Direct Near Infrared Light–Activatable Phthalocyanine Catalysts

The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activated by NIR light to transform small organic molecules. The desired photocatalytic properties were achieved in the phthalocyanines by introducing the appropriate peripheral substituents and central metal. These phthalocyanine photocatalysts promote cross-dehydrogenative-coupling (CDC) under irradiation with 810 nm NIR light. The choice of solvent is important, and a mixture of a reaction-accelerating (pyridine) and -decelerating (methanol) solvents was particularly effective. Moreover, we demonstrate photoreactions under visible-light-shielded conditions through the transmission of NIR light. A combined experimental and computational mechanistic analysis revealed that this NIR reaction does not involve a photoredox-type mechanism with electron transfer, but instead a singlet-oxygen-mediated mechanism with energy transfer.     

Diverse Approaches for Enantioselective C−H Functionalization Reactions Using Group 9 CpxMIII Catalysts

Transition-metal-catalyzed C−H functionalization reactions with Cp*M^III catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties in achieving catalytic stereocontrol using these catalysts due to their lack of additional coordination sites for external chiral ligands and the conformational flexibility of the Cp ligand, catalytic enantioselective C−H functionalization reactions using the Group 9 metal triad with Cp-type ligands have been intensively studied since 2012. In this minireview, the progress in these reactions according to the type of the chiral catalyst used are summarized and discussed. The development of chiral Cp^x ligands the metal complexes thereof, artificial metalloenzymes, chiral carboxylate-assisted enantioselective C−H activations, enantioselective alkylations assisted by chiral carboxylic acids or chiral sulfonates, and chiral transient directing groups are discussed.     

Synthesis of the racemic and optically active forms of gizzerosine,the inducer of gizzard erosion in chicks

The racemate and both the (R)- and (S)-forms of gizzerosine [2-amino-9-(4-imidazolyl)-7-azanonanoic acid] were synthesised, and the (S)-isomer was identified as the toxic substance in fish meal causing severe gizzard erosion (black vomit) in chicks.     

Polynomial time perfect sampling algorithm for two‐rowed contingency tables

This paper proposes a polynomial time perfect (exact) sampling algorithm for 2 × n contingency tables. The algorithm is based on monotone coupling from the past (monotone CFTP) algorithm. The expected running time is bounded by O(n³ lnN) where n is the number of columns and N is the total sum of all entries. © 2005 Wiley Periodicals, Inc. Random Struct. Alg., 2006     

Performance analysis for an all-optical wavelength converter using four-wave mixing (FWM) in a single mode fiber

An analytical approach is presented to determine the performance of a tunable wavelength converter based on four wave mixing (FWM) in a single mode fiber (SMF) with two pump lasers. The analysis is carried out for an intensity modulated (IM) signal taking into considerations the effects of spectral broadening due to FWM and laser phase noise. The results evaluated at a bit rate of 10 Gb/s show that the signal power is substantially higher at lower values of wavelength separation. For example, for input powers of 10 mW each, wavelength separation of 4 nm between the pump-2 and the input signal, the output converted power is found to be –10 dBm corresponding to wavelength separation of 2 nm between pump-1 and converter signal. The corresponding crosstalk power is found to be –25 dBm at a channel separation of 3 times bit rate.     

A theoretical study of photoelectron spectra of NbO2, MoO2 and RuO2 by cluster models

DV-Xα calculations have been applied to various small clusters of rutile-family dioxides (NbO₂, MoO₂ RuO₂). It appears that by taking into consideration the potential due to the atomic charges, the density, the ionization cross sections of the energy levels, and by summing the density of states (DOS) of the two different clusters representing surface structures, computations on even small clusters provide information which compares well with the experimental XPS spectra.     

Simultaneous direct determination of aluminum, calcium and iron in silicon carbide and silicon nitride powders by slurry-sampling graphite furnace AAS.

A fast and accurate analytical method was established for the simultaneous direct determination of aluminum, calcium and iron in silicon carbide and silicon nitride powders by graphite furnace atomic absorption spectrometry using a slurry sampling technique and a Hitachi Model Z-9000 atomic absorption spectrometer. The slurry samples were prepared by the ultrasonication of silicon carbide or silicon nitride powders with 0.1 M nitric acid. Calibration curves were prepared by using a mixed standard solution containing aluminum, calcium, iron and 0.1 M nitric acid. The analytical results of the proposed method for aluminum, calcium and iron in silicon carbide and silicon nitride reference materials were in good agreement with the reference values. The detection limits for aluminum, calcium and iron were 0.6 microg/g, 0.15 microg/g and 2.5 microg/g, respectively, in solid samples, when 200 mg of powdered samples were suspended in 20 ml of 0.1 M nitric acid and a 10 microl portion of the slurry sample was then measured. The relative standard deviation of the determination of aluminum, calcium and iron was 5 - 33%.     

Synthesis of CuO---Al2O3---SiO2 glasses from the sol-gel method and properties

The synthesis of CuO---Al₂O₃---SiO₂ glasses by the sol-gel method was investigated and the thermal expansion of bulk glasses was measured. Phase separation was observed in these glasses and apparently consisted of a copper-rich dispersed phase and a network former-rich matrix phase. The low thermal expansion coefficient of these glasses was governed by the matrix phase.     

Synthesis of phosphate-type fluorocarbon-hydrocarbon hybrid surfactants and their adsorption onto calcium hydroxyapatite

Five novel phosphate-type hybrid surfactants, C_mF_2m+1C₆H₄CH[OPO₂(OC₆H₅)Na]C_nH_2n+1 (FmPHnPPhNa: m = 4, 6, 8; n = 3, 5; C₆H₄ = p-phenylene, C₆H₅ = phenyl), have been synthesized. When compared with sulfate-type hybrid surfactants, C_mF_2m+1C₆H₄CH(OSO₃Na)C_nH_2n+1 (C₆H₄ = p-phenylene), the new hybrid surfactants are found to have comparable abilities to lower surface tension of water. The critical micelle concentrations of FmPHnPPhNa follow Klevens rule and their occupied areas per molecule increase with increasing m and n. Calcium hydroxyapatite (CaHAp) pellets modified with FmPH3PPhNa gives high hydrophobic and lipophobic surfaces. The hybrid surfactants are expected as new dental reagents for oral hygiene.     

Study on Semi-Glycinecresol Red complexes with bivalent metal ions

Semi-Glycinecresol Red (SGCR or H(3)SGCR) was purified by means of chromatography on cellulose and by cation-exchange. A potentiometric, spectrophotometric and ESR study on the complex formation equilibria of several bivalent metal ions with SGCR was performed. The acid-base and metal-ligand stoichiometries were determined, and the formation constants, lambda(max) and absorptivities of the visible-region absorption spectra of the corresponding proton and metal complexes were determined. The copper complexes were examined by ESR spectroscopy. Each metal ion was found to form the 1:1 and 1:2 (metal:ligand) complex species, MSGCR(-) and M(SGCR)(4-)(2), in alkaline solution. However, only Cu(II) was found to form the protonated complexes, CuHSGCR and Cu(HSGCR)(2-)(2), in weakly acidic media. SGCR is suitable as an indicator for Cu(II) in a weakly acidic solution and for Cu(II), Zn(II) and Pb(II) in alkaline solution.