Achieving complete electrooxidation of ethanol by single atomic Rh decoration of Pt nanocubes.

SignificanceDirect ethanol fuel cells are attracting growing attention as portable power sources due to their advantages such as higher mass-energy density than hydrogen and less toxicity than methanol. However, it is challenging to achieve the complete electrooxidation to generate 12 electrons per ethanol, resulting in a low fuel utilization efficiency. This manuscript reports the complete ethanol electrooxidation by engineering efficient catalysts via single-atom modification. The combined electrochemical measurements, in situ characterization, and density functional theory calculations unravel synergistic effects of single Rh atoms and Pt nanocubes and identify reaction pathways leading to the selective C-C bond cleavage to oxidize ethanol to CO2. This study provides a unique single-atom approach to tune the activity and selectivity toward complicated electrocatalytic reactions.

Freestanding Penta-Twinned Palladium Nanosheets.

Control over the morphology of nanomaterials to have a 2D structure and manipulating the surface strain of nanostructures through defect control have proved to be promising for developing efficient catalysts for sustainable chemical and energy conversion. Here a one-pot aqueous synthesis route of freestanding Pd nanosheets with a penta-twinned structure (PdPT NSs) is presented. The generation of the penta-twinned nanosheet structure can be succeeded by directing the anisotropic growth of Pd under the controlled reduction kinetics of Pd precursors. Experimental and computational investigations showed that the surface atoms of the PdPT NSs are effectively under a compressive environment due to the strain imposed by their twin boundary defects. Due to the twin boundary-induced surface strain as well as the 2D structure of the PdPT NSs, they exhibited highly enhanced electrocatalytic activity for oxygen reduction reaction compared to Pd nanosheets without a twin boundary, 3D Pd nanocrystals, and commercial Pd/C and Pt/C catalysts.

Exploiting Plasmonic Hot Spots in Au-Based Nanostructures for Sensing and Photocatalysis.

ConspectusLocalized surface plasmon resonance is a unique property appearing in certain metal nanostructures, which can generate hot carriers (electrons and holes) and bring about an intense electromagnetic field localized near the surface of nanostructures. Specific locations, such as the rough surfaces and gaps in nanostructures, where a strong electromagnetic field is formed are referred to as hot spots. Hot-spot-containing plasmonic nanostructures have shown great promise in molecular sensing and plasmon-induced catalytic applications by exploiting the unique optical properties of hot spots. In this Account, we will review our recent developments in the synthesis of Au nanostructures consisting of multiple hot spots and Au-based heteronanostructures combining secondary active metals or semiconductors with Au nanostructures as promising plasmonic platforms for hot-spot-induced sensing and photocatalysis. We first provide a brief introduction to Au nanocrystals and Au nanoparticle assemblies with multiple hot spots. High-index-faceted hexoctahedral Au nanocrystals having multiple high-curvature vertices and edges are beneficial for the generation of an intense and reproducible electromagnetic field, which can enhance the performance of surface-enhanced Raman scattering-based molecular sensing. In addition, the engineering of interparticle gaps in Au nanoparticle assemblies to have a controlled size and a certain number of gaps can lead to the enhancement of plasmonic properties due to the significant amplification of the electromagnetic field at interparticle gaps. We then discuss hot-spot-containing Au-based heteronanostructures prepared by growing secondary components on the aforementioned Au nanostructures. With a combination of merit from strong plasmon energy formed by hot spots and catalytically active secondary materials, Au-based heteronanostructures have emerged as an attractive and versatile catalyst platform for various photocatalytic reactions. Through the control of key factors governing the photocatalysis of Au-based heteronanostructures, such as the coupling manner, shell thickness of secondary materials, and intimacy of contact, the plasmon energy formation of heteronanostructures and its transfer to catalytically active materials can be optimized, leading to the promotion of photocatalysis, such as photocatalytic hydrogen evolution. The rational design of Au nanostructures and Au-based heteronanostructures with multiple hot spots not only could realize enhanced sensing and photocatalysis but also could enable the understanding of the geometry-performance relationship. It is envisioned that the developed strategies can offer new opportunities for the design of various high-efficiency catalytic platforms.

