount of VEGF expression from P12 hMSCs so that it is comparable to the amount of VEGF expression from low passage number (passage 6, P6), without treatment. Furthermore, we injected the CM retrieved from P12 MSCs treated with AuFe NPs in the mouse skin wound model (AuFe P12 group). AuFe P12 group revealed significantly enhanced angiogenesis in the mouse skin wound model compared to the high passage hMSC CM-injected group. Moreover, the result from the AuFe P12 group was similar to that of the low passage hMSC CM-injected group. Both the AuFe P12 group and low passage hMSC CM-injected group presented significantly enhanced re-epithelization, angiogenesis, and tissue remodeling compared to the high passage hMSC CM-injected group. This study reveals a new strategy for tissue regeneration based on CM injection without considering the high cell passage count.

DNA-coated inorganic particles can be prepared simply by physical adsorption of azide-functionalized diblock copolymers (polystyrene-b-poly(ethylene oxide)-azide, PS-b-PEO-N3) onto hydrophobically-modified inorganic particles, followed by strain-promoted azide–alkyne cycloaddition (SPAAC, copper-free click chemistry). This approach is applied to organosilica, silica and titania particles. The DNA-coated colloids are successfully crystallized into colloidal superstructures by a thermal annealing process using DNA-mediated assembly.

Au@Ag core–shell structures have received particular interest due to their localized surface plasmon resonance properties and great potential as oxygen reduction reaction catalysts and building blocks for self-assembly. In this study, Au@Ag core–shell nanocubes (Au@AgNCs) were fabricated in a facile manner via stepwise Ag reduction on Au nanoparticles (AuNPs). The size of the Au@AgNCs and their optical properties can be simply modulated by changing the Ag shell thickness. Structural characterization has been carried out by TEM, SAED, and XRD. The metal-induced fluorescence properties of probe molecules near the Au@AgNCs were measured during sedimentation of the Au@AgNCs. The unique ring-like building block of Au@AgNCs has dual optical functions as a fluorescence quencher or fluorescence enhancement medium depending on the assembled regions.

Fiber-based electronics or textronics are spotlighted as a promising strategy to develop stretchable and wearable devices for conformable machine-human interface and ubiquitous healthcare systems. We have prepared a highly sensitive fiber-type strain sensor (maximum gauge factor (GF) = 863) with a broad range of strain (ε400%) by introducing a single active layer onto the fiber. In contrast to other metal-based fiber-type electronics, our hierarchical fiber sensors are based on coating carbon-based nanomaterials with responsive microbeads onto elastic fibers. Utilizing the formation of uniform cracks around the microbeads, the device performance was maximized by adjusting the number of microbeads in the carbon-coating layer. We overcoated the carbon-based coating layer of the elastic fiber with a protective polymeric layer and verified no effects on the GF and the range of strain. Our fiber sensors were repeatedly tested more than 5000 times, exhibiting excellent cyclic responses to on/off switching behaviors. For practical applications, the hierarchical fiber sensors were sewed into electrical fabric bands, which are integrable to a wireless transmitter to monitor waveforms of pulsations, respirations, and various postures of level of bending a spinal cord.

Hollow carbon-silica nanospheres that exhibit angle-independent structural color with high saturation and minimal absorption are made. Through scattering calculations, it is shown that the structural color arises from Mie resonances that are tuned precisely by varying the thickness of the shells. Since the color does not depend on the spatial arrangement of the particles, the coloration is angle independent and vibrant in powders and liquid suspensions. These properties make hollow carbon-silica nanospheres ideal for applications, and their potential in making flexible, angle-independent films and 3D printed films is explored.

This study presents a combined strategy of bidisperse boron nitride (BN) and surface modification to improve the thermal conductivity (κ) of the BN-epoxy composite. Surface modification of hexagonal BN was carried out with benzoic acid (BA). The optimal weight ratio of large and small BN (BNl and BNs) was 8:2 for their connectivity in the epoxy matrix. For 50 wt% filler content, the BNl8s2-BA composite has a much higher κ of 2.71 W/m K (out-plane direction), which is 12.3, 1.32, and 1.50 times higher than that of the pure epoxy, and its composite with BNl10s0-BA and BNl8s2, respectively. The chemical-sensitive analyses indicate that carboxyl-carboxylate interaction occurred in partially deprotonated benzoic acid on BN during the epoxy curing process, resulting in in-situ formation of a continuously thermal conductive pathway, which is responsible for the improved κ.

