Heterogeneous continuous flow synthetic system using cyclohexane-based multiphase electrolyte solutions

The discovery that supporting electrolytes can be effectively confined in typical organic solvents in a c-Hex-based multiphase electrolyte solution has led to the development of a novel heterogeneous continuous flow synthetic system. PTFE fiber functions as a separation filter that can efficiently isolate the c-Hex phase from multiphase electrolyte solutions. This system has demonstrated both electrochemical solvating and carbon-carbon bond forming reactions. Hydrophobic substrates can be introduced into the reactor as c-Hex solutions, which are then electrochemically transformed into the target hydrophobic products that pass through the PTFE fiber as c-Hex solutions.     

Combination of sp2‐ and sp3‐Type Phosphorus Atoms for Gold Chemistry: Preparation,Structure, and Catalytic Activity of Gold Complexes That Bear Ligated 2‐Silyl‐1,3‐diphosphapropenes

Kinetically protected 2‐silyl‐1,3‐diphosphapropenes that bear both sp²‐ and sp³‐type phosphorus atoms were employed in the preparation of gold complexes. The structural properties of the 1,3‐diphosphapropene digold(I) complexes were characterized by spectroscopic and crystallographic analyses, which revealed unique aurophilic interactions and conformational properties of the ligand. The 2‐silyl‐1,3‐diphosphapropene‐bis(chlorogold) complexes catalyzed cycloisomerization reactions of 1,6‐enyne derivatives even in the absence of silver co‐catalyst, and were able to be recovered after the reaction. The catalytic activity of the digold complexes primarily depended on the sp²‐type phosphorus atom and the silyl group, and could be tuned by the sp³‐phosphino group. Additionally, results on the catalytic activity of the digold complex in the presence and absence of silver salts showed considerable differences.     

Proposal for generation of high-intensity monochromatic Cherenkov radiation in THz range by femtosecond electron bunches in impurity-doped semiconductor tube

A novel method to generate high-power THz radiation is proposed. If a beam with a bunch length on the order of 100 fs is injected into an electron–hole plasma of a semiconductor with a plasma frequency on the order of THz, THz wake fields are coherently generated. If the beam moves on the axis of a hollow tube covered by a metal, the frequency spectrum of the radiation is composed of discrete components. Monochromatic radiation is obtained by making only the lowest frequency component coherent.     

Mass balance method for purity assay of phthalic acid esters: development of primary reference materials as traceability sources in the Japan Calibration Service System

Purity assay of high-purity materials (HPMs) of phthalic acid esters (PAEs) was carried out by means of a mass balance method. In this method, chromatographic methods such as gas chromatography-flame ionization detector (GC-FID) and/or high-performance liquid chromatography (HPLC) in combination with other methods such as Karl-Fischer (KF) titration and vacuum evaporation (VE) were applied. The sum of the impurities estimated by these methods allowed the estimation of the purity of the main component by difference. Seven PAEs with varying side chain structures and levels of impurities were analysed on a systematic way in which impurities were classified into several groups in terms of their abundance, availability of qualitative information and availability of authentic compounds, etc. The absolute quantity of each impurity was determined by GC-FID and/or HPLC based on the calibration made by the authentic compounds of impurities whenever available. The purities in mass fraction of these PAEs were certified at the National Metrology Institute of Japan (NMIJ), and the PAEs were registered as primary reference materials playing an essential role in linking the metrological traceability of the Japan Calibration Service System (JCSS) to the International System of Units (SI).     

Electrochemical Synthesis of Thienoacene Derivatives: Transition-Metal-Free Dehydrogenative C−S Coupling Promoted by a Halogen Mediator

The first electrochemical dehydrogenative C−S bond formation leading to thienoacene derivatives is described. Several thienoacene derivatives were synthesized by dehydrogenative C−H/S−H coupling. The addition of ⁿBu₄NBr, which catalytically promoted the reaction as a halogen mediator, was essential.     

Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State

Femtosecond time-resolved absorption and picosecond time-resolved emission measurements were carried out for highly concentrated aqueous solutions of K₂[Pt(CN)₄] to investigate excited-state dynamics of the [Pt(CN)₄²⁻] oligomers formed with metallophilic interactions. Time-resolved absorption spectra exhibit complicated dynamics that are represented with five time constants. Among them, the 90-ps and 400-ps dynamics were assigned to the S₁ → T₁ intersystem crossing of the trimer and tetramer coexisting in the solution by comparison with the fluorescence decays. Clear oscillations of transient absorption were observed in the first few picoseconds, and the frequency-detected-wavelength 2D analysis revealed that the 135-cm⁻¹ and 65-cm⁻¹ oscillations arise from the Pt–Pt stretch motions of the S₁ trimer and S₁ tetramer, respectively. The obtained time-resolved spectroscopic data provide a clear view of the excited-state dynamics of the [Pt(CN)₄²⁻] oligomers in the femto-/picosecond time region.     

Estimation of 47Sc and 177Lu production rates from their natural targets in Kyoto University Research Reactor

Journal of Radioanalytical and Nuclear Chemistry - To assess the capability of Kyoto University Research Reactor to supply the domestic needs of medical isotopes, its neutron flux has been fully...     

Reaction of a Dialumene‐Benzene Adduct with Diphenylacetylene: Formation of 3,4‐Dialuminacyclobutene and 5,6‐Dialuminabicyclo[2.1.1]hex‐2‐ene Derivatives

Reaction of a dialumene‐benzene adduct bearing bulky aryl substituents with diphenylacetylene was found to give a novel 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene derivative in addition to the 3,4‐dialuminacyclobutene derivative, the formal [2+2]cycloadduct of an intermediary dialumene with diphenylacetylene. The molecular structure of the newly obtained 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene has been elucidated by X‐ray crystallographic analysis.