Role of Surface Strain at Nanocrystalline Pt{110} Facets in Oxygen Reduction Catalysis.

We have developed a synthesis method of rhombic dodecahedral Pd@Pt core-shell nanocrystals bound exclusively by {110} facets with controlled numbers of Pt atomic layers to study the surface strain-catalytic activity relationship of Pt{110} facets. Through control over growth kinetics, the epitaxial and conformal overgrowth of Pt shells on the {110} facets of rhombic dodecahedral Pd nanocrystals could be achieved. Notably, the electrocatalytic activity of the Pd@Pt nanocrystals toward oxygen reduction reaction decreased as their Pt shells became thinner and thus more in-plane compressive surface strain was applied, which is in sharp contrast to previous reports on Pt-based catalysts. Density functional theory calculations revealed that the characteristic strain-activity relationship of Pt{110} facets is the result of the counteraction of out-of-plane surface strain against the applied in-plane surface strain, which can effectively impose a tensile environment on the surface atoms of the Pd@Pt nanocrystals under the compressive in-plane strain.

Surface Engineering of Palladium Nanocrystals: Decoupling the Activity of Different Surface Sites on Nanocrystal Catalysts.

The existence of various surface active sites within a nanocrystal (NC) catalyst complicates understanding their respective catalytic properties and designing an optimal catalyst structure for a desired catalytic reaction. Here, we developed a novel approach that allows unequivocal investigation on the intrinsic catalytic reactivity of the edge and terrace atoms of NCs. Through the comparison of the catalytic behaviors of edge-covered Pd NCs, which were prepared by the selective deposition of catalytically inactive Au atoms onto the edge sites of rhombic dodecahedral (RD) Pd NCs, with those of the pristine RD Pd NCs toward alkyne hydrogenation and Suzuki-Miyaura coupling reactions, we could decouple the activity of the edge and {110}-plane atoms of the Pd NCs without uncertainties. We expect that this study will provide an opportunity to scrutinize the surface properties of various NC catalysts to a more precise level and devise ideal catalysts for intended catalytic reactions.

Controlled Photoinduced Electron Transfer from InP/ZnS Quantum Dots through Cu Doping: A New Prototype for the Visible-Light Photocatalytic Hydrogen Evolution Reaction.

Photoexcited electron extraction from semiconductors can be useful for converting solar energy into useful forms of energy. Although InP quantum dots (QDs) are considered alternative materials for solar energy conversion, the inherent instability of bare InP QDs demands the use of passivation layers such as ZnS for practical applications, which impedes carrier extraction from the QDs. Here, we demonstrate that Cu-doped InP/ZnS (InP/Cu:ZnS) QDs improve the electron transfer ability due to hole capture by Cu dopants. Steady-state and time-resolved photoluminescence studies confirmed that electrons were effectively transferred from the InP/Cu:ZnS QDs to a benzoquinone acceptor by retarding the electron-hole recombination within the QD. We evaluated the photocatalytic H2 evolution performance of InP/Cu:ZnS QDs under visible light, which showed outstanding photocatalytic H2 evolution activity and stability under visible light illumination. The photocatalytic activity was preserved even in the absence of a cocatalyst.

Exosomes derived from chemically induced human hepatic progenitors inhibit oxidative stress induced cell death.

The emerging field of regenerative medicine has revealed that the exosome contributes to many aspects of development and disease through intercellular communication between donor and recipient cells. However, the biological functions of exosomes secreted from cells have remained largely unexplored. Here, we report that the human hepatic progenitor cells (CdHs)-derived exosome (EXOhCdHs ) plays a crucial role in maintaining cell viability. The inhibition of exosome secretion treatment with GW4869 results in the acceleration of reactive oxygen species (ROS) production, thereby causing a decrease of cell viability. This event provokes inhibition of caspase dependent cell death signaling, leading to a ROS-dependent cell damage response and thus induces promotion of antioxidant gene expression or repair of cell death of hypoxia-exposed cells. Together, these findings show the effect of exosomes in regeneration of liver cells, and offer valuable new insights into liver regeneration.

