start-ver=1.4 cd-journal=joma no-vol= cd-vols= no-issue= article-no= start-page= end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2025 dt-pub=20250430 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=High-Resolution HPLC for Separating Peptide-Oligonucleotide Conjugates en-subtitle= kn-subtitle= en-abstract= kn-abstract=Peptide-oligonucleotide conjugates (POCs) are chimeric molecules that combine the specificity of oligonucleotides with the functionality of peptides, improving the delivery and therapeutic potential of nucleic acid-based drugs. However, the analysis of POCs, particularly those containing arginine-rich sequences, poses major challenges because of aggregation caused by electrostatic interactions. In this study, we developed an optimized high-performance liquid chromatography (HPLC) method for analyzing POCs. Using a conjugate of DNA and nona-arginine as a model compound, we systematically investigated the effects of various analytical parameters, including column type, column temperature, mobile-phase composition, and pH. A column packed with C18 resin with wide pores combined with butylammonium acetate as the ion-pairing reagent and an optimal column temperature of 80 degrees C provided superior peak resolution and sensitivity. The optimized conditions gave clear separation of POCs from unlinked oligonucleotides and enabled the detection of nucleic acid fragments lacking an alkyne moiety as a linkage part, which is critical for quality control. Our HPLC method is robust and reproducible and substantially reduces the complexity, time, and cost associated with the POC analysis. The method may improve the efficiency of quality control in the production of POCs, thereby supporting their development as promising therapeutic agents for clinical applications. en-copyright= kn-copyright= en-aut-name=NaganumaMiyako en-aut-sei=Naganuma en-aut-mei=Miyako kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=TsujiGenichiro en-aut-sei=Tsuji en-aut-mei=Genichiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=AmiyaMisato en-aut-sei=Amiya en-aut-mei=Misato kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=HiraiReira en-aut-sei=Hirai en-aut-mei=Reira kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=HiguchiYuki en-aut-sei=Higuchi en-aut-mei=Yuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=HataNaoko en-aut-sei=Hata en-aut-mei=Naoko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=NozawaSaoko en-aut-sei=Nozawa en-aut-mei=Saoko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=WatanabeDaishi en-aut-sei=Watanabe en-aut-mei=Daishi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=NakajimaTaeko en-aut-sei=Nakajima en-aut-mei=Taeko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=DemizuYosuke en-aut-sei=Demizu en-aut-mei=Yosuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= affil-num=1 en-affil=Division of Organic Chemistry, National Institute of Health Sciences kn-affil= affil-num=2 en-affil=Division of Organic Chemistry, National Institute of Health Sciences kn-affil= affil-num=3 en-affil=YMC CO., LTD. kn-affil= affil-num=4 en-affil=YMC CO., LTD. kn-affil= affil-num=5 en-affil=YMC CO., LTD. kn-affil= affil-num=6 en-affil=YMC CO., LTD. kn-affil= affil-num=7 en-affil=YMC CO., LTD. kn-affil= affil-num=8 en-affil=Division of Organic Chemistry, National Institute of Health Sciences kn-affil= affil-num=9 en-affil=YMC CO., LTD. kn-affil= affil-num=10 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Division of Pharmaceutical Science, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=9 cd-vols= no-issue=50 article-no= start-page=50041 end-page=50048 dt-received= dt-revised= dt-accepted= dt-pub-year=2024 dt-pub=20241205 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Conformational Flexibility of D1-Glu189: A Crucial Determinant in Substrate Water Selection, Positioning, and Stabilization within the Oxygen-Evolving Complex of Photosystem II en-subtitle= kn-subtitle= en-abstract= kn-abstract=Photosynthetic water oxidation is a vital process responsible for producing dioxygen and supplying the energy necessary to sustain life on Earth. This fundamental reaction is catalyzed by the oxygen-evolving complex (OEC) of photosystem II, which houses the Mn4CaO5 cluster as its catalytic core. In this study, we specifically focus on the D1-Glu189 amino acid residue, which serves as a direct ligand to the Mn4CaO5 cluster. Our primary goal is to explore, using density functional theory (DFT), how the conformational flexibility of the D1-Glu189 side chain influences crucial catalytic processes, particularly the selection, positioning, and stabilization of a substrate water molecule within the OEC. Our investigation is based on a hypothesis put forth by Li et al. (Nature, 2024, 626, 670), which suggests that during the transition from the S2 to S3 state, a specific water molecule temporarily coordinating with the Ca ion, referred to as O6*, may exist as a hydroxide ion (OH-). Our results demonstrate a key mechanism by which the detachment of the D1-Glu189 carboxylate group from its coordination with the Ca ion allows the creation of a specialized microenvironment within the OEC that enables the selective attraction of O6* in its deprotonated form (OH-) and stabilizes it at the catalytic metal (MnD) site. Our findings indicate that D1-Glu189 is not only a structural ligand for the Ca ion but may also play an active and dynamic role in the catalytic process, positioning O6* optimally for its subsequent participation in the oxidation sequence during the water-splitting