Chemical Bonding in Polarised Push–Pull Ethylenes

1,1‐Diamino‐2,2‐bis(triflyl)ethylenes with both twisted and planar structures around the partial “C=C” bond were synthesised. Bonding properties in these compounds were analysed by an experimental approach using high‐resolution X‐ray diffraction data treated with X‐ray wavefunction refinement (XWR). In the twisted compound, a dominant contribution of the charge‐separated resonance structure was revealed. On the contrary, the nearly planar compound still showed π‐bonding character, however, with a considerable contribution of the charge‐separated resonance structure.     

Core–Shell‐Structured LaTaON2 Transformed from LaKNaTaO5 Plates for Enhanced Photocatalytic H2 Evolution

LaTaON₂ is a photocatalyst with intense visible light absorption up to 650 nm, but exhibits low H₂ evolution activity owing to uncontrolled facets and high defect densities. In this work, core–shell‐structured plate‐like LaKNaTaO₅/LaTaON₂ was synthesized by nitriding a layered perovskite‐type LaKNaTaO₅. The volatilization of K and Na species during the nitridation promoted the rapid transformation of LaKNaTaO₅ into LaTaON₂ along [010] direction with the plate‐like shape retained. This yielded high‐quality LaTaON₂ shells exposing (010) facets on the lattice‐matched LaKNaTaO₅ cores. After loading with a Rh co‐catalyst, LaKNaTaO₅/LaTaON₂ showed photocatalytic H₂ evolution activity four times greater than that obtained from conventional irregular‐shaped LaTaON₂ powders and utilized visible light up to 620 nm. This work provides a novel strategy yielding oxynitrides with well‐defined facets and low defect densities by selecting lattice‐matched oxide precursors containing volatile components.     

Extending spin-symmetry projected coupled-cluster to large model spaces using an iterative null-space projection technique

Recently, we introduced an orbital-invariant approximate coupled-cluster (CC) method in the spin-projection manifold. The multi-determinantal property of spin-projection means that the parametrization in the spin-extended CC (ECC) ansatz is nonorthogonal and overcomplete. Therefore, the linear dependencies must be removed by an orthogonalization procedure to obtain meaningful solutions. Multi-reference methods often achieve this by diagonalizing a metric of the equation system, but this is not feasible with ECC because of the enormous size of the metric, a consequence of the incomplete active space of the spin-projected Hartree–Fock reference. As a result, the applicability of ECC has been limited to small benchmark systems, for which the ansatz was shown to be superior to the configuration interaction and linearized approximations. In this article, we provide a solution to this problem that completely avoids the metric diagonalization by iteratively projecting out its null-space from the working equations. As the additional computational cost required for this iterative projection is only marginal, it greatly expands the application range of ECC. We demonstrate the potential of approximate ECC by studying the complete basis set limit of F₂ and transition metal complexes such as NiO, Mn₂, and [Cu₂O₂]²⁺ , which have all been hindered by the prohibitively large metric size. We also identify the potential inadequacy of the molecular orbitals given by spin-projected Hartree–Fock in some cases, and propose possible solutions. © 2018 Wiley Periodicals, Inc.     

Chemical constituents from the flowers of Satsuma mandarin and their free radical scavenging and α-glucosidase inhibitory activities

Flowers of Citrus plants are used as mild sedatives and for the treatment of insomnia in traditional medicines. In Japan, tea made from the flowers of Satsuma mandarin is consumed as healthy drink. Hesperidin (1), hesperetin (2), rutin (3), quercetin (4), nicotiflorin (5), eriocitrin (6), narirutin (7), phenylethyl glucoside (8) and unshuoside A (9) were isolated from the MeOH extract of fresh flowers. Structure elucidation of these compounds was performed on the basis of NMR spectroscopic data. Among them, rutin (3), quercetin (4) and eriocitrin (6) showed potent free radical scavenging activity, whereas hesperetin (2) and quercetin (4) showed potent α-glucosidase inhibitory activity.     

Laser‐Induced Fluorometry for Capillary Electrophoresis

Laser‐induced fluorometry (LIF) has achieved the detection of single molecules, which ranks it among the most sensitive of detection techniques, whereas capillary electrophoresis (CE) is known as a powerful separation method with resolution that is beyond the reach of many other types of chromatography. Therefore, a coupling of LIF with CE has established an unrivaled analytical technique in terms of sensitivity and resolution. CE‐LIF has demonstrated excellent performance in bioanalytical chemistry for the high‐resolution separation and highly sensitive detection of DNAs, proteins, and small bioactive molecules. This review describes the CE‐LIF methods developed by the author's group that include indirect and direct detection using diode lasers, post‐column derivatization, and Hadamard transformation, as well as applications to the binding assays of specific DNA immunoassays of proteins and to the determination of anticancer drugs.     

Coherent transfer of light polarization to electron spins in a semiconductor

We demonstrate that the superposition of light polarization states is coherently transferred to electron spins in a semiconductor quantum well. By using time-resolved Kerr rotation, we observe the initial phase of Larmor precession of electron spins whose coherence is transferred from light. To break the electron-hole spin entanglement, we utilized the big discrepancy between the transverse g factors of electrons and light-holes. The result encourages us to make a quantum media converter between flying photon qubits and stationary electron-spin qubits in semiconductors.     

Direct observation of dark excitons in micelle-wrapped single-wall carbon nanotubes

We have performed electroabsorption spectroscopy on micelle-wrapped single-wall carbon nanotubes. In semiconducting nanotubes, many oscillating structures composed of the increase and decrease of absorption are observed in the spectra in the region of the first and second absorption bands, E11 and E22. The spectral shape is reproduced mainly by the second-derivative curve of the absorption spectrum, which indicates the presence of nearly degenerate bright and dark excitonic states.     

Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.