Nanoparticles Are Separated in a Different Pattern from Microparticles with Focused Flow Control.

Separation of particles is essential to ensure the reliability and reproducibility of experiments for nanometer-scale materials. There are several methods, such as ultracentrifugation, precipitation, filtration, etc., for separation. However, the separation of nanoparticles in a continuous operation has not been examined widely. Here, we report the separation of nanometer-scale particles on a microfluidic system and related separation phenomena of nanoparticles from microparticles. We also describe not-yet-confirmed reversed behaviors of nanoparticle separation in the process of continuous operation. The present system along with elucidated operational conditions could be applied to treat relatively large quantities of nanometer-scale particles.

Tuning Chemical Interface Damping: Interfacial Electronic Effects of Adsorbate Molecules and Sharp Tips of Single Gold Bipyramids.

The optimization of the localized surface plasmon resonance (LSPR)-decaying channels of hot-electrons is essential for efficient optical and photochemical processes. Understanding and having the ability to control chemical interface damping (CID) channel contributions will bring about new possibilities for tuning the efficiency of plasmonic hot-electron energy transfer in artificial devices. In this scanning electron microscopy-correlated dark-field scattering study, the CID was controlled by focusing on the electronic nature of disubstituted benzene rings acting as adsorbates, as well as the effects of sharp tips on gold bipyramids (AuBPs) with similar aspect ratios to those of gold nanorods. The results showed that the sharp tips on single AuBPs, as well as the electronic effects of the adsorbate molecules, increase the interfacial contact between the nanoparticles and adsorbate molecules. Electron withdrawing groups (EWGs) on the adsorbates induce larger homogeneous LSPR line widths compared to those of electron donating groups (EDGs). Depending on the location (ortho, meta, and para) of the EDG, the effect of benzene rings with an EDG, which was considered to be induced by sulfur atoms bound to the nanoparticle surface, is weakened by the back transfer of electrons facilitated by the difference in the availability of the electrons of the EDG. Therefore, this study reports that the CID in the LSPR total decay channels can be tuned by controlling the electron withdrawing and electron donating features of adsorbate molecules with the surface topology of metal.

Ultrathin-Polyaniline-Coated Pt-Ni Alloy Nanooctahedra for the Electrochemical Methanol Oxidation Reaction.

Controlling the morphology and composition of nanocatalysts constructed from metals and conductive polymers has attracted attention owing to their great potential for the development of high-efficiency catalysts for various catalytic applications. Herein, a facile synthetic approach for ultrathin-polyaniline-coated Pt-Ni nanooctahedra (Pt-Ni@PANI hybrids) with controllable PANI shell thicknesses is presented. Pt-Ni nanooctahedra/C catalysts enclosed by PANI shells with thicknesses from 0.6 to 2.4 nm were obtained by fine control over the amount of aniline. The various Pt-Ni@PANI hybrids exhibited electrocatalytic activity toward the methanol oxidation reaction that is highly dependent on the thickness of the PANI shell. Pt-Ni@PANI hybrids with the thinnest PANI shells (0.6 nm) showed markedly improved electrocatalytic performance for the methanol oxidation reaction compared with Pt-Ni@PANI hybrids with thicker PANI shells, Pt-Ni nanooctahedra/C, and commercial Pt/C due to synergistic benefits of ultrathin PANI shells and Pt-Ni alloy.

Properties of phase transition of ice binding protein from Arctic yeast (LeIBP) utilizing differential scanning calorimetry (DSC) and Raman spectroscopy.

