Helically aligned fused carbon hollow nanospheres with chiral discrimination ability.

While the functions of carbon materials with precisely controlled nanostructures have been reported in many studies, their chiral discriminating abilities have not been reported yet. Herein, chiral discrimination is achieved using helical carbon materials devoid of chiral attachments. A Fe3O4 nanoparticle template with ethyl cellulose (carbon source) is self-assembled on dispersed multiwalled carbon nanotubes (MWCNTs) fixed in a lamellar structure, with helical nanoparticle alignment induced by the addition of a binaphthyl derivative. Carbonization followed by template removal produces helically aligned fused carbon hollow nanospheres (CHNSs) with no chiral molecules left. Helicity is confirmed using vacuum-ultraviolet circular dichroism spectroscopy. Chiral discrimination, as revealed by the electrochemical reactions of binaphthol and a chiral ferrocene derivative in aqueous and nonaqueous electrolytes, respectively, is attributable to the chiral space formed between the CHNS and MWCNT surfaces.

Microbial community composition in iron deposits and manganese crusts formed in riverine environments around the Aso area in Japan.

The Kurokawa river flowing through the Aso Caldera in Southwest Japan is influenced by groundwater containing high concentration of dissolved metals (Fe2+ and Mn2+) and is associated with orange deposits in the upstream and thick black crusts on the wall of artificial waterway tunnel with several km lengths in the midstream regions. X-ray fluorescence analysis revealed that the orange deposits contained up to 34.4% Fe and black crusts comprised up to 25.4% and 10.6% Mn and Fe, respectively. Although naturally occurring Mn-oxides and crusts are considered biogenic in pH-neutral freshwater environments, the whole microbial community in Mn crust and their contribution to Mn crust formation in these environments remain unclear. High-throughput molecular sequencing for bacteria and eukaryotes including fungi revealed black Mn crusts had a high abundance of Sphingomonas, Hyphomicrobium, Bacillus, Pseudomonas, and Mortierella, previously reported genera including several species with Mn-oxidizing activity in Mn crusts or nodules of other marine and freshwater environments. In addition, one bacterial isolate and one fungal isolate with Mn-oxidizing activity were obtained from black Mn crust. These results suggest that multiple Mn-oxidizing bacteria including Pseudomonas and fungi are involved in Mn crust formation on the wall of dark waterway tunnel in the oligotrophic environment of the Kurokawa river.

Helical Pore Alignment on Cylindrical Carbon.

Interest in chiral substances has mainly focused on the substances themselves, but not on the accompanying space, especially regarding the pore alignment. As a method to form both the chiral substance and the accompanying space, cylindrical self-assembly of uniform polystyrene nanoparticles with fructose is carried out in the presence of both carbon and sodium alginate, which is followed by heat treatment in an inert atmosphere. The carbonization generates fructose-derived honeycomb-like carbon walls with helically aligned nanopores left after the polystyrene decomposition. The diffuse reflectance circular dichroism measurements give peaks with opposite signs for the d- and l-fructose-derived cylindrical carbons. Circularly polarized light sensitivity in transient photoconductivity is confirmed apparently in the carbon-based helical structures. This sensitivity as well as straightforward formation of composites with another component to give helicity shows potential applications of the helically aligned pores.

Concurrent nanoscale surface etching and SnO2 loading of carbon fibers for vanadium ion redox enhancement.

Facile and efficient methods to prepare active electrodes for redox reactions of electrolyte ions are required to produce efficient and low-cost redox flow batteries (RFBs). Carbon-fiber electrodes are widely used in various types of RFBs and surface oxidation is commonly performed to enhance the redox reactions, although it is not necessarily efficient. Quite recently, a technique for nanoscale and uniform surface etching of the carbon fiber surface was developed and a significant enhancement of the negative electrode reaction of vanadium redox flow batteries was attained, although the enhancement was limited to the positive electrode reaction. In this study, we attempted to obtain an additional enhancement effect of metal-oxide nanoparticles without the need for further processing steps. A coating with carbonaceous thin films was obtained coating by sublimation, deposition, and pyrolysis of tin(II) phthalocyanine (SnPc) on a carbon fiber surface in a single heat-treatment step. The subsequent thermal oxidation concurrently achieved nanoscale surface etching and loading with SnO2 nanoparticles. The nanoscale-etched and SnO2-loaded surface was characterized by field-emission scanning electron microscopy (FESEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The activity for the vanadium ion redox reactions was evaluated by cyclic voltammetry (CV) to demonstrate the enhancement of both the positive and negative electrode reactions. A full cell test of the vanadium redox flow battery (VRFB) showed a significant decrease of the overpotential and a stable cycling performance. A facile and efficient technique based on the nanoscale processing of the carbon fiber surface was presented to substantially enhance the activity for the redox reactions in redox flow batteries.