Although sonodynamic therapy (SDT) has emerged as a potential alternative to conventional photodynamic therapy, the low quantum yield of the sonosensitizer such as TiO2 nanoparticles (NPs) is still a major concern. Here, we have developed hydrophilized Au-TiO2 nanocomposites (HAu-TiO2 NCs) as sonosensitizers for improved SDT. The physicochemical properties of HAu-TiO2 NCs were thoroughly studied and compared with their counterparts without gold deposition. Upon exposure of HAu-TiO2 NCs to ultrasound, a large quantity of reactive oxygen species (ROS) were generated, leading to complete suppression of tumor growth after their systemic administration in vivo. Overall, it was evident that the composites of gold with TiO2 NPs significantly augmented the levels of ROS generation, implying their potential as SDT agents for cancer therapy.

To enhance cellular uptake and site-specific drug release in the tumor microenvironment, zwitterionic mesoporous silica nanoparticles (Z-MSN) were prepared by introducing a bioresponsive gatekeeper composed of negatively charged carboxylic groups and positively charged quaternary amine groups. When these Z-MSN encountered a mildly acidic environment, their surface charge readily switched from negative to positive by cleavage of an acid-labile maleic amide linkage, thus allowing for effective cellular uptake into tumor tissue. Doxorubicin (DOX) encapsulated in Z-MSN was not significantly released in physiological conditions (pH 7.4), whereas the release rate of DOX remarkably increased in mildly acidic conditions through disintegration of the gatekeeper. The antitumor efficacy of DOX-loaded Z-MSN (DOX-Z-MSN) was evaluated after their systemic administration to tumor-bearing mice. Compared to free DOX and DOX-loaded MSN without the gatekeeper, DOX-Z-MSN exhibited much higher antitumor efficacy in vivo. Overall, these results demonstrated that the hydrophilic negative surface of Z-MSN, with their closed gate, allowed for their effective accumulation in tumor tissue after systemic administration, and that their charge-swapping and gate-opening in the tumor environment enhanced their cellular uptake and drug release rate simultaneously, implying a highly promising potential for development of Z-MSN as a drug carrier for cancer therapy.In an attempt to address the issues of enhanced cellular uptake and site-specific drug release of nanoparticles, we herein report on zwitterionic MSN (Z-MSN) with a pH-responsive gatekeeper which can be internalized into cancer cells via switching their surface charge from negative, in physiological conditions, to positive, in the tumor microenvironment. We hypothesized that the hydrophilic negative surface of Z-MSN with a closed gate allows for their accumulation into tumor tissue after systemic administration, whereas their charge-swapping and gate-opening in the tumor environment enhance cellular uptake and drug release rate simultaneously. Overall, Z-MSN constitute a promising drug delivery carrier for cancer therapy.

The ability to reconfigure elementary building blocks from one structure to another is key to many biological systems. Bringing the intrinsic adaptability of biological systems to traditional synthetic materials is currently one of the biggest scientific challenges in material engineering. Here we introduce a new design concept for the experimental realization of self-assembling systems with built-in shape-shifting elements. We demonstrate that dewetting forces between an oil phase and solid colloidal substrates can be exploited to engineer shape-shifting particles whose geometry can be changed on demand by a chemical or optical signal. We find this approach to be quite general and applicable to a broad spectrum of materials, including polymers, semiconductors and magnetic materials. This synthetic methodology can be further adopted as a new experimental platform for designing and rapidly prototyping functional colloids, such as reconfigurable micro swimmers, colloidal surfactants and switchable building blocks for self-assembly., Mimicking the intrinsic adaptability of biological systems in synthetic materials has been a challenge. Here, Sacanna and co-workers have used dewetting forces between an oil phase and solid colloidal substrate to facilitate shape shifting particles that can change geometry by chemical and optical signals.

