Loading effects of silver oxides upon generation of reactive oxygen species in semiconductor photocatalysis

Superoxide anion radical (O(2)(-*)) and OH radical generations in suspensions of Ag metal-, Ag(2)O-, or AgO-loaded TiO(2) and BiVO(4) photocatalysts in alkaline conditions (pH 12.0) were examined by means of a luminol chemiluminescence (CL) technique and a spin-trapping fluorescence one in which terephthalic acid reacts with an OH radical to afford the highly fluorescent 2-hydroxyterephthalic acid (TAOH), respectively. The observed luminol CL intensity was remarkably enhanced by the AgO loading on TiO(2) as well as BiVO(4). This can be explained by enhancement of O(2)(-*) production on the AgO-loaded photocatalysts caused by the synergetic effects on the thermocatalytic activity upon the AgO surface and the efficient electron-hole separation at the photocatalyst/AgO interface. On the other hand, loading effects of AgO on the TAOH formation were not so significant compared to those on the CL observation, though the TAOH formation rates for the TiO(2) samples were much larger than those for the BiVO(4) ones by about three orders of magnitude. The properties of O(2)(-*) and OH radical generations on these photocatalysts are discussed on the basis of the luminol CL kinetics and approximate band edge positions of TiO(2), BiVO(4), and silver oxides.     

Synthesis and structural characterization of a new aluminum oxycarbonitride, Al5(O, C, N)4

A new aluminum oxycarbonitride, Al₅(O_xC_yN_4−x−y) (x∼1.4 and y∼2.1), has been synthesized and characterized by X-ray powder diffraction, transmission electron microscopy and electron energy loss spectroscopy (EELS). The title compound was found to be hexagonal with space group P6₃/mmc, Z=2, and unit-cell dimensions a=0.328455(6) nm, c=2.15998(3) nm and V=0.201805(6) nm³. The atom ratios O:C:N were determined by EELS. The final structural model, which is isomorphous with that of (Al_4.4Si_0.6)(O_1.0C_3.0), showed the positional disordering of one of the three types of Al sites. The maximum-entropy method-based pattern fitting (MPF) method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The reliability indices calculated from the MPF were R_wp=6.94% (S=1.22), R_p=5.34%, R_B=1.35% and R_F=0.76%. The crystal was an inversion twin. Each twin-related individual was isostructural with Al₅C₃N (space group P6₃mc, Z=2).     

Di-, tri-, and tetra-arylterephthalic acids as novel clathrate host compounds

Novel terephthalic acid host compounds having aromatic substituent 1-4 have been prepared and their inclusion properties were investigated. These host compounds enclathrated several kinds of alcohols, ethers, ketones, amides, and sulfoxides. The X-ray structures of 1:1 2a/EtOH, 1:2 2b/DMF, 1:2 3/MeOH, and 1:1 4/EtOH complexes revealed complexation mode.     

Synergistic hybrid catalyst for cyclic carbonate synthesis: remarkable acceleration caused by immobilization of homogeneous catalyst on silica

The catalytic activity of phosphonium salts towards cyclic carbonate synthesis from propylene oxide and CO2 has been enormously enhanced by their immobilization onto silica that itself has no catalytic activity.     

Biobased contents of biodegradable poly(epsilon-caprolactone) composites polymerized and directly molded using aluminium triflate from caprolactone with cellulose and inorganic filler

Poly(epsilon-caprolactone) (PCL) composite samples were prepared by polymerization and direct molding. The starting compound was epsilon-caprolactone monomer liquid combined with cellulose and inorganic fillers, using aluminium triflate as a catalyst at 80 degrees C, for 6 or 24 h. Cylinder-shaped PCL composite samples with a homogeneously dispersed cellulose filler were prepared with (-)M(n) = 4 600 ((-)M(w)/(-)M(n) = 2.9). The mechanical properties of the PCL composite samples were studied using compression test methods. The strength of a PCL composite with 50 wt.-% cellulose filler (10.8 MPa) was found to be lower than the PCL sample without fillers (19.2 MPa). The biobased content of the PCL composite with 50 wt.-% cellulose filler (51.67%) measured using accelerated mass spectrometry (AMS) was slightly higher than the carbon ratio of cellulose in the starting powder samples (41.3 mol-%). The biobased content of the polymer composite powders by AMS was found not to be affected by the presence of inorganic fillers, such as talc. The rate and extent of biodegradation, caused by Amano Lipase PS, of the PCL composite sample with cellulose filler (40% degradation in 4 d) was the same as that of a PCL sample without the cellulose filler.     

Isolation and structures of biselyngbyasides B,C, and D from the marine cyanobacterium Lyngbya sp., and the biological activities of biselyngbyasides

Bioassay-guided fractionation of the marine cyanobacterium Lyngbya sp. led to the isolation of biselyngbyasides B (3), C (4), and D (5), novel analogs of biselyngbyaside (1) and biselyngbyolide A (2). The gross structures of 3–5 were determined by NMR spectral analyses, and their stereochemistries were established based on NOESY spectra and CD data. Biselyngbyasides (1–3) showed growth-inhibitory activity and apoptosis-inducing activity against both HeLa S₃ cells and HL60 cells. The fura-2 method revealed that biselyngbyasides (1–3) increased the cytosolic Ca²⁺ concentration in HeLa S₃ cells.     

Wellfoundedness proofs by means of non-monotonic inductive definitions II: First order operators

In this paper, we give two proofs of the wellfoundedness of a recursive notation system for Π_N-reflecting ordinals. One is based on distinguished classes, and the other is based on -inductive definitions.     

Derivatives of normal functions and $$\omega $$-models

In this note the well-ordering principle for the derivative \(\mathsf{g}^{\prime }\) of normal functions \(\mathsf{g}\) on ordinals is shown to be equivalent to the existence of arbitrarily large countable coded \(\omega \)-models of the well-ordering principle for the function \(\mathsf{g}\).     

Synthesis of ketimines via palladium complex-catalyzed cross-coupling of imidoyl chlorides with organotin compounds

Imidoyl chlorides were successfully transformed into ketimines when treated with organotin compounds in the presence of palladium complex catalysts.