Enhancement of keratinocyte survival and migration elicited by interleukin 24 upregulation in dermal microvascular endothelium upon welding-fume exposure.

Occupational exposure to welding fumes constitutes a serious health concern. Although the effects of fumes on the respiratory tract have been investigated, few apparent reports were published on their effects on the skin. The purpose of this study was to investigate the effects of exposure to welding fumes on skin cells, focusing on interleukin-24 (IL-24), a cytokine involved in the pathophysiology of skin conditions, such as atopic dermatitis and psoriasis. Treatment with welding fumes increased IL-24 expression and production levels in human dermal microvascular endothelial cells (HDMEC) which were higher than that in normal human epidermal keratinocytes. IL-24 levels in Trolox and deferoxamine markedly suppressed welding fume-induced IL-24 expression in HDMEC, indicating that oxidative stress may be involved in this cytokine expression. IL-24 released from HDMEC protected keratinocytes from welding fume-induced damage and enhanced keratinocyte migration. Serum IL-24 was higher in welding workers than in general subjects and was positively correlated with elevated serum levels of 8-hydroxy-2'-deoxyguanosine, an oxidative stress marker. In summary, welding fumes enhanced IL-24 expression in HDMEC, stimulating keratinocyte survival and migration. IL-24 expression in endothelial cells may act as an adaptive response to welding-fume exposure in the skin.

Synthesis of 2-(Pyridin-2-yl)phenols and 2-(Pyridin-2-yl)anilines.

Herein, we report a new synthetic strategy for 2-(pyridin-2-yl)phenols and 2-(pyridin-2-yl)anilines catalyzed by a Pd/C-ethylene system. The starting materials, 2-(pyridin-2-yl)cyclohexan-1-ones, can be easily prepared by the reaction of substituted pyridine N-oxide and cyclohexanones. The most useful feature of this method is that both 2-(pyridin-2-yl)phenols and 2-(pyridin-2-yl)anilines are easily synthesized independently using the same compound as a starting material, simply by adding or not adding a nitrogen source.

Sensitizer-Free Photochemical Regeneration of Benzimidazoline Organohydride.

Organohydrides are an important class of organic compounds that can provide hydride anions for chemical and biochemical reactions, as demonstrated by reduced nicotinamide adenine dinucleotides serving as important natural redox cofactors. The coupling of hydride transfer from the organohydride to the substrate and subsequent regeneration of the organohydride from its oxidized form can realize organohydride-catalyzed reduction reactions. Depending on the structure of the organohydride, its hydridicity and ease of regeneration vary. Benzimidazoline (BIH) is one of the strongest synthetic C-H hydride donors; however, its reductive regeneration requires highly reducing conditions. In this study, we synthesized various oxidized and reduced forms of BIH derivatives with aryl groups at the 2-position and investigated their photophysical and electrochemical properties. 4-(Dimethylamino)phenyl-substituted BIH exhibited salient red-shifted absorption compared with other synthesized BIH derivatives, and visible-light-driven regeneration without using an external photosensitizer was achieved. This knowledge has significant implications for the future development of solar-energy-based catalytic photoreduction technologies that utilize organohydride regeneration strategies.

Dithiothreitol-Measured Oxidative Potential of Reference Materials of Mineral Dust: Implications for the Toxicity of Mineral Dust Aerosols in the Atmosphere.

Oxidative stress is a mechanism that might raise the toxicity of mineral dust aerosols. We evaluated the oxidative potential (OP) of four reference materials (RMs) of mineral dusts using dithiothreitol assay. The OP of the water-soluble fraction of the dust RMs accounts for 40%-70% of the OP of the total fraction. The values of total and water-soluble OP normalized by the surface area of insoluble particles showed agreement among the different dust RMs. The surface area of insoluble dust particles was therefore inferred as an important factor affecting the OP of mineral dust. Using the relation between total OP and the surface area of insoluble particles of the dust RMs, we estimated the total OPs of fine and coarse atmospheric mineral dust aerosols assuming a typical particle size distribution of Asian dust aerosols observed in Japan. Mass-normalized total OPs were estimated at 44 and 23 pmol min-1 µg-1 for fine and coarse atmospheric mineral dust particles. They closely approximate the values observed for urban aerosols in Japan, which suggests that mineral dust plume advection can lead to a marked increase in human exposure to redox-active aerosols, even far downwind from mineral dust source regions.