cycle. en-copyright= kn-copyright= en-aut-name=IsobeHiroshi en-aut-sei=Isobe en-aut-mei=Hiroshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=SugaMichihiro en-aut-sei=Suga en-aut-mei=Michihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=ShenJian-Ren en-aut-sei=Shen en-aut-mei=Jian-Ren kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=YamaguchiKizashi en-aut-sei=Yamaguchi en-aut-mei=Kizashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=2 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=3 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=4 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=5 en-affil=Center for Quantum Information and Quantum Biology, Osaka University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=9 cd-vols= no-issue=19 article-no= start-page=21287 end-page=21297 dt-received= dt-revised= dt-accepted= dt-pub-year=2024 dt-pub=20240501 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Superstructure of Fe5–xGeTe2 Determined by Te K-Edge Extended X-ray Absorption Fine Structure and Te Kα X-ray Fluorescence Holography en-subtitle= kn-subtitle= en-abstract= kn-abstract=The local structure of the two-dimensional van der Waals material, Fe5–xGeTe2, which exhibits unique structural/magnetic phase transitions, was investigated by Te K-edge extended X-ray absorption fine structure (EXAFS) and Te Kα X-ray fluorescence holography (XFH) over a wide temperature range. The formation of a trimer of Te atoms at low temperatures has been fully explored using these methods. An increase in the Te–Fe distance at approximately 150 K was suggested by EXAFS and presumably indicates the formation of a Te trimer. Moreover, XFH displayed clear atomic images of Te atoms. Additionally, the distance between the Te atoms shortened, as confirmed from the atomic images reconstructed from XFH, indicating the formation of a trimer of Te atoms, i.e., a charge-ordered (3⎯⎯√×3⎯⎯√)𝑅30◦ superstructure. Furthermore, Te Kα XFH provided unambiguous atomic images of Fe atoms occupying the Fe1 site; the images were not clearly observed in the Ge Kα XFH that was previously reported because of the low occupancy of Fe and Ge atoms. In this study, EXAFS and XFH clearly showed the local structure around the Te atom; in particular, the formation of Te trimers caused by charge-ordered phase transitions was clearly confirmed. The charge-ordered phase transition is fully discussed based on the structural variation at low temperatures, as established from EXAFS and XFH. en-copyright= kn-copyright= en-aut-name=EguchiRitsuko en-aut-sei=Eguchi en-aut-mei=Ritsuko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SekharHalubai en-aut-sei=Sekhar en-aut-mei=Halubai kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=KimuraKoji en-aut-sei=Kimura en-aut-mei=Koji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=MasaiHirokazu en-aut-sei=Masai en-aut-mei=Hirokazu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=HappoNaohisa en-aut-sei=Happo en-aut-mei=Naohisa kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=IkedaMitsuki en-aut-sei=Ikeda en-aut-mei=Mitsuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=YamamotoYuki en-aut-sei=Yamamoto en-aut-mei=Yuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=UtsumiMasaki en-aut-sei=Utsumi en-aut-mei=Masaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=GotoHidenori en-aut-sei=Goto en-aut-mei=Hidenori kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=TakabayashiYasuhiro en-aut-sei=Takabayashi en-aut-mei=Yasuhiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= en-aut-name=TajiriHiroo en-aut-sei=Tajiri en-aut-mei=Hiroo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=11 ORCID= en-aut-name=HayashiKoichi en-aut-sei=Hayashi en-aut-mei=Koichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=12 ORCID= en-aut-name=KubozonoYoshihiro en-aut-sei=Kubozono en-aut-mei=Yoshihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=13 ORCID= affil-num=1 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=2 en-affil=Department of Physical Science and Technology, Nagoya Institute of Technology kn-affil= affil-num=3 en-affil=Department of Physical Science and Technology, Nagoya Institute of Technology kn-affil= affil-num=4 en-affil=Department of Materials and Chemistry, National Institute of Advanced Industrial Science and Technology (AIST) kn-affil= affil-num=5 en-affil=Graduate School of Information Sciences, Hiroshima City University kn-affil= affil-num=6 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=7 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=8 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=9 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=10 en-affil=Department of Physical Science and Technology, Nagoya Institute of Technology kn-affil= affil-num=11 en-affil=Japan Synchrotron Radiation Research Institute (JASRI) kn-affil= affil-num=12 en-affil=Department of Physical Science and Technology, Nagoya Institute of Technology kn-affil= affil-num=13 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=3 cd-vols= no-issue=5 article-no= start-page=394 end-page=405 dt-received= dt-revised= dt-accepted= dt-pub-year=2023 dt-pub=20230911 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Highly Stretchable Stress-Strain Sensor from Elastomer Nanocomposites with Movable Cross-links and Ketjenblack en-subtitle= kn-subtitle= en-abstract= kn-abstract=Practical applications like very thin stress-strain sensors require high strength, stretchability, and conductivity, simultaneously. One of the approaches is improving the