Recent topics of gold catalyst featuring Z-type ligands

In the long history regarding the development of the transition metal-catalyzed reactions, almost all ligands in metals are classified as the covalent X-type and/or dative L-type ligands. Therefore, exploring the reactivity of the metal complexes bearing the σ-acceptor, i.e., the Z-ligand, is required. This digest briefly describes our recent results regarding 1) the syntheses of gold complexes featuring the Z-type ligand, and 2) their catalytic reactions, which would be speculated that the electron-withdrawing effect of the Z-ligand on the neighboring gold activated the catalytic reactivity due to the increase in the Lewis acidity.     

Neutron activation analysis of carbonate reference materials: coral (JCp-1) and giant clam (JCt-1)

Journal of Radioanalytical and Nuclear Chemistry - Two kinds of carbonate reference materials, coral (JCp-1) and giant clam (JCt-1), were subjected to neutron activation analysis (NAA) using the...     

Initial quantum levels of captured muons in CO,CO2, and COS

The role of valence electrons for the muon capture process by molecules is experimentally investigated with the aid of cascade calculations. Low-momentum muons are introduced to gas targets of CO, CO₂, and COS below atmospheric pressure. The initial states of captured muons are determined from the measured muonic X-ray structure of the Lyman and Balmer series. We propose that the lone pair electrons in the carbon atom of CO significantly contribute to the capture of a muon with large angular momenta.

     

Transition between internal transport barriers with different temperature-profile curvatures in JT-60U Tokamak plasmas

A spontaneous transition phenomena between two states of a plasma with an internal transport barrier (ITB) is observed in the steady-state phase of the magnetic shear in the negative magnetic shear plasma in the JT-60U tokamak. These two ITB states are characterized by different profiles of the second radial derivative of the ion temperature inside the ITB region (one has a weak concave shape and the other has a strong convex shape) and by different degrees of sharpness of the interfaces between the L mode and the ITB region, which is determined by the turbulence penetration into the ITB region.     

Tetrahedral Oligothiophenes; Synthesis,X‐ray Analysis,and Optoelectronic Properties of Highly Symmetrical, 3D‐Branched Oligothiophenes

Tetrakis(bithienyl)methane and tetrakis(terthienyl)methane have been synthesized from tetrakis(2‐thienyl)methane by use of Suzuki–Miyaura coupling as a key reaction. Their trimethylsilyl (TMS) derivatives are also synthesized. X‐ray analysis reveals that each oligothiophene moiety tends to adopt anti‐conformations and show relatively small torsion angles between the adjacent thiophene rings. While the longest absorption maxima of these tetrakis(oligothienyl)methanes exhibit only a slight bathochromic shift compared to the corresponding linear oligothiophene derivative, tetrakis(bithienyl)methane and its TMS derivative exhibit an appreciable red‐shift in their fluorescence spectra. The intramolecular interaction between thienyl groups of tetrakis(2‐thienyl)methane is supported by DFT calculation.     

Syntheses of novel di- and trinucleating ligands having a triethylbenzene core with N,N-bidentate tethers: their complexation toward Pd and Rh organometallic fragments

A series of di- and trinucleating ligands with a 1,3,5-triethylbenzene core connected to N,N-bidentate tethers was synthesized. The ligands readily reacted with monuclear Rh and Pd precursors to give the corresponding di- and trinuclear complexes, which were characterized by using NMR and ESI mass spectroscopy. In the solid state, the trinuclear complexes with ligands having pyridylpyrazolyl tethers adopt the most stable ababab configuration, in which the organometallic fragments are on the same side of the benzene plane. On the other hand, in solution, the linker moieties between the benzene core and the metals are flexible enough to interconvert between other configurations, that is, they exhibit dynamic behavior, and the rotational barrier was dependent on the length of the linkers. From variable temperature (VT) 1H NMR measurements, the rotational barrier for a trinuclear Rh-CO complex with a ligand having methylene linkers was estimated to be approximately 12.6 kcal mol(-1). However, no spectral changes were observed for the ethylene derivative in the temperature range of -60 degrees C to 50 degrees C, indicating that the rotation was not frozen out on the 1H NMR timescale, even at -60 degrees C.     

Direct detection method of oligosaccharides by high-performance liquid chromatography with charged aerosol detection

A simple and rapid detection method of oligosaccharides using high-performance liquid chromatography with a charged aerosol detection (HPLC-CAD) was studied. The direct detection of a sialylglycopeptide (SGP) derived from egg yolk was accomplished by HPLC-CAD using an amido-silica column, and its limit of detection was 0.40 pmol [signal-to-noise ratio (S/N) = 3]. The sensitivity of this method was lower than that of the fluorescence detection; however, the method showed approximately 5 times higher sensitivity than that using the conventional UV absorbance detection. Furthermore, this method was used for the analysis of the acid hydrolysis products of SGP. Monosialo- and asialo-oligosaccharides as well as free sialic acid were detected without using fluorescent derivatization. These results indicate that the present method is a new tool for the analysis of oligosaccharides.     

Determination of cadmium in grains by isotope dilution ICP–MS and coprecipitation using sample constituents as carrier precipitants

A coprecipitation method using sample constituents as carrier precipitants was developed that can remove molybdenum, which interferes with the determination of cadmium in grain samples via isotope dilution inductively coupled plasma mass spectrometry (ID-ICPMS). Samples were digested with HNO₃, HF, and HClO₄, and then purified 6 M sodium hydroxide solution was added to generate colloidal hydrolysis compounds, mainly magnesium hydroxide. Cadmium can be effectively separated from molybdenum because the cadmium forms hydroxides and adsorbs onto and/or is occluded in the colloid, while the molybdenum does not form hydroxides or adsorb onto the hydrolysis colloid. The colloid was separated by centrifugation and then dissolved with 0.2 M HNO₃ solution to recover the cadmium. The recovery of Cd achieved using the coprecipitation was >97%, and the removal efficiency of Mo was approximately 99.9%. An extremely low procedural blank (below the detection limit of ICPMS) was achieved by purifying the 6 M sodium hydroxide solution via Mg coprecipitation using Mg(NO₃)₂ solution. The proposed method was applied to two certified reference materials (NIST SRM 1567a wheat flour and SRM 1568a rice flour) and CCQM-P64 soybean powder. Good analytical results with small uncertainties were obtained for all samples. This method is simple and reliable for the determination of Cd in grain samples by ID-ICPMS. Figure Overview of a coprecipitation method using sample constituents     

Thermal [2+2] cycloaddition of allenynes: easy construction of bicyclo[6.2.0]deca-1,8-dienes, bicyclo[5.2.0]nona-1,7-dienes, and bicyclo[4.2.0]octa-1,6-dienes

The simple refluxing of allenynes, having a phenylsulfonyl functionality on the allenyl group, in xylene (or mesitylene) without microwave irradiation resulted in the efficient formation of bicyclo[5.2.0]nona-1,7-dienes and bicyclo[4.2.0]octa-1,6-dienes in high yields. This method was shown to be successfully applicable to the first construction of bicyclo[6.2.0]deca-1,8-dienes. Construction of the corresponding oxa- and azabicyclo[m.2.0] frameworks could also be attained. This thermal ring-closing reaction involves the formal [2+2] cycloaddition in which the distal double bond of an allenyl moiety exclusively served as one of the pi-components regardless of the position of the phenysulfonyl functionality on the allenyl moiety.