One-Pot Synthesis of 3-Substiuted Indoles from 2-(2-Nitro-1-phenylethyl)cyclohexanone Derivatives.

Herein, a one-pot synthesis of 3-substituted indoles from 2-(2-nitro-1-phenylethyl)cyclohexanone derivatives catalyzed by Pd/C is reported. The starting materials can be easily prepared by the reaction of substituted ketones and nitroalkenes. The facile experimental procedure comprises the treatment of 2-(2-nitro-1-phenylethyl)cyclohexanone derivatives with H2 as a hydrogen donor in the presence of 10 mol % Pd/C. Subsequently, the exchange of H2 with CH2═CH2 as a hydrogen acceptor affords a variety of 3-substituted indoles in high yields. The formation of intermediate nitrones is essential for a smooth reaction.

Direct imaging and astrometric detection of a gas giant planet orbiting an accelerating star.

Direct imaging of gas giant exoplanets provides information on their atmospheres and the architectures of planetary systems. However, few planets have been detected in blind surveys with direct imaging. Using astrometry from the Gaia and Hipparcos spacecraft, we identified dynamical evidence for a gas giant planet around the nearby star HIP 99770. We confirmed the detection of this planet with direct imaging using the Subaru Coronagraphic Extreme Adaptive Optics instrument. The planet, HIP 99770 b, orbits 17 astronomical units from its host star, receiving an amount of light similar to that reaching Jupiter. Its dynamical mass is 13.9 to 16.1 Jupiter masses. The planet-to-star mass ratio [(7 to 8) × 10-3] is similar to that of other directly imaged planets. The planet's atmospheric spectrum indicates an older, less cloudy analog of the previously imaged exoplanets around HR 8799.

Metal-free reduction of CO2 to formate using a photochemical organohydride-catalyst recycling strategy.

Increasing levels of CO2 in the atmosphere is a problem that must be urgently resolved if the rise in current global temperatures is to be slowed. Chemically reducing CO2 into compounds that are useful as energy sources and carbon-based materials could be helpful in this regard. However, for the CO2 reduction reaction (CO2RR) to be operational on a global scale, the catalyst system must: use only renewable energy, be built from abundantly available elements and not require high-energy reactants. Although light is an attractive renewable energy source, most existing CO2RR methods use electricity and many of the catalysts used are based on rare heavy metals. Here we present a transition-metal-free catalyst system that uses an organohydride catalyst based on benzimidazoline for the CO2RR that can be regenerated using a carbazole photosensitizer and visible light. The system is capable of producing formate with a turnover number exceeding 8,000 and generates no other reduced products (such as H2 and CO).

Assessing oxidative stress induction ability and oxidative potential of PM2.5 in cities in eastern and western Japan.

Oxidative stress is an important cause of respiratory diseases associated with exposure to PM2.5. Accordingly, acellular methods for assessing the oxidative potential (OP) of PM2.5 have been evaluated extensively for use as indicators of oxidative stress in living organisms. However, OP-based assessments only reflect the physicochemical properties of particles and do not consider particle-cell interactions. Therefore, to determine the potency of OP under various PM2.5 scenarios, oxidative stress induction ability (OSIA) assessments were performed using a cell-based method, the heme oxygenase-1 (HO-1) assay, and the findings were compared with OP measurements obtained using an acellular method, the dithiothreitol assay. For these assays, PM2.5 filter samples were collected in two cities in Japan. To quantitatively determine the relative contribution of the quantity of metals and subtypes of organic aerosols (OA) in PM2.5 to the OSIA and the OP, online measurements and offline chemical analysis were also performed. The findings showed a positive relationship between the OSIA and OP for water-extracted samples, confirming that the OP is generally well suited for use as an indicator of the OSIA. However, the correspondence between the two assays differed for samples with a high water-soluble (WS)-Pb content, which had a higher OSIA than would be expected from the OP of other samples. The results of reagent-solution experiments showed that the WS-Pb induced the OSIA, but not the OP, in 15-min reactions, suggesting a reason for the inconsistent relationship between the two assays across samples. Multiple linear regression analyses and reagent-solution experiments showed that WS transition metals and biomass burning OA accounted for approximately 30-40% and 50% of the total OSIA or the total OP of water-extracted PM2.5 samples, respectively. This is the first study to evaluate the association between cellular oxidative stress assessed by the HO-1 assay and the different subtypes of OA.

