Water splitting reaction on a polynaphthoquinone catalyst a polynaphthoquinone-SO2-I2 system for H2O decomposition

The water splitting reaction in a polynaphthoquinone-SO₂-I₂ system under mild conditions is reported. One mole H₂O was decomposed to form 2 moles HI and 1 mole H₂SO₄ by the following two successive hydrogen transfer reactions in conjunction with the redox cycle of quinones(Q)-hydroquinones(QH₂) in the polynaphthoquinone catalyst:

$\text{2H}{}_2\text{O +SO}{}_2\text{+ Q ? QH}{}_2\text{+ H}{}_2\text{SO}{}_4\text{, QH}{}_2\text{+ I}{}_2\text{? 2HI + Q}$

The hydrogen transfer reaction from H₂O to Q was accelerated by a factor of 3–5 by light irradiation and hence this system could work also as a hybrid thermochemical cycle. When the catalytic hydrogen transfer reactions on the polynaphthoquinone are combined with the thermal decompositions of HI(2 HI ? H₂ + I₂) and H₂SO₄ ($\text{H}{}_2\text{SO}{}_4\text{? H}{}_2\text{O + SO}{}_2\text{+}\text{1}\text{2}\text{O}{}_2$), a closed water splitting cycle for the hydrogen production could be constructed. The reaction mechanism is also discussed.     

3D attitude measurement by means of spread spectrum modulated ultrasonic wave

Local position and attitude measurement methods are necessary for the navigation of autonomous robots and the other applications. In this paper, a 3D attitude measurement method is proposed. This method uses the spread spectrum modulated ultrasonic wave for the measurement of the pseudo-distance of each pathway between transmitter and receiver elements that are arranged in an array. The relative attitude between transmitter and receiver unit could be calculated from the relationship between these pseudo-distances. The use of spread spectrum modulation enables the high accuracy, noise tolerance, and coexistence of multiple transmitter devices by code division multiple access (CDMA) between transmitter and receiver elements. A pair of transmitter and receiver prototype for proposed method was manufactured, and the fundamental performance was examined in experiments. As a result, accuracy of σ=0.78 mm in the pseudo-distance measurement of each pathway between transmitter and receiver elements was confirmed, and about 0.01 rad resolution in the attitude measurement was also confirmed.     

Self-crack healing ability and strength recovery in ytterbium disilicate/silicon carbide nanocomposites

The SiO₂ volatility and SiC recession in hydrocarbon-rich combustion atmosphere is the main problem of SiC-reinforced ceramics when they are utilized as coating materials for gas turbine blades. The composite of Yb₂Si₂O₇-Yb₂SiO₅/SiC is expected as a self-crack healing material that can avoid this problem because the monosilicate can react with the SiO₂ glass to form disilicate and hence further reinforce the composite. In this study, the composites, fabricated with various morphology of SiC nanofillers, were precracked and then heat-treated in an oxidizing environment to activate their crack healing behavior. The healing effect as a function of filler morphology and annealing time was investigated. Healing mechanism and future applications of these composites were also discussed.     

Preparation of supported gold catalysts from gold complexes and their catalytic activities for CO oxidation

A phosphine-stabilized mononuclear gold complex Au(PPh₃)(NO₃) (1) and a phosphine-stabilized gold cluster [Aug(PPh₃)₈](NO₃)₃ (2) were used as precursors for preparation of supported gold catalysts. Both complexes 1 and 2 supported on inorganic oxides such as -Fe₂O₃, TiO₂, and SiO₂ were inactive for CO oxidation, whereas the 1 or 2/ oxides treated under air or CO or 5% h₂/Ar atmosphere were found to be active for CO oxidation. The catalytic activity depended on not only the treatment conditions but also the kinds of the precursor and the supports used. The catalysts derived from 1 showed higher activity than those derived from 2. -Fe₂O₃ and TiO₂ were much more efficient supports than SiO₂ for the gold particles which were characterized by XRD and EXAFS.     

Ferulic acid production from clove oil by Pseudomonas fluorescens E118

For the production of the useful antioxidant ferulic acid from clove oil containing abundant eugenol, the growth of eugenol-degrading microorganisms in the presence of clove oil was examined. Pseudomonas fluorescens E118, a clove-oil-tolerant strain, accumulated 6.1 g/l ferulic acid under optimized culture conditions with the intermittent addition of eugenol. When the bacterium was applied to ferulic acid production from clove oil, 5.8 g/l ferulic acid was produced with the intermittent addition of clove oil. Since clove oil is much cheaper than eugenol, ferulic acid production from clove oil by the bacterium is promising for the industrial production of ferulic acid.     

Characterization of a highly selective hydrogen permeable silica membrane

The permeability properties of a new type of silica membrane for the small gas molecules CO₂, CO, Ne, CH₄, He, and H₂ are presented. The new membrane, denoted as Nanosil, has unusually high permeance for H₂, but also allows passage of He and to a smaller extent Ne, while excluding all other molecules. The membrane is formed by the decomposition of a silica precursor (tetraethyl orthosilicate) onto a Vycor glass substrate. Nitrogen physisorption isotherms of the Vycor glass substrate indicate that it is a microporous solid with slit-like pores of 3.6 nm diameter, that remains unchanged after the silica deposition. Atomic force microscopy (AFM) shows that the Vycor substrate is made up of rectangular plate-like elements of size 90 nm × 30 nm. Between the plates are found rectangular features of 4 nm breadth which are likely to be the pore mouths. The deposited silica forms a thin layer on top of these plates so as to erase fine structures and increase the average feature size to 110 nm × 50 nm.     

