Observation by an air-shower array in Tibet of the multi-TeV cosmic-ray anisotropy due to terrestrial orbital motion around the Sun

We report on the solar diurnal variation of the galactic cosmic-ray intensity observed by the Tibet III air shower array during the period from 1999 to 2003. In the higher-energy event samples (12 and 6.2 TeV), the variations are fairly consistent with the Compton-Getting anisotropy due to the terrestrial orbital motion around the Sun, while the variation in the lower-energy event sample (4.0 TeV) is inconsistent with this anisotropy. This suggests an additional anisotropy superposed at the multi-TeV energies, e.g., the solar modulation effect. This is the highest-precision measurement of the Compton-Getting anisotropy ever made.     

Generation of organo-alkaline earth metal complexes from non-polar unsaturated molecules and their synthetic applications

Organomagnesium compounds, represented by the Grignard reagents, are one of the most classical yet versatile carbanion species which have widely been utilized in synthetic chemistry. These reagents are typically prepared via oxidative addition of organic halides to magnesium metals, via halogen–magnesium exchange between halo(hetero)arenes and organomagnesium reagents or via deprotonative magnesiation of prefunctionalized (hetero)arenes. On the other hand, recent studies have demonstrated that the organo-alkaline earth metal complexes including those based on heavier alkaline earth metals such as calcium, strontium and barium could be generated from readily available non-polar unsaturated molecules such as alkenes, alkynes, 1,3-enynes and arenes through unique metallation processes. Nonetheless, the resulting organo-alkaline earth metal complexes could be further functionalized with a variety of electrophiles in various reaction modes. In particular, organocalcium, strontium and barium species have shown unprecedented reactivity in the downstream functionalization, which could not be observed in the reactivity of organomagnesium complexes. This perspective will focus on the newly emerging protocols for the generation of organo-alkaline earth metal complexes from non-polar unsaturated molecules and their applications in chemical synthesis and catalysis.

In this perspective, we highlight the recent development of metallation protocols of non-polar unsaturated molecules for the generation of organo-alkaline earth metal compounds and their applications in chemical synthesis and catalysis.     

Determination of optical properties in double integrating sphere measurement by artificial neural network based method

Optical Review - An accurate inversion technique in double integrating sphere (DIS) measurement is essential for determining the optical properties of biological tissue. Although there are several...     

Removal of fluoride from water through ion exchange by mesoporous Ti oxohydroxide

In our previous study, we found that Ti(OH)(4) exhibited fluoride ion exchange properties. In order to improve the ion exchange capacity, mesoporous Ti oxohydroxide (TiOx(OH)y) had been prepared by using dodecylamine as template. Zirconia and silica had been introduced into the mesoporous Ti oxohydroxide to enhance the ion exchange capacity. The mesoporous structure and the morphology of the mesoporous materials obtained were confirmed using XRD and SEM, respectively. A fluoride ion exchange study was done on each sample. Results showed that mesoporous Ti oxohydroxide containing zirconia exhibited the highest fluoride ion exchange capacity, as it has the smallest particle size, with high uniformity among the mesoporous materials prepared.     

Catalytic degradation of polyethylene and polypropylene to fuel oil

Thermal and catalytic degradation of plastic polymers, polyethylene and polypropylene to fuel oil were carried out in batch operations. The catalysts employed were acid silica-alumina (SA-1, SA-2) and zeolite ZSM-5, and non-acidic mesoporous silica FSM (folded sheet material). The yields of product gas, liquid and residues, recovery rate of liquid products, and boiling point ranges of liquid products due to degradation were compared with those of non-catalytic thermal degradation. Both the effect of catalytic contact mode and of catalyst type on the degradation were studied. In liquid-phase degradation of PP over SA-1, liquid hydrocarbon products were obtained in a yield of 69 wt.-% with a boiling point range 36-270°C, equivalent to the boiling point of normal paraffins C6 - C15. The liquid products from catalytic degradation have a carbon-number distribution very similar to commercial motor gasoline. In vapor-phase contact, the yield of liquid products was much lower (54%) and the rate of liquid recovery was much slower. With FSM, the initial rate of degradation of PP and PE to liquid products was as fast as that over acid catalyst SA-1, but the yield of liquid products was higher. The liquid products from catalytic degradation over FSM have a carbon-number distribution similar to kerosene and diesel oil. In repeated use, SA-1 deactivated very rapidly due to coke deposition on the catalyst, whereas FSM deactivated much more slowly. These findings suggest that mesopores surrounded by the silica sheet may act as reservoir for radical species, which accelerate the degradation of plastic melt.     

Selective reduction of NOX with C3H6 over Cu incorporated into silicoalumino-phosphate (SAPO)

Cu ion-exchanged SAPO-34 which is a highly active catalyst for selective reduction of NO with C₃H₆, was synthesized and the Cu ion was characterized in the SAPO-34 by ESR, XPS, IR, and XAFS. ESR study indicated that two kinds of Cu(II) with different environments exist in SAPO-34. The Cu(II) species disappeared immediately by C₃H₆ treatment and recovered by oxygen treatment. XAFS study indicated that most of the Cu(II) was reduced to Cu(I) under the presence of C₃H₆. These studies revealed that a selective NO reduction by C₃H₆ over SAPO-34 should proceed by the redox reaction of a copper ion between Cu(I) and Cu(II).     

Synthesis and properties of fullerene (C70) complexes of 2,6-bis(porphyrin)-substituted pyrazine derivatives bound to a Pd(II) ion

2,6-Bis(porphyrin)-substituted 3,5-dimethylpyrazine and its zinc complex bound C₇₀ to yield 1:1 inclusion complexes, which were characterised by ESI-MS, UV–vis, fluorescence and NMR spectroscopies. Association constants of the C₇₀ complexes were determined by fluorescence and NMR spectral analyses. A decrease in absorbance of the Soret band of the pyrazine derivative by the effect of C₇₀ was observed, suggesting the existence of a charge transfer interaction between C₇₀ and porphyrin. Experimentally reliable values for the association constants were obtained by the NMR method and were about six times larger than those of the corresponding C₆₀ complexes. Palladium complexation of the porphyrin–pyrazine ligand was found to enhance the association with fullerene. The association constant of 2,6-bis(porphyrin-Zn)-substituted 3,5-dimethylpyrazine-Pd(II) complex with C₇₀ was determined to be 8400 ± 900 M^? 1. From the comparison of the association constants, it was found that inclusion room for C₇₀ in the Pd(II) complex was maintained, juxtaposed between porphyrins attached to the opposite sides of the pyrazine ligands.

     

Catalytic decomposition of CFCs

Catalytic decomposition of CCI₂F₂ was studied over a number of single and complex metal oxides using a fixed-bed reactor. The ZrO₂–Cr₂O₂ catalyst exhibited the highest activity and CO₂ and CCIF₃ were formed at 350–450°C. Selective decomposition of CCI₂F₂ required the presence of both oxygen and water vapor over the catalyst. Catalytic activity gradually declined with time on stream because of the fluorination of ZrO₂. Treatment of the catalyst with both oxygen and water vapor promoted the removal of fluoride ions in sub-surface layers of the catalyst, which is effective for the recovery of the activity. CCI₂F₂ was decomposed at 300–450°C over AIPO₄. No fluorination of the AIPO₄ catalyst took place after the reaction for 1000 h. CH₂FCF₃, an alternative CFC, was completely decomposed over the mixed catalyst of Ce promoted AIPO₄ and Cr₂O₃ at 400–500°C. Catalytic decomposition is a rational method for destruction of used CFCs.