Ammonia Oxidation Enhanced by Photopotential Generated by Plasmonic Excitation of a Bimetallic Electrocatalyst

We study how visible light influences the activity of an electrocatalyst composed of Au and Pt nanoparticles. The bimetallic composition imparts a dual functionality: the Pt component catalyzes the electrochemical oxidation of ammonia to liberate hydrogen and the Au component absorbs visible light by the excitation of localized surface plasmon resonances. Under visible-light excitation, this catalyst exhibits enhanced electrochemical ammonia oxidation kinetics, outperforming previously reported electrochemical schemes. We trace the enhancement to a photochemical potential resulting from electron–hole carriers generated in the electrocatalyst by plasmonic excitation. The photopotential responsible for enhanced kinetics scales linearly with the light intensity—a general design principle for eliciting superlative photoelectrochemical performance from catalysts comprised of plasmonic metals or hybrids. We also determine a photochemical conversion coefficient.     

Assessing the role of chemical components in cellular responses to atmospheric particle matter (PM) through chemical fractionation of PM extracts

In order to further our understanding of the influence of chemical components and ultimately specific sources of atmospheric particulate matter (PM) on pro-inflammatory and other adverse cellular responses, we promulgate and apply a suite of chemical fractionation tools to aqueous aerosol extracts of PM samples for analysis in toxicity assays. We illustrate the approach with a study that used water extracts of quasi-ultrafine PM (PM_0.25) collected in the Los Angeles Basin. Filtered PM extracts were fractionated using Chelex, a weak anion exchanger diethylaminoethyl (DEAE), a strong anion exchanger (SAX), and a hydrophobic C18 resin, as well as by desferrioxamine (DFO) complexation that binds iron. The fractionated extracts were then analyzed using high-resolution sector field inductively coupled plasma mass spectrometry (SF-ICPMS) to determine elemental composition. Cellular responses to the fractionated extracts were probed in an in vitro rat alveolar macrophages model with measurement of reactive oxygen species (ROS) production and the cytokine tumor necrosis factor-α (TNF-α). The DFO treatment that chelates iron was very effective at reducing the cellular ROS activity but had only a small impact on the TNF-α production. In contrast, the hydrophobic C18 resin treatment had a small impact on the cellular ROS activity but significantly reduced the TNF-α production. The use of statistical methods to integrate the results across all treatments led to the conclusion that sufficient iron must be present to participate in the chemistry needed for ROS activity, but the amount of ROS activity is not proportional to the iron solution concentration. ROS activity was found to be most related to cationic mono- and divalent metals (i.e., Mn and Ni) and oxyanions (i.e., Mo and V). Although the TNF-α production was not significantly affected by the chelexation of iron, it was greatly impacted by the removal of organics with the C18 resin and all other metal removal methods, suggesting that iron is not a critical pathway leading to TNF-α production, but a wide range of soluble metals and organic compounds in particulate matter play a role. Although the results are specific to the Los Angeles Basin, where the samples used in the study were collected, the method employed in the study can be widely employed to study the role of components of particulate matter in in vitro or in vivo assays.     

Development of a mobile radon calibration system at KRISS

Journal of Radioanalytical and Nuclear Chemistry - A mobile radon calibration system was developed with a high-sensitivity radon detector, a movable calibration chamber, and a 226Ra solid source at...     

Hybrid Curdlan Poly(γ ‐Glutamic Acid) Nanoassembly for Immune Modulation in Macrophage