Density Functional Theory Study on the Re Cluster/HZSM-5 Catalysis for Direct Phenol Synthesis from Benzene and Molecular Oxygen: Active Re Structure and Reaction Mechanism

DFT calculations have been achieved to obtain a convincing model for the active structure in a Re cluster/HZSM-5 catalyst active for direct phenol synthesis from benzene and molecular oxygen. Re₁₀ clusters with interstitial N atoms composed of two Re octahedra edge-shared with each other were concluded as a stable active structure in agreement with the EXAFS analysis. The adsorption and behavior of benzene, oxygen atom and molecule and phenol on the Re cluster were examined to obtain the energy diagram for the phenol synthesis including intermediate and transition states, which explains the reaction steps for the phenol synthesis.     

Comparative antimicrobial activity of RP 59,500 (quinupristin-dalfopristin), the first semisynthetic injectable streptgramin, against gram-positive cocci and other recent clinical pathogens

RP 59,500 (Quinupristin-Dalfopristin) is the first semisynthetic injectable streptogramin antimicrobial agent, which is a combination of quinupristin and dalfopristin in a 30:70 ratio. The components of RP 59,500 act synergically to provide bactericidal activity through action at different sites on bacterial ribosomes. In the present study, the antimicrobial activity of RP 59,500 was compared with those of four macrolides (erythromycin, clarithromycin, azithromycin, roxithromycin). Susceptibility testing was carried out by microdilution method on 303 strains of 10 species, especially antibiotic-resistant Gram-positive cocci. RP 59,500 was active against a wide range of Gram-positive cocci including methicillin-resistant Staphylococci and penicillin-resistant Streptococcus pneumoniae. The MICs90 of RP 59,500 against methicillin-resistant Staphylococcus aureus (MRSA) and Staphylococcus epidermidis were both 0.25 microgram/ml, although those of four macrolides were higher than 32 micrograms/ml. The MICs90 of RP 59,500 against penicillin-sensitive, -intermediate and -resistant S. pneumoniae were all 0.5 microgram/ml, although those of four macrolides against penicillin-resistant S. pneumoniae were higher than 32 micrograms/ml. RP 59,500 also exhibited equivalent activities to the four macrolides against strains of Streptococcus pyogenes. Streptococcus agalactiae and Moraxella catarrhalis. RP 59,500 exhibited the highest activities against Enterococcus faecalis, Enterococcus faecium and Enterococcus avium strains which are intrinsically resistant to most antimicrobial agents. No cross-resistance was observed between RP 59,500 and the four macrolides, which will merit attention in future clinical trials of the agent. The effect of human serum on the MIC of RP 59,500 was studied with strains of S. aureus, S. epidermidis and E. faecalis. The presence of 20% (V/V) serum had little or no effect on the MIC, although 50% (V/V) serum increased MICs by 4-8 folds. Laboratory-induced resistance to RP 59,500 occurred in a stepwise fashion in broth cultures of S. aureus, S. epidermidis and E. facalis strains and the induction rate was slow and no more than four fold increases were observed. Population analysis was performed on RP 59,500 and the reference macrolides against S. aureus ATCC 25,923 strain. Although low frequencies (less than 0.01%) of resistant sub-population were detected with EM, CAM, AZM and RXM, no RP 59,500-resistant sub-population was detected in this study.     

Michael Reactions Catalyzed by Basic Alkylamines and Dialkylaminopyridine Immobilized on Acidic Silica–Alumina Surfaces

Acid–base bifunctional catalysts were prepared by immobilization of basic amines on acidic silica–alumina (SA) surfaces. Silane-coupling reagents with various amino-functional groups, such as primary, secondary, and tertiary alkylamines, alkyldiamine, and dialkylaminopyridine, were examined as anchoring reagents for the amines in the preparation of catalysts. The obtained immobilized catalysts (SA–NR′R′′) were characterized by solid-state ¹³C and ²⁹Si MAS NMR and elemental analysis. The catalytic activity of tertiary alkylamines for Michael reactions increased dramatically by the immobilization on silica–alumina, whereas a homogeneous tertiary amine scarcely promoted the reaction. Regarding the kind of amines, the dialkylaminopyridine immobilized silica–alumina with low Al content (SA_L) showed the highest catalytic performance among the amine immobilized catalysts. The solid-state ¹³C NMR analysis revealed the interaction between the nitrogen atom on pyridine ring and a surface strong acid site of the silica–alumina support.     

CERTIFIED CALIBRATION SOLUTION REFERENCE MATERIAL FOR THE DETERMINATION OF BENZO[A]PYRENE FROM THE NATIONAL METROLOGY INSTITUTE OF JAPAN (NMIJ)

A new calibration solution reference material (NMIJ CRM 4213-a) for benzo[a]pyrene (BaP) analysis was prepared and certified by the National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Certification of CRM 4213-a was carried out at NMIJ using a freezing point depression method and gravimetric preparation. Certified concentration of this CRM was obtained by multiplying the dilution ratio of raw material BaP in a prepared solution with purity of the raw material. Purity of our raw material was calibrated by a gas chromatograph with flame ionization detection using that of high-purity BaP purified by using a high performance liquid chromatograph with a normal phase column, because purity determination of the raw material by a differential scanning calorimeter (DSC) couldn't be assessed directly. The purity of high-purity BaP was assessed in the molar fraction by DSC, and then the purity of the mass fraction was calculated based on average molecular weight of impurities and the purity of the molar fraction. CRM 4213-a has been developed with a certified value of 99.2 mg/kg. Uncertainty was evaluated from purity assessment as well as homogeneity and stability of the CRM, and expanded uncertainty was estimated as 3.9 mg/kg with coverage factor k = 2, corresponding to an estimated confidence interval of approximately 95%.