Origin of surface water in the Southern Ocean: Implications of soluble radionuclide distributions.

Concentration data of soluble radionuclides in the southern South Indian Ocean and Southern Ocean transition zone are rare or insufficient for the study of its current system. We examined the lateral surface variations in soluble natural (226Ra and 228Ra) and anthropogenic (134Cs and 137Cs) radionuclide activity concentrations in the surface waters in this area from November 2021 to March 2022. The surface distributions of 226Ra and 137Cs concentrations were classified into Subantarctic Mode Water-, Antarctic Intermediate Water-, and Upper Circumpolar Deep Water (UCDW)-dominated areas along latitudinal band (40°S-65°S, 110°E-120°E). Notably, the highest 226Ra concentrations occurred along the longitudinal band (60°S-65°S, 40°E-120°E). Significantly lower 137Cs concentrations in the Southern Ocean than those in surface waters in other global oceans were observed along with depletion of 228Ra. Additionally, 226Ra and 137Cs concentrations appeared to show small variations between eastern and western areas (2.5-3.0 mBq/L and 0.06-0.03 mBq/L, respectively). Lateral profiles in the Southern Ocean are governed by a large contribution from deep/old waters (e.g., UCDW), with a small effect from southward transport of Subantarctic Mode Water.

Furoxan Incorporation into C-H Bonds Enabling Nitrogen-Containing Functional Group Installation into the Same.

A C-C bond forming method was developed, whereby a furoxan ring is incorporated into various types of C-H bonds. The protocol not only offers a concise synthetic route to a variety of alkylated furoxan derivatives but also provides an efficient strategy for the insertion of various nitrogen-containing functional groups into C-H bonds via transformation of the resultant furoxan ring.

Borylfuroxans: Synthesis and Applications.

Herein we report the first synthesis of borylfuroxans via the reaction of sulfonylfuroxans with Lewis base-ligated boranes under radical conditions. As a synthetic application, the transformation of borylfuroxans to a range of 1,2-dioximes and their derivatives is demonstrated.

Regiodivergent Desymmetrization Reaction of meso-Azabicycloheptene Providing Two Enantioenriched Structural Isomers.

A novel catalytic asymmetric reaction is reported where the regiodivergent desymmetrisation of meso-azabicycloheptene via allylic oxidation using a single chiral copper catalyst produced two different, enantioenriched structural isomers in high optical purity starting from a single compound. The enantioselectivity of the two structurally isomeric compounds was enriched to >99.5% ee after derivatization.

Effects of ambient particulate matter on a reconstructed human corneal epithelium model.

We evaluated the effects of ambient particulate matter (PM) on the corneal epithelium using a reconstructed human corneal epithelium (HCE) model. We collected two PM size fractions [aerodynamic diameter smaller than 2.4 µm: PM0.3-2.4 and larger than 2.4 µm: PM>2.4] and exposed these tissues to PM concentrations of 1, 10, and 100 µg/mL for 24 h. After exposure, cell viability and interleukin (IL) IL-6 and IL-8 levels were determined, and haematoxylin and eosin and immunofluorescence staining of the zonula occludens-1 (ZO-1) were performed on tissue sections. In addition, the effects of a certified reference material of urban aerosols (UA; 100 µg/mL) were also examined as a reference. The viability of cells exposed to 100 µg/mL UA and PM>2.4 decreased to 76.2% ± 7.4 and 75.4% ± 16.1, respectively, whereas PM0.3-2.4 exposure had a limited effect on cell viability. These particles did not increase IL-6 and IL-8 levels significantly even though cell viability was decreased in 100 µg/mL UA and PM>2.4. ZO-1 expression was reduced in a dose-dependent manner in all groups. Reconstructed HCE could be used as an in vitro model to study the effects of environmental PM exposure on ocular surface cell viability and inflammation.

Synthesis of Substituted Anilines from Cyclohexanones Using Pd/C-Ethylene System and Its Application to Indole Synthesis.