Ice binding proteins (IBPs) have been attracting significant interest on account of their characteristic of inhibiting ice growth and recrystallization. Owing to their unique characteristics, IBPs have been studied for applications in food, pharmaceuticals, and medicine, as well as from a general scientific point of view. In this study, we have used differential scanning calorimetry (DSC) and Raman spectroscopy as tools to understand the ice binding activity of the Arctic-yeast-originating extracellular ice binding glycoprotein (LeIBP) isolated from Leucosporidium sp. AY30. From the DSC results, an increase in the specific heat capacity was confirmed for 1 mg/mL LeIBP, which suggested that additional heat flow was required for the change in temperature. In addition, the temperature corresponding to the phase change of the solution was measured, and Raman spectroscopy was carried out on the frozen and molten phases, respectively. From the results of Raman analysis, we confirmed that the helical vibrations related to the ice binding sites on LeIBP were dramatically suppressed when the LeIBP solution was frozen. Furthermore, principal component analysis (PCA) of the Raman spectra yielded the contrast factor between the freezing and melting states. Both DSC and Raman spectroscopy are widely used to study the ice binding activity and the structural changes associated with molecular vibrations in cryobiology.

Oxygen-Carrying Micro/Nanobubbles: Composition, Synthesis Techniques and Potential Prospects in Photo-Triggered Theranostics.

Microbubbles and nanobubbles (MNBs) can be prepared using various shells, such as phospholipids, polymers, proteins, and surfactants. MNBs contain gas cores due to which they are echogenic and can be used as contrast agents for ultrasonic and photoacoustic imaging. These bubbles can be engineered in various sizes as vehicles for gas and drug delivery applications with novel properties and flexible structures. Hypoxic areas in tumors develop owing to an imbalance of oxygen supply and demand. In tumors, hypoxic regions have shown more resistance to chemotherapy, radiotherapy, and photodynamic therapies. The efficacy of photodynamic therapy depends on the effective accumulation of photosensitizer drug in tumors and the availability of oxygen in the tumor to generate reactive oxygen species. MNBs have been shown to reverse hypoxic conditions, degradation of hypoxia inducible factor 1α protein, and increase tissue oxygen levels. This review summarizes the synthesis methods and shell compositions of micro/nanobubbles and methods deployed for oxygen delivery. Methods of functionalization of MNBs, their ability to deliver oxygen and drugs, incorporation of photosensitizers and potential application of photo-triggered theranostics, have also been discussed.

Yun Il-sun's Studies in Japan and Medical Research during the Colonial Period.

In this article, I looked at the life of Yun Il-sun, a representative medical scientist of modern Korea, and examined the following problems. First, I took note of the position of the Korean people in the academic system of the Japanese colonial empire and restored the life of Yun Il-sun as specifically as possible. Yun was educated among Japanese people from elementary school to university. Although he received the best education at Old System High School and Imperial University and grew to be a prominent medical scientist, he could not overcome his identity as a colonized. Yun Il-sun, who moved from Keijo Imperial University to Severance Union Medical College, involved in activities founding of the Korean Medical Association and the Korean Medical Journal. Second, I the meaning of 'culture' to the intellectuals in the periphery. Old System High School and Imperial University where Yun Il-sun was educated were the hotbed of 'culturalism.' Yun's college days were the heyday of Taisho Democracy, and students were attracted to Marxism, Christian poverty movement, Buddhist cultivation movement and so on. Yun sought to overcome the ideological of young people through the acquisition of 'culture.' The 'culture' emphasized by Yun had an enlightenment characteristic that emphasized education, but it also functioned as a'identity culture of educated elites.' Third, I used the concept of 'colonial academism' and examined the aspects and characteristics of the colonial-periphery academic field, focusing on medicine. Yun Il-sun was a Korean professor at the Keijo Imperial University. He founded an academic society and published an academic journal for Koreans. He attempted to reproduce scholarship by doctoral dissertations. At the same time, several facts show that he was also in the affected area of 'colonial academism': the fact that he was kicked out of the Keijo Imperial University, the fact that the Korean Medical Association and the Korean Medical Journal were banned by Governor General, the fact that his students asked for doctoral degrees from Kyoto Imperial University where he studied. Yun Il-sun crossed the limits of 'colonial academism' and acted as the agent of empire. This was made possible by the characteristics of the academic discipline of medicine, the environment of the Severance Union Medical College, and personal traits of superior ability and indifference to politics. I the postcolonial evolution of the 'colonial academism' and 'culturalism.' The mix of continuity and discontinuity from 'colonial academism' and the hybrid of Japanese academism and American academism, the Korean characteristics of 'postcolonial academism.' Yun tried to harmonize the American academism with the Japanese academism and the purity of academism. This effort was revealed as an emphasis on basic medicine and natural sciences. As combined with culturalism and indifference to politics, he was recognized as the symbol of ivory tower and academism.