The smallness of natural molecules and atoms with respect to the wavelength of light imposes severe limits on the nature of their optical response. For example, the well-known argument of Landau and Lifshitz and its recent extensions that include chiral molecules show that the electric dipole response dominates over the magneto-electric (bianisotropic) and an even smaller magnetic dipole optical response for all natural materials. Here, we experimentally demonstrate that both these responses can be greatly enhanced in plasmonic nanoclusters. Using atomic force microscopy nanomanipulation technique, we assemble a plasmonic metamolecule that is designed for strong and simultaneous optical magnetic and magneto-electric excitation. Angle-dependent scattering spectroscopy is used to disentangle the two responses and to demonstrate that their constructive/destructive interplay causes strong directional scattering asymmetry. This asymmetry is used to extract both magneto-electric and magnetic dipole responses and to demonstrate their enhancement in comparison to ordinary atomistic materials.

Monodisperse Fe3O4 particles are prepared by solvothermal reaction, in which negatively charged sulfate groups are formed on the surface by adding potassium sulfate during the high-pressure reaction. Then, those particles are successfully dispersed in the polar solvent propylene carbonate and manipulated electrophoretically between transparent electrodes. By applying an external electric field, they showed structural colors which can be tuned precisely over the visible range depending on the strength of the electric field. Because sulfate groups on the particle surface are chemically stable or inert, those particles are highly stable against irreversible deposition on the electrode during electrophoretic operation. Therefore, we demonstrate highly stable color switches over at least hundreds of cyclic operations, which may be useful in real electronic paper display applications.

WO3/BiVO4 is one of the attractive Type II heterojunctions for photoelectrochemical (PEC) water splitting due to its well-matched band edge positions and visible light harvesting abilities. However, two light absorption components generally suffer from poor charge collection and cannot be efficiently utilized because of non-ideal interfaces. Herein, a triple-deck three-dimensional (3D) architecture was designed through a one-step shaping process with an additional stress relaxation WO3 underlayer. The final photoanodes showed a promising photocurrent density of 5.1 mA cm(-2) at 1.23 V vs. RHE under AM 1.5G illumination. Using the uniformly distributed oxygen evolution co-catalyst (OEC) layer as the outer most shell of the WO3/BiVO4/OEC triple-deck 3D structure with a dense WO3 underlayer, the water splitting efficiency was improved dramatically by facilitating the charge transfer process at the electrode/electrolyte interface.

A hierarchically spherical and ordered meso–macroporous silica (MMS) support was applied for the hydrogenation reaction of CO to hydrocarbons using a cobalt-based Fischer–Tropsch synthesis (FTS) catalyst, which was synthesized using dual templates of polystyrene beads for the macroporous structures and an amphiphilic triblock copolymer positioned inside emulsion droplets for the mesoporous structures. A higher surface area with a bimodal pore size distribution on the cobalt-impregnated MMS (Co/MMS) revealed a higher catalytic activity and stability by enhancing the mass transport rate of the heavier hydrocarbons formed inside the macropores with a larger wax entrapping capacity due to their large pore cavity compared with the conventional SiO2 support. The enhanced CO conversion and C5+ selectivity while using the Co/MMS even under a higher space velocity were mainly attributed to the presence of heavy hydrocarbons formed during the FTS reaction in the larger regular macropores' entrapping cavity resulting in the suppression of the wax deposition on the active cobalt sites. Even though the wax deposition seems to be inevitable during the FTS reaction, it was also easily and efficiently removed by intermittently feeding liquid octane during the FTS reaction for an in situ regeneration of the regular meso–macroporous Co/MMS.

Heat management is one of the key technologies for reliable and high-performance electric devices. We have developed thermally conductive adhesives based on a commercial thermally conductive epoxy, Stycast 2850FT (S2850), with an additional unfilled resin and boron nitride (BN). The optimal mixing ratio of BN to epoxy resin was 10 wt%, and the thermal conductivity (κ) of this mixture was 1.65 W/m·K at 25 °C, 1.6 times higher than that of S2850. Such enhancement of κ may be attributed to the formation of more thermal conductive paths generated by the effective additives inside the composite adhesive layers, which was confirmed with elemental mapping analysis. Our epoxy-based thermally conductive adhesives with improved κ was then implemented for a superconducting magnet. Because of the enhanced heat dissipation of our composite adhesive, the superconducting magnet showed enhancement of 42.7%, 14.8%, and 76.6% in the cooling rate, the minimum quench energy, and the normal zone propagation velocity in the longitudinal direction at 70% of the current-carrying capacity, respectively, which are important parameters in the operational performance of a superconducting magnet, compared to a coil with S2850.