A nanoformulation composed of curdlan, a linear polysaccharide of 1,3‐β‐linked d ‐glucose units, hydrogen bonded to poly(γ ‐glutamic acid) (PGA), was developed to stimulate macrophage. Curdlan/PGA nanoparticles (C‐NP) are formulated by physically blending curdlan (0.2 mg mL^?1 in 0.4 m NaOH) with PGA (0.8 mg mL^?1). Forster resonance energy transfer (FRET) analysis demonstrates a heterospecies interpolymer complex formed between curdlan and PGA. The ¹H‐NMR spectra display significant peak broadening as well as downfield chemical shifts of the hydroxyl proton resonances of curdlan, indicating potential intermolecular hydrogen bonding interactions. In addition, the cross peaks in ¹H‐¹H 2D‐NOESY suggest intermolecular associations between the OH‐2/OH‐4 hydroxyl groups of curdlan and the carboxylic‐/amide‐groups of PGA via hydrogen bonding. Intracellular uptake of C‐NP occurs over time in human monocyte‐derived macrophage (MDM). Furthermore, C‐NP nanoparticles dose‐dependently increase gene expression for TNF‐α, IL‐6, and IL‐8 at 24 h in MDM. C‐NP nanoparticles also stimulate the release of IL‐lβ, MCP‐1, TNF‐α, IL‐8, IL‐12p70, IL‐17, IL‐18, and IL‐23 from MDM. Overall, this is the first demonstration of a simplistic nanoformulation formed by hydrogen bonding between curdlan and PGA that modulates cytokine gene expression and release of cytokines from MDM.     

Alkoxide-Promoted Selective Hydroboration of N-Heteroarenes: Pivotal Roles of in situ Generated BH3 in the Dearomatization Process

While numerous organo(metallic)catalyst systems were documented for dearomative hydroboration of N-aromatics, alkoxide base catalysts have not been disclosed thus far. Described herein is the first example of alkoxide-catalyzed hydroboration of N-heteroaromatics including pyridines, providing a broad range of reduced N-heterocycles with high efficiency and selectivity. Mechanistic studies revealed an unprecedented counterintuitive dearomatization pathway, in which 1) pyridine-BH₃ adducts undergo a hydride attack by alkoxyborohydrides, 2) in situ generated BH₃ serves as a catalytic promoter, and 3) 1,4-dihydropyridyl borohydride is in a predominant resting state.     

Aggregation of reduced graphene oxide and its nanohybrids with magnetite and elemental silver under environmentally relevant conditions

Journal of Nanoparticle Research - Utilizing solar energy for hydrogen evolution is a great challenge for its insufficient visible-light power conversion. In this paper, we report a facile...     

Investigation on the stress behavior of cellulose acetate and the development of highly moisture‐resistant optical films for display devices

An optical film with high optical anisotropy was prepared by the stretching of a cellulose acetate film and the consequential orienting of a retardation‐enhancing additive. The change in retardation in response to moisture absorption was explored and it was found that the degree of the retardation variation is strongly related to the stretching temperature. Stress generated by the stretching and its relaxation was systematically investigated to elucidate the effect of stretching temperature on the irreversible change in retardation upon moisture absorption. The results show that the magnitude of releasable stress plays an important role in controlling changes in optical properties. In addition, the difference in the deformation behavior between glassy and rubbery states should be taken into account in the development of a moisture‐resistant optical film. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1470–1478     

Readily Accessible and Predictable Naphthalene‐Based Two‐Photon Fluorophore with Full Visible‐Color Coverage

Herein we report 22 acedan‐derived, two‐photon fluorophores with synthetic feasibility and full coverage of visible wavelength emission. The emission wavelengths were predicted by computational analysis, which enabled us to visualize multicolor images by two‐photon excitation with single wavelength, and to design a turn‐on, two‐photon fluorescence sensor for endogenous H₂O₂ in Raw 264.7 macrophage and rat brain hippocampus ex vivo.     

Influence of growth temperature and post-annealing on an n-ZnO/p-GaN heterojunction diode

We report on an n-ZnO/p-GaN heterojunction diode fabricated from zinc oxide (ZnO) films at various growth temperatures (450, 500, 550, and 600 °C) by RF sputtering. The films were subsequently annealed at 700 °C in N₂ ambient. To investigate the influence of the growth temperature of n-ZnO films, the microstructural, optical, and electrical properties were measured using scanning electron microscopy (SEM), X-ray diffraction (XRD), photoluminescence (PL), and Hall measurements. The XRD pattern showed the preferred orientation along the c-axis (002) regardless of growth temperature. The PL spectra showed a dominant sharp near-band-edge (NBE) emission. Current–voltage (I–V) curves showed excellent rectification behavior. The turn-on voltage of the diode was observed to be 3.2 V for the films produced at 500 °C. The ideality factor of ZnO film was observed to be 1.37, which showed the best performance of the diode.