toughness of the stress-strain sensing materials. Polymeric materials with movable cross-links in which the polymer chain penetrates the cavity of cyclodextrin (CD) demonstrate enhanced strength and stretchability, simultaneously. We designed two approaches that utilize elastomer nanocomposites with movable cross-links and carbon filler (ketjenblack, KB). One approach is mixing SC (a single movable cross-network material), a linear polymer (poly(ethyl acrylate), PEA), and KB to obtain their composite. The electrical resistance increases proportionally with tensile strain, leading to the application of this composite as a stress- strain sensor. The responses of this material are stable for over 100 loading and unloading cycles. The other approach is a composite made with KB and a movable cross-network elastomer for knitting dissimilar polymers (KP), where movable cross-links connect the CD-modified polystyrene (PSCD) and PEA. The obtained composite acts as a highly sensitive stress-strain sensor that exhibits an exponential increase in resistance with increasing tensile strain due to the polymer dethreading from the CD rings. The designed preparations of highly repeatable or highly responsive stress-strain sensors with good mechanical properties can help broaden their application in electrical devices. en-copyright= kn-copyright= en-aut-name=IkuraRyohei en-aut-sei=Ikura en-aut-mei=Ryohei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KajimotoKota en-aut-sei=Kajimoto en-aut-mei=Kota kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=ParkJunsu en-aut-sei=Park en-aut-mei=Junsu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=MurayamaShunsuke en-aut-sei=Murayama en-aut-mei=Shunsuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=FujiwaraYusei en-aut-sei=Fujiwara en-aut-mei=Yusei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=OsakiMotofumi en-aut-sei=Osaki en-aut-mei=Motofumi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=SuzukiTomohiro en-aut-sei=Suzuki en-aut-mei=Tomohiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=ShirakawaHidenori en-aut-sei=Shirakawa en-aut-mei=Hidenori kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=KitamuraYujiro en-aut-sei=Kitamura en-aut-mei=Yujiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=TakahashiHiroaki en-aut-sei=Takahashi en-aut-mei=Hiroaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= en-aut-name=OhashiYasumasa en-aut-sei=Ohashi en-aut-mei=Yasumasa kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=11 ORCID= en-aut-name=ObataSeiji en-aut-sei=Obata en-aut-mei=Seiji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=12 ORCID= en-aut-name=HaradaAkira en-aut-sei=Harada en-aut-mei=Akira kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=13 ORCID= en-aut-name=IkemotoYuka en-aut-sei=Ikemoto en-aut-mei=Yuka kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=14 ORCID= en-aut-name=NishinaYuta en-aut-sei=Nishina en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=15 ORCID= en-aut-name=UetsujiYasutomo en-aut-sei=Uetsuji en-aut-mei=Yasutomo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=16 ORCID= en-aut-name=MatsubaGo en-aut-sei=Matsuba en-aut-mei=Go kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=17 ORCID= en-aut-name=TakashimaYoshinori en-aut-sei=Takashima en-aut-mei=Yoshinori kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=18 ORCID= affil-num=1 en-affil=Department of Macromolecular Science, Graduate School of Science and Forefront Research Center for Fundamental Sciences, Osaka University kn-affil= affil-num=2 en-affil=Department of Macromolecular Science, Graduate School of Science, Osaka University kn-affil= affil-num=3 en-affil=Department of Macromolecular Science, Graduate School of Science and Forefront Research Center for Fundamental Sciences, Osaka University kn-affil= affil-num=4 en-affil=Graduate School of Organic Materials Engineering, Yamagata University kn-affil= affil-num=5 en-affil=Department of Mechanical Engineering, Osaka Institute of Technology kn-affil= affil-num=6 en-affil=Department of Macromolecular Science, Graduate School of Science and Forefront Research Center for Fundamental Sciences, Osaka University kn-affil= affil-num=7 en-affil=Kanagawa Technical Center, Yushiro Chemical Industry Co., Ltd. kn-affil= affil-num=8 en-affil=Kanagawa Technical Center, Yushiro Chemical Industry Co., Ltd. kn-affil= affil-num=9 en-affil=Kanagawa Technical Center, Yushiro Chemical Industry Co., Ltd. kn-affil= affil-num=10 en-affil=Kanagawa Technical Center, Yushiro Chemical Industry Co., Ltd. kn-affil= affil-num=11 en-affil=Kanagawa Technical Center, Yushiro Chemical Industry Co., Ltd. kn-affil= affil-num=12 en-affil=Research Core for Interdisciplinary Sciences, Okayama University kn-affil= affil-num=13 en-affil=SANKEN (The Institute of Scientific and Industrial Research), Osaka University kn-affil= affil-num=14 en-affil=Japan Synchrotron Radiation Research Institute kn-affil= affil-num=15 en-affil=Research Core for Interdisciplinary Sciences, Okayama University kn-affil= affil-num=16 en-affil=Department of Mechanical Engineering, Osaka Institute of Technology kn-affil= affil-num=17 en-affil=Graduate School of Organic Materials Engineering, Yamagata University kn-affil= affil-num=18 en-affil=Department of Macromolecular Science, Graduate School of Science and Forefront Research Center for Fundamental Sciences, Osaka University kn-affil= en-keyword=stress-strain sensor kn-keyword=stress-strain sensor en-keyword=carbon composite kn-keyword=carbon composite en-keyword=movable cross-link kn