Metal-Semiconductor Heteronanocrystals with Desired Configurations for Plasmonic Photocatalysis.

Precise control over the topology of plasmonic metal-semiconductor heteronanostructures is essential for fully harnessing their plasmonic function and hence for designing innovative solar energy conversion platforms. Here, we present a rational synthesis strategy for the realization of plasmonic metal-semiconductor heteronanocrystals with intended configurations through the site-selective overgrowth of semiconductor Cu2O on desired sites of anisotropic Au nanocrystals. Both the exploitation of structural characteristics of Au nanocrystals and the selective stabilization of their surfaces are keys to the construction of heteronanocrystals with a specific configuration. Our approach can provide an opportunity to precisely explore the link between the solar energy conversion efficiency and the structure of heteronanocrystals as well as to obtain important insights into the underpinning mechanism. Heteronanocrystals produced by Cu2O overgrowth preferentially on the multiple high-curvature sites of Au nanocrystals exhibited prominent photocatalytic hydrogen production activity due to efficient charge separation by strong plasmon excitation at the Au-Cu2O interface and subsequent sustainable hot electron transfer from Au to Cu2O.

Ultrathin Free-Standing Ternary-Alloy Nanosheets.

A synthesis strategy for the preparation of ultrathin free-standing ternary-alloy nanosheets is reported. Ultrathin Pd-Pt-Ag nanosheets with a thickness of approximately 3 nm were successfully prepared by co-reduction of the metal precursors in an appropriate molar ratio in the presence of CO. Both the presence of CO and the interplay between the constituent metals provide fine control over the anisotropic two-dimensional growth of the ternary-alloy nanostructure. The prepared Pd-Pt-Ag nanosheets were superior catalysts of ethanol electrooxidation owing to their specific structural and compositional characteristics. This approach will pave the way for the design of multicomponent 2D nanomaterials with unprecedented functions.

Shape-dependent adhesion and friction of Au nanoparticles probed with atomic force microscopy.

The relation between surface structure and friction and adhesion is a long-standing question in tribology. Tuning the surface structure of the exposed facets of metal nanoparticles is enabled by shape control. We investigated the effect of the shape of Au nanoparticles on friction and adhesion. Two nanoparticle systems, cubic nanoparticles with a low-index (100) surface and hexoctahedral nanoparticles with a high-index (321) surface, were used as model nanoparticle surfaces. Atomic force microscopy was used to probe the nanoscale friction and adhesion on the nanoparticle surface. Before removing the capping layers, the friction results include contributions from both the geometric factor and the presence of capping layers. After removing the capping layers, we can see the exclusive effect of the surface atomic structure while the geometric effect is maintained. We found that after removing the capping layer, the cubic Au nanoparticles exhibited higher adhesion and friction, compared with cubes capped with layers covering 25% and 70%, respectively. On the other hand, the adhesion and friction of hexoctahedral Au nanoparticles decreased after removing the capping layers, compared with nanoparticles with capping layers. The difference in adhesion and friction forces between the bare Au surfaces and Au nanoparticles with capping layers cannot be explained by geometric factors, such as the slope of the nanoparticle surfaces. The higher adhesion and friction forces on cubic nanoparticles after removing the capping layers is associated with the atomic structure of (100) and (321) (i.e., the flat (100) surfaces of the cubic nanoparticles have a larger contact area, compared with the rough (321) surfaces of the hexoctahedral nanoparticles). This study implies an intrinsic relation between atomic structure and nanomechanical properties, with potential applications for controlling nanoscale friction and adhesion via colloid chemistry.

