Preparation and Photophysical and Photoelectrochemical Properties of a Covalently Fixed Porphyrin–Chemically Converted Graphene Composite

Chemically converted graphene (CCG) covalently linked with porphyrins has been prepared by a Suzuki coupling reaction between iodophenyl‐functionalized CCG and porphyrin boronic ester. The covalently linked CCG–porphyrin composite was designed to possess a short, rigid phenylene spacer between the porphyrin and the CCG. The composite material formed stable dispersions in DMF and the structure was characterized by spectroscopic, thermal, and microscopic measurements. In steady‐state photoluminescence spectra, the emission from the porphyrin linked to the CCG was quenched strongly relative to that of the porphyrin reference. Fluorescence lifetime and femtosecond transient absorption measurements of the porphyrin‐linked CCG revealed a short‐lived porphyrin singlet excited state (38 ps) without yielding the porphyrin radical cation, thereby substantiating the occurrence of energy transfer from the porphyrin excited state to the CCG and subsequent rapid decay of the CCG excited state to the ground state. Consistently, the photocurrent action spectrum of a photoelectrochemical device with a SnO₂ electrode coated with the porphyrin‐linked CCG exhibited no photocurrent response from the porphyrin absorption. The results obtained here provide deep insight into the interaction between graphenes and π‐conjugated systems in the excited and ground states.     

Electronic spectra of the jet-cooled 1-methylvinylthio radical

Electronic spectra of the B?-X? transition of the 1-methylvinylthio radical were observed in a discharged jet of propylene sulfide by laser-induced fluorescence spectroscopy. Identification of the spectral carrier was made by comparing the observed spectra with results of molecular orbital calculations, in particular, for vibrational frequencies, rotational contour simulations, and the Franck-Condon simulations. Vibrational structures observed in the electronic spectra indicate that the 1-methylvinylthio radical can be regarded as a molecule with C(s) symmetry at the zero-point levels of both the excited and ground states.     

Novel sample preparation technique with needle-type micro-extraction device for volatile organic compounds in indoor air samples

A novel needle-type sample preparation device was developed for the effective preconcentration of volatile organic compounds (VOCs) in indoor air before gas chromatography–mass spectrometry (GC–MS) analysis. To develop a device for extracting a wide range of VOCs typically found in indoor air, several types of particulate sorbents were tested as the extraction medium in the needle-type extraction device. To determine the content of these VOCs, air samples were collected for 30 min with the packed sorbent(s) in the extraction needle, and the extracted VOCs were thermally desorbed in a GC injection port by the direct insertion of the needle. A double-bed sorbent consisting of a needle packed with divinylbenzene and activated carbon particles exhibited excellent extraction and desorption performance and adequate extraction capacity for all the investigated VOCs. The results also clearly demonstrated that the proposed sample preparation method is a more rapid, simpler extraction/desorption technique than traditional sample preparation methods.     

Synthesis of arylglycine and mandelic acid derivatives through carboxylations of α-amido and α-acetoxy stannanes with carbon dioxide

Incorporation reactions of carbon dioxide (CO(2)) with N-Boc-α-amido and α-acetoxy stannanes were developed using CsF as a mild tin activator. Monoprotected α-amido stannanes could be used, and the corresponding arylglycine derivatives were obtained in moderate-to-high yields under 1 MPa (10 atm) of CO(2) pressure. α-Acetoxy stannanes also underwent carboxylation to afford mandelic acid derivatives in excellent yields under ambient CO(2) pressure. Both transformations enabled the synthesis of α-tertiary and α-quaternary carboxylic acid derivatives. In addition, the chirality of (S)-N-tert-butylsulfonyl-α-amido stannanes was transferred with up to 90% inversion of configuration at 100 °C.     

Oligonucleotide-templated reactions for sensing nucleic acids

Oligonucleotide-templated reactions are useful for applying nucleic acid sensing. Various chemistries for oligonucleotide-templated reaction have been reported so far. Major scientific interests are focused on the development of signal amplification systems and signal generation systems. We introduce the recent advances of oligonucleotide-templated reaction in consideration of the above two points.     

Synthesis and properties of naphthobisbenzo[b]thiophenes: structural curvature of higher acene frameworks for solubility enhancement and high-order orientation in crystalline states

The syntheses of naphtho[2,3-b:7,6-b′]- and naphtho[2,1-b:5,6-b′]bisbenzo[b]thiophenes (NBBTs) are achieved via inter- and intramolecular stepwise Friedel–Crafts-type reactions. The structural curvature of these NBBTs are found to improve their solubility in organic solvents, and to form well-defined herringbone structures in single crystals, especially when the C_2v symmetrical naphtho[2,3-b:7,6-b′]bisbenzo[b]thiophene takes the form of asymmetric space groups in a parallel direction with each other, and having exhibited OFET characteristics with a hole mobility of 7 × 10^?5 cm² V^?1 s^?1.     

Magnetic and neutron diffraction study on melilite-type oxides Sr2MGe2O7 (M = Mn, Co)

The crystal structures and magnetic properties of melilite-type oxides Sr(2)MGe(2)O(7) (M = Mn, Co) were investigated. These compounds crystallize in the melilite structure with space group P ?42(1)m, in which the M and Ge ions occupy two kinds of tetrahedral sites in an ordered manner. The magnetic M ions form a square-planar lattice in the ab plane. Both compounds do not show the structural phase transition down to 2.5 K. The temperature dependence of magnetic susceptibility for Sr(2)MnGe(2)O(7) shows a broad peak at ~6.0 K because of a two-dimensional magnetic interaction between Mn ions in the ab plane. At 4.4 K, an antiferromagnetic transition was observed. The magnetic structure was determined by the neutron powder diffraction measurements at 2.5 K. It can be represented by the propagation vector k = (0, 0, 1/2), and the magnetic moments of Mn(2+) (3.99 μ(B)) ions order antiferromagnetically in a collinear manner along the c axis. On the other hand, Sr(2)CoGe(2)O(7) shows an antiferromagnetic transition at 6.5 K with divergence between zero-field-cooled and field-cooled susceptibilities. Its magnetic structure determined at 2.5 K has a magnetic propagation vector k = (0, 0, 0), and the ordered magnetic moment of Co(2+) (2.81 μ(B)) adopts a collinear arrangement lying on the ab plane.