Mononuclear nonheme ferric-peroxo complex in aldehyde deformylation

A mononuclear nonheme ferric-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [(TMC)Fe(III)-O2]+, was prepared and used in mechanistic studies of aldehyde deformylation; a catalytic aldehyde deformylation by a nonheme iron(II) complex, [Fe(II)(TMC)]2+, and molecular oxygen is reported as well.     

Construction of a 2,6-difunctionalized 2-methyl-2H-1-benzopyran library by using a solid-phase synthesis protocol

[reaction: see text] A library containing 1200 analogues of 2,6-difunctionalized 2-methyl-2H-1-benzopyran was constructed by using a solid-phase synthesis protocol. Polymer-bound 6-amido-, 6-sulfonamido-, and 6-uredo-functionalized 2-hydroxymethyl-2-methylbenzopyrans 10 were prepared as part of a first-generation diversification step by employing reactions of respective acid halides, sulfonyl chlorides, and isocyanates with the amine precursor 7. Transformations of the resin-bound intermediates 10 by reactions with alkyl and acid halides were then used to produce a diverse series of 2,6-difunctionalized 2-methyl-2H-1-benzopyran analogues 12 and 14.     

First preparation of biotinylated gradient polyethylene surface to bind photoactive caged streptavidin

A gradient polyethylene (PE) surface was created through corona treatment, in which the corona power increased along the 5 cm length of the PE. The gradient surface was treated with polyethyleneimine and then biotin. Fluorescein-conjugated streptavidin (SAV) caged within 5-carboxymethoxy-2-nitrobenzyl (CMNB) adsorbed onto the biotinylated gradient PE surface following molecular recognition principles. Photoirradiation decomposed the CMNB cage and allowed the fluorescein-conjugated SAV to fluoresce, the intensity of which increased gradually along the PE surface.     

Effects of gamma irradiation on the yields of volatile extracts of Angelica gigas Nakai

The study was carried out to determine the effects of gamma irradiation on the volatile flavor components including essential oils, of Angelica gigas Nakai. The volatile organic compounds from non- and irradiated A. gigas Nakai at doses of 1, 3, 5, 10 and 20 kGy were extracted by a simultaneous steam distillation and extraction (SDE) method and identified by GC/MS analysis. A total of 116 compounds were identified and quantified from non- and irradiated A. gigas Nakai. The major volatile compounds were identified 2,4,6-trimethyl heptane, α-pinene, camphene, α-limonene, β-eudesmol, α-murrolene and sphatulenol. Among these compounds, the amount of essential oils in non-irradiated sample were 77.13%, and the irradiated samples at doses of 1, 3, 5, 10 and 20 kGy were 84.98%, 83.70%, 83.94%, 82.84% and 82.58%, respectively. Oxygenated terpenes such as β-eudesmol, α-eudesmol, and verbenone were increased after irradiation but did not correlate with the irradiation dose. The yields of active substances such as essential oil were increased after irradiation; however, the yields of essential oils and the irradiation dose were not correlated. Thus, the profile of composition volatiles of A. gigas Nakai did not change with irradiation.     

Electrolytic production of metallic uranium from U3O8 in a 20-kg batch scale reactor</p> </p>

Summary The electrolytic reduction of U₃O₈ powder was carried out using LiCl-Li₂O molten salt in a 20-kg U₃O₈ batch cell to verify the feasibility of the process. As the current passes the cell, the decomposition of Li₂O and the reduction of U₃O₈ occur simultaneously in a cathode assembly and oxygen gas evolvs at the anode. The results from a 20-kg U₃O₈ scale cell were compared with data obtained from a bench scale cell. The results suggest a successful demonstration of this process, exhibiting a reduction conversion of U₃O₈ of more than 99% in a batch.</p> </p>     

Microfluidics: from dynamic lattices to periodic arrays of polymer disks

We used coupling of flow and geometric confinement to assemble emulsion droplets in two-dimensional gliding lattices with a high degree of order and symmetry. Highly monodisperse discoid droplets with circular shapes were generated in a microfluidic flow-focusing device. Originally, close-packed lattices formed from these circular discoid droplets. Progressive confinement led to the gradual deformation of the circular disks: first, they elongated in the direction parallel to the direction of flow and then transformed into hexagons. Assembly driven by the combination of flow and confinement also allowed for the formation of lattices from droplets with a bimodal size distribution. We used photopolymerization of the monomer droplets to trap the lattice structure in the solid state and produce highly periodic arrays of solid polymer disks.     