Microgravity Separation of Alginate Empty Capsules from Encapsulated Pancreatic Islets Using a Microfluidic System.

Although microencapsulated pancreatic islets have merits, such as ease of transplantation, viability and functionality improvement, and immune protection in vivo, the co-production of alginate empty capsules during the encapsulation of islets with alginate makes them unusable for biomedical application. In previous research, the removal of empty alginate capsules with high yield was achieved using density-gradient centrifugation. Here, we report advanced microgravity-based separation techniques in a microfluidic format for alginate empty capsules. The optimal separation conditions were mathematically evaluated using Stokes' law and the separation of the encapsulation product was accomplished. A microfluidic chip was designed with two inlets and two outlets at different elevations to mimic the vertical percoll gradient in density-gradient centrifugation. The separation of alginate empty capsules using microgravitational force resulted in effective separation of encapsulated islets from alginate empty capsules with more than 70% efficiency. Moreover, no loss of encapsulated islets was expected because the process is a one-pot separation, unlike the previous method. This type of microgravitational particle separation could be used both for the fractionization of heterogeneous encapsulated cells and to remove empty capsules.

Universal sulfide-assisted synthesis of M-Ag heterodimers (M = Pd, Au, Pt) as efficient platforms for fabricating metal-semiconductor heteronanostructures.

We report a universal sulfide-assisted synthesis strategy to prepare dumbbell-like M-Ag heterodimers (M = Pd, Au, Pt). Sulfide ions can give fine control over the reaction kinetics of Ag precursors, resulting in the anisotropic overgrowth of Ag to realize the dumbbell-like heterodimers irrespective of the surface facets or components of the M domain. The M-Ag heterodimers were facilely transformed to M-Ag2S heterodimers via a simple sulfidation reaction. This study provides a versatile approach to realizing not only metal-metal heterodimers but also semiconductor-metal heterodimers and will pave the way for designing heteronanostructures with unprecedented morphologies and functions.

Cytoprotective alginate/polydopamine core/shell microcapsules in microbial encapsulation.

Chemical encapsulation of microbes in threedimensional polymeric microcapsules promises various applications, such as cell therapy and biosensors, and provides a basic platform for studying microbial communications. However, the cytoprotection of microbes in the microcapsules against external aggressors has been a major challenge in the field of microbial microencapsulation, because ionotropic hydrogels widely used for microencapsulation swell uncontrollably, and are physicochemically labile. Herein, we developed a simple polydopamine coating for obtaining cytoprotective capability of the alginate capsule that encapsulated Saccharomyces cerevisiae. The resulting alginate/ polydopamine core/shell capsule was mechanically tough, prevented gel swelling and cell leakage, and increased resistance against enzymatic attack and UV-C irradiation. We believe that this multifunctional core/shell structure will provide a practical tool for manipulating microorganisms inside the microcapsules.

Cell-based dose responses from open-well microchambers.

Cell-based assays play a critical role in discovery of new drugs and facilitating research in cancer, immunology, and stem cells. Conventionally, they are performed in Petri dishes, tubes, or well plates, using milliliters of reagents and thousands of cells to obtain one data point. Here, we are introducing a new platform to realize cell-based assay capable of increased throughput and greater sensitivity with a limited number of cells. We integrated an array of open-well microchambers into a gradient generation system. Consequently, cell-based dose responses were examined with a single device. We measured IC50 values of three cytotoxic chemicals, Triton X-100, H2O2, and cadmium chloride, as model compounds. The present system is highly suitable for the discovery of new drugs and studying the effect of chemicals on cell viability or mortality with limited samples and cells.