Changes in radiocesium contamination from Fukushima in foliar parts of 10 common tree species in Japan between 2011 and 2013.

Yearly changes in radiocesium ((137)Cs) contamination, primarily due to the Fukushima accident of March 2011, were observed in the foliar parts of 10 common woody species in Japan (Chamaecyparis obtusa, Cedrus deodara, Pinus densiflora, Cryptomeria japonica, Phyllostachys pubescens, Cinnamomum camphora, Metasequoia glyptostroboides, Prunus × yedoensis, Acer buergerianum, and Aesculus hippocastanum). The samples were obtained from Abiko (approximately 200 km SSW of the Fukushima Dai-ichi Nuclear Power Plant) during each growing season between 2011 and 2013, and the foliar parts were examined based on their year of expansion and location in each trees. The radiocesium concentrations generally decreased with time; however, the concentrations and rates of decrease varied among species, age of foliar parts, and locations. The radiocesium concentrations in the 2012 current-year foliar parts were 29%-220% of those from 2011, while those from 2013 fell to between 14% and 42% of the 2011 values. The net decontamination in the foliage was higher in evergreen species than in deciduous species. The radiocesium concentrations in the upper foliar parts were higher than those in the lower parts particularly in C. japonica. In addition, the radiocesium concentrations were higher in the current-year foliar parts than in the 1-year-old foliar parts, particularly in 2013. Thus, the influence of the direct deposition of the fallout was reduced with time, and the translocation ability of radiocesium from old to new tissues became more influential. Similar to the behavior of potassium in trees, Cs redistribution probably occurred primarily due to internal nutrient translocation mechanisms.

Radiocesium contaminations of 20 wood species and the corresponding gamma-ray dose rates around the canopies at 5 months after the Fukushima nuclear power plant accident.

Radiocesium ((134)Cs + (137)Cs) deposition from the Fukushima nuclear power plant accident was measured in 20 woody plants (12 evergreen and 8 deciduous species) grown in Abiko (approximately 200 km SSW from the NPP). Leaves (needles) and twigs were sampled from each of three foliar positions (top, middle, and bottom) in the plant canopy in early August 2011. At the time, soils around the plants were also sampled, and gamma radiation dose rates were measured at each sampling position. The average radiocesium activity in the observed leaves of the evergreen species was 7.7 times that in the leaves of the deciduous species. Among the observed evergreen coniferous species, the activity in pre-fallout-expanded leaves was 2.4 times that in the post-fallout-expanded leaves. Notably, a distinct variation in the activity among the evergreen coniferous species could be observed for the post-fallout-expanded leaves but not for the pre-fallout-expanded leaves. Although these differences depend on whether the leaves had expanded at the time of the fallout, it is probable that a considerable amount of radiocesium was translocated to newly developed leaves at a species-specific rate. In addition, it was demonstrated that dose rates around woody plants were not consistent with the prevailing prediction that general dose rates correspondingly decrease with monitoring height from the ground. Thus, the dose rates in the top foliar layer of the deciduous species decreased more than predicted, whereas those in the top foliar layer of the coniferous species did not decrease. This may be due to differences in the balance between the attenuation resulting from a shielding effect of the plant bodies and the higher radiocesium accumulation in the leaves.

Cross-laboratory experimental study of non-noble-metal electrocatalysts for the oxygen reduction reaction.

Nine non-noble-metal catalysts (NNMCs) from five different laboratories were investigated for the catalysis of O(2) electroreduction in an acidic medium. The catalyst precursors were synthesized by wet impregnation, planetary ball milling, a foaming-agent technique, or a templating method. All catalyst precursors were subjected to one or more heat treatments at 700-1050 degrees C in an inert or reactive atmosphere. These catalysts underwent an identical set of electrochemical characterizations, including rotating-disk-electrode and polymer-electrolyte membrane fuel cell (PEMFC) tests and voltammetry under N(2). Ex situ characterization was comprised of X-ray photoelectron spectroscopy, neutron activation analysis, scanning electron microscopy, and N(2) adsorption and its analysis with an advanced model for carbonaceous powders. In PEMFC, several NNMCs display mass activities of 10-20 A g(-1) at 0.8 V versus a reversible hydrogen electrode, and one shows 80 A g(-1). The latter value corresponds to a volumetric activity of 19 A cm(-3) under reference conditions and represents one-seventh of the target defined by the U.S. Department of Energy for 2010 (130 A cm(-3)). The activity of all NNMCs is mainly governed by the microporous surface area, and active sites seem to be hosted in pore sizes of 5-15 A. The nitrogen and metal (iron or cobalt) seem to be present in sufficient amounts in the NNMCs and do not limit activity. The paper discusses probable directions for synthesizing more active NNMCs. This could be achieved through multiple pyrolysis steps, ball-milling steps, and control of the powder morphology by the addition of foaming agents and/or sulfur.