Reduction of the IgE-binding ability and maintenance of immunogenicity of gamma-irradiated Dermatophagoides farinae

House dust mites, Dermatophagoides farinae (DF) and Dermatophagoides pteronyssinus, are major allergens in the most common indoor allergen and are important risk factor for asthma. The modified antigen has been studied to treat allergic disorder. This study was carried out to measure possibility of modified allergen using gamma irradiation to treat allergy such as asthma. DF solutions (2 mg/ml) as target allergen were irradiated with Co-60 at 50 and 100 kGy. Conformational alternation of irradiated DF was observed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). Levels of anti-irradiated DF mouse IgGs (sub-isotypes) against intact DF were measured similar to that of anti-intact DF IgGs. The binding abilities of house dust mite-allergic patients’ IgE were reduced depending on radiation dose, and irradiation could inhibit the binding ability of patients’ IgE more than 40%. This study has shown that the binding ability of IgE was reduced by conformational alteration by irradiation and the irradiated DF had epitopes capable to induce immunogeniciy.     

Tuning chirality of single-wall carbon nanotubes by selective etching with carbon dioxide

CO2 molecule chemisorbs selectively on the zigzag tube edge without an activation barrier, whereas it physisorbs on the armchair edge of nanotubes. In addition, carbon nanotubes can be etched by an adsorbed oxygen atom of CO2 molecule. From our results, we suggest a selective etching mechanism for tuning the chirality of the mass-produced carbon nanotubes.     

Characteristics of major dioxin/furan congeners in melted slag of ash from municipal solid waste incinerators

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in slag of fly ash from three municipal solid waste (MSW) incinerators were analyzed to observe any changes in characteristics and distribution of their congeners by melting process. Actual concentration and Toxic Equivalent (TEQ) concentration profiles of 17 major congeners of PCDDs/PCDFs for gas, fly ash and melted slag were compared. The distributions of PCDDs/PCDFs in different streams macroscopically showed similarities with the generally known profiles for emission gas from a municipal waste incinerator. The total concentrations of PCDDs/PCDFs in off-gas and fly ash have been known to be a function of incineration conditions and of air pollution control device utilization; however, their normalized distributions were independent of such conditions. The concentrations of PCDDs/PCDFs in the melted slag of fly ash were not related to the concentrations of PCDDs/PCDFs congeners in fly ash but were rather a function of the melting furnace type and operation. The total amount of PCDDs/PCDFs in the melted slag of fly ash contained almost 150–27,000 times less dioxin than that in fly ash, however, the TEQ of dioxin in the slag was reduced by 435–43,500 times, which could enable them to be utilized as recycled construction materials. In normalized TEQ concentration profiles of 17 congeners of PCDDs/PCDFs, the ratio of PCDFs to PCDDs changed from 1.32 to 2.19 by melting, which showed relatively higher portion of furans left in melted slag than those in fly ash. By comparing reduction ratios of different congeners, PCDDs (dioxins) were relatively easier to destruct than PCDFs (furans) during melting process. The most difficult congener to destruct could be octa-chlorinated dibenzofuran (OCDF) among major congeners. For slag cooling methods, dioxin concentration in TEQ of slow cooled slag by air was four times higher than that of fast cooled slag by water. Thus cooling by water is more appropriate with the added beneficial effect of producing granules/particles, which can be utilized as roadbed materials.