The synthesis of anilines and indoles from cyclohexanones using a Pd/C-ethylene system is reported. A simple combination of NH4OAc and K2CO3 under nonaerobic conditions was found to be the most suitable to perform this reaction. Hydrogen transfer between cyclohexanone and ethylene generates the desired products. The reaction tolerates a variety of substitutions on the starting cyclohexanones.

Photocatalytic Reductive C-O Bond Cleavage of Alkyl Aryl Ethers by Using Carbazole Catalysts with Cesium Carbonate.

Methods to activate the relatively stable ether C-O bonds and convert them to other functional groups are desirable. One-electron reduction of ethers is a potentially promising route to cleave the C-O bond. However, owing to the highly negative redox potential of alkyl aryl ethers (Ered < -2.6 V vs SCE), this mode of ether C-O bond activation is challenging. Herein, we report the visible-light-induced photocatalytic cleavage of the alkyl aryl ether C-O bond using a carbazole-based organic photocatalyst (PC). Both benzylic and non-benzylic aryl ethers underwent C-O bond cleavage to form the corresponding phenol products. Addition of Cs2CO3 was beneficial, especially in reactions using a N-H carbazole PC. The reaction was proposed to occur via single-electron transfer (SET) from the excited-state carbazole to the substrate ether. Interaction of the N-H carbazole PC with Cs2CO3 via hydrogen bonding exists, which enables a deprotonation-assisted electron-transfer mechanism to operate. In addition, the Lewis acidic Cs cation interacts with the substrate alkyl aryl ether to activate it as an electron acceptor. The high reducing ability of the carbazole combined with the beneficial effects of Cs2CO3 made this otherwise formidable SET event possible.

Selective Synthesis of Some Aminosugars via Catalytic Aminohydroxylation of Protected 2,3-Unsaturated d-Gluco- and d-Galacto-2-hexenopyranosides.

The aminohydroxylation of methyl 4,6-di-O-(tert-butyldimethylsilyl)-2,3-unsaturated α-d-glucopyranoside proceeds in the presence of chloramine-T, OsO4 (4 mol %), (DHQ)2PHAL (5 mol %), and triethylbenzylammonium chloride (TEBAC) in both a stereoselective and a regioselective manner to produce protected methyl α-d-mannosamide as the sole product. In contrast, the reaction of methyl 2,3-unsaturated ß-d-galactopyranoside under the same conditions produced a mixture of regioisomers, although the stereochemistry was perfectly controlled. The regioisomeric ratio was dependent on the nature of the protecting group and the ligand used.

Synthesis and Synthetic Application of Chloro- and Bromofuroxans.

Furoxans are potentially useful heteroaromatic units in pharmaceuticals and agrichemicals. However, the applications for furoxan-based compounds have been hampered due to the underdevelopment of their synthetic methods. Herein, we report a new synthetic approach for the synthesis of chloro- and bromofuroxans. The starting materials were dichloro- and dibromofuroxans, and the substituents were directly introduced to the furoxan ring in a modular fashion. The synthesized monohalofuroxans served as substrates for the installation of a second substituent to prepare further functionalized furoxans.

Modular Synthesis of Carbon-Substituted Furoxans via Radical Addition Pathway. Useful Tool for Transformation of Aliphatic Carboxylic Acids Based on "Build-and-Scrap" Strategy.

Utilizing radical chemistry, a new general C-C bond formation on the furoxan ring was developed. By taking advantage of the lability of furoxans, a wide variety of transformation of the synthesized furoxans have been demonstrated. Thus, this developed methodology enabled not only the modular synthesis of furoxans but also short-step transformations of carboxylic acids to a broad range of functional groups.

9-Aryl-3-aminocarbazole as an Environment- and Stimuli-Sensitive Fluorogen and Applications in Lipid Droplet Imaging.

Environment-sensitive luminophoric molecules have played an important role in the fields of smart materials, sensing, and bioimaging. In this study, it was demonstrated that depending on the substituents, 9-aryl-3-aminocarbazoles can display aggregation-induced emission and solvatofluorochromism, and the operating mechanism was clarified. The application of these compounds to lipid droplet imaging and fluorescent probes for cysteamine was demonstrated.