Sonodynamic therapy has received increasing attention for cancer treatments as an alternative to photodynamic therapy. However, its clinical applications have been limited by the lack of a sonosensitizer that is capable of producing sufficient amounts of reactive oxygen species (ROS) in response to ultrasound (US) exposure. Herein, PEGylated mesoporous silica-titania nanoparticles (P-MSTNs) are prepared and used as US-responsive nanocarriers for cancer sonotheranostics. Perfluorohexane (PFH), which is chosen as the gas precursor, is physically encapsulated into P-MSTNs using the oil-in-water emulsion method. Owing to the vaporization of the gas precursor, PFH@P-MSTNs (137 nm in diameter) exhibit a strong photoacoustic signal in vivo for at least 6 h. Compared to P-MSTNs, PFH@P-MSTNs generate significantly higher amounts of ROS due to the nanobubble-induced cavitation in the presence of US. When systemically administered to tumor-bearing mice, PFH@P-MSTNs effectively accumulate in the tumor site due to the passive targeting mechanism. Consequently, PFH@P-MSTNs show much higher antitumor efficacy than P-MSTNs due to the enhanced cavitation-mediated ROS generation in response to US exposure. It is considered that PFH@P-MSTNs may hold significant potential for cancer sonotheranostics.

Photonic crystals (PCs) are ideal candidates for reflective color pigments with high color purity and brightness due to tunable optical stop band. Herein, the generation of PC microspheres through 3D confined supramolecular assembly of block copolymers (polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP) and small molecules (3-n-pentadecylphenol, PDP) in emulsion droplets is demonstrated. The intrinsic structural colors of the PC microspheres are effectively regulated by tuning hydrogen-bonding interaction between P2VP blocks and PDP, where reflected color can be readily tuned across the whole visible spectrum range. Also, the effects of both PDP and homopolymer (hPS) on periodic structure and optical properties of the microspheres are investigated. Moreover, the spectral results of finite element method (FEM) simulation agree well with the variation of structural colors by tuning the periodicity in PC microspheres. The supramolecular microspheres with tunable intrinsic structural color can be potentially useful in the various practical applications including display, anti-counterfeit printing and painting.

Four 1-butyl-3-methylimidazolium halide ionic liquids were synthesized via metathesis and anion exchange reactions. Silver nanoparticles (AgNPs) colloids were synthesized in four ionic liquids in the pressurized reactor by reduction of silver nitrate with hydrogen gas, without adding solvents or stabilizing agents. Antibacterial activities of base ionic liquids and AgNPs colloids in ionic liquids were reviewed by well-diffusion method for gram-positive Bacillus cereus (NCIM-2155) and gram-negative Escherichia coli (NCIM-2931) bacteria. Antibacterial activities of ionic liquids and AgNPs colloids in ionic liquids were observed to be controlled by ionic liquids anions and AgNPs particle size. The 1-butyl-3-methylimidazolium iodide ionic liquid exhibited higher antibacterial activities among the studied ionic liquids. Further, the presence of AgNPs in 1-butyl-3-methylimidazolium iodide, ionic liquid enhanced its antibacterial activity for Bacillus cereus and Escherichia coli bacteria.

Non-spherical colloidal building blocks introduce new design principles for self-assembly, making it possible to realize optical structures that could not be assembled previously. With this added complexity, the phase space expands enormously so that computer simulation becomes a valuable tool to design and assemble structures with useful optical properties. We recently demonstrated that tetrahedral clusters and spheres, interacting through a DNA-mediated short-range attractive interaction, self-assemble into a superlattice of interpenetrating diamond and pyrochlore sublattices, but only if the clusters consist of partially overlapping spheres. Here we show how the domain of crystallization can be extended by implementing a longer range potential and consider how the resultant structures affect the photonic band gaps of the underlying pyrochlore sublattice. We show that with the proper design, using clusters of overlapping spheres lead to larger photonic band gaps that open up at lower optical contrast.

To create printing substrates for colorimetric sensor arrays, chemically resistant membranes are prepared by coating cellulose filter paper with perfluoroalkoxy (PFA) polymer nanoparticles. A water-based fluorothermoplastic polymer dispersion was diluted with an organic solvent that causes weak aggregation of polymer nanoparticles. The resulting solution improved adhesion between the polymer and the cellulose membrane, providing a more mechanically stable substrate. These PFA polymer-coated substrates demonstrated superior chemical resistance against strong alkalines and had relatively uniform nanoporous structures that substantially improved the printability of a colorimetric sensor array. Finally, colorimetric sensor arrays printed on these substrates were evaluated for the detection of four different toxic industrial chemicals (e.g., ammonia, hydrogen sulfide, nitrogen dioxide, and sulfur dioxide) at or below their permissible exposure limits.

Correction for ‘Compressible colloidal clusters from Pickering emulsions and their DNA functionalization’ by In-Seong Jo et al., Chem. Commun., 2018, 54, 8328–8331.

Colloidal clusters were prepared by assembling azide-functionalized non-crosslinked polymer particles using fluorinated oil-in-water emulsion droplets. The particles were adsorbed onto the droplet interface, which were packed to form clusters during slow evaporation of the oil. Then, the clusters were coated by DNA using an alkyne–azide cycloaddition (SPAAC) reaction. As the particles are not crosslinked, the shape of the DNA-coated clusters can be further modified to control the compression ratio through plasticization.

A simple yet versatile solution-based process to produce colloidal silica hexapods is developed in which various shapes of silica rods are grown on the faces of cubes in a controlled manner. In the presence of hematite cubic particles, water droplets nucleate on the surface of hematite by phase separation in pentanol. By adjusting the water concentration, six droplets can form on each face of the hematite cube. A silica precursor is then administered into the system, which gradually diffuses into the water droplets through the oil phase. Within the droplets, hydrolysis and condensation of the precursors take place, leading to formation of silica rods. As a result, silica hexapods on a magnetic hematite cubic seed are produced. Furthermore, when the emulsions are aged at 60 °C prior to the silica growth, the water content in the solution decreases gradually due to evaporation and spiky sharp hexapods are produced. On the other hand, when organosilane precursor is added, pancake-like hexapods are formed due to the reduction of interfacial tension. These colloidal hexapods can further be utilized as new building blocks for self-assembly to construct functional materials or as a model system to understand collective behaviors.

Mesoporous silica nanoparticles (MSNs) with stimuli-responsive gatekeepers have been extensively investigated for controlled drug delivery at the target sites. Herein, we developed reactive oxygen species (ROS)-responsive MSNs (R-MSNs), consisting of a gadolinium (Gd)-DOTA complex as the ROS-responsive gatekeeper and polyethylene glycol (PEG)-conjugated chlorin e6 as the ROS generator, for magnetic resonance (MR) imaging-guided photodynamic chemotherapy. Doxorubicin (DOX), chosen as an anticancer drug, was physically encapsulated into DOTA-conjugated MSNs, followed by chemical crosslinking via the addition of GdCl3. DOX-R-MSNs could effectively maintain their structural integrity in a physiological environment for 7 days and show an enhanced in vitro T1-MR imaging signal for the Gd-DOTA complex. Upon 660 nm laser irradiation, the release rate of DOX from DOX-R-MSNs remarkably increased along with the disintegration of the gatekeeper, whereas DOX release was significantly retarded without irradiation. When DOX-R-MSNs were intravenously injected into tumor-bearing mice, they were effectively accumulated in tumor tissue, which was demonstrated using MR imaging. In addition, tumor growth was significantly suppressed by DOX-R-MSNs, allowing for site-specific release of DOX in a photodynamically maneuvered manner. Overall, these results suggest that R-MSNs have potential as drug carriers for MR imaging-guided photodynamic chemotherapy.

Hypoxia, or low oxygen tension, is a common feature of solid tumors. Here, we report hypoxia-responsive mesoporous silica nanoparticles (HR-MSNs) with a 4-nitroimidazole-β-cyclodextrin (NI-CD) complex that is acting as the hypoxia-responsive gatekeeper. When these CD-HR-MSNs encountered a hypoxic environment, the nitroimidazole (NI) gatekeeper portion of CD-HR-MSNs disintegrated through bioreduction of the hydrophobic NI state to the hydrophilic NI state. Under hypoxic conditions, the release rate of doxorubicin (DOX) from DOX-loaded CD-HR-MSNs (DOX-CD-HR-MSNs) increased along with the disintegration of the gatekeeper. Conversely, DOX release was retarded under normoxic conditions. In vitro experiments confirmed that DOX-CD-HR-MSNs exhibit higher toxicity to hypoxic cells when compared to normoxic cells. Confocal microscopy images indicated that DOX-CD-HR-MSNs effectively release DOX into SCC-7 cells under hypoxic conditions. These results demonstrate that CD-HR-MSNs can release drugs in a hypoxia-responsive manner, and thus are promising drug carriers for hypoxia-targeted cancer therapy.

Wrinkling is a well-known example of instability-driven surface deformation that occurs when the accumulated compressive stress exceeds the critical value in multilayered systems. A number of studies have investigated the instability conditions and the corresponding mechanisms of wrinkling deformation. Force balance analysis of bilayer systems, in which the thickness of the capping layer is importantly considered, has offered a useful approach for the quantitative understanding of wrinkling. However, it is inappropriate for multilayer wrinkling (layer number > 3) consisting of heterogeneous materials (e.g. polymer/metal or inorganic), in which the thickness variation in the substrate is also crucial. Therefore, to accommodate the additive characteristics of multilayered systems, we thermally treated tri- or quad-layer samples of polymer/metal multilayers to generate surface wrinkles and used a cumulative energy balance analysis to consider the individual contribution of each constituent layer. Unlike the composite layer model, wherein the thickness effect of the capping layer is highly overestimated for heterogenously stacked multilayers, our approach precisely reflects the bending energy contribution of the given multilayer system, with results that match well with experimental values. Furthermore, we demonstrate the feasibility of this approach as a metrological tool for simple and straightforward estimation of the thermomechanical properties of polymers, whereby a delicate change in the Young's modulus of a thin polymeric layer near its glass transition temperature can be successfully monitored.

We demonstrate a method to create high-density DNA coatings on colloidal particles that can be used for DNA-mediated self-assembly of single- and multiple-component colloidal crystals. First, we modify an amphiphilic diblock copolymer consisting of a hydrophobic polystyrene (PS) block and a hydrophilic poly(ethylene oxide) (PEO) block with azide functional groups at the end (poly(ethylene oxide)-N3). Then, we introduce the diblock copolymers into an aqueous suspension of colloidal polymer particles swollen with a solvent. The hydrophobic PS anchoring block is incorporated into the swollen polymer spheres and physically trapped when the solvent is removed, resulting in a dense PEO polymer brush with azide functional end groups. Finally, single-stranded DNA strands with sticky ends are attached to the azide groups using strain-promoted azide–alkyne cycloaddition (SPAAC, a copper-free click chemistry). This procedure results in a high areal coverage of up to 225 000 DNA strands on 1-μm-diameter particles. Th...

Surface carbon coating to improve the inherent poor electrical conductivity of lithium iron phosphate (LiFePO4, LFP) has been considered as most efficient strategy. Here, we also report one of the conventional methods for LFP but exhibiting a specific capacity beyond the theoretical value, ultrahigh rate performance, and excellent long-term cyclability: the specific capacity is 171.9 mAh/g (70 μm-thick electrode with ∼10 mg/cm(2) loading mass) at 0.1 C (17 mA/g) and retains 143.7 mAh/g at 10 C (1.7 A/g) and 95.8% of initial capacity at 10 C after 1000 cycles. It was found that the interior conformal N-C coating enhances the intrinsic conductivity of LFP nanorods (LFP NR) and the exterior reduced graphene oxide coating acts as an electrically conducting secondary network to electrically connect the entire electrode. The great electron transport mutually promoted with shorten Li diffusion length on (010) facet exposed LFP NR represents the highest specific capacity value recorded to date at 10 C and ultralong-term cyclability. This conformal carbon coating approach can be a promising strategy for the commercialization of LFP cathode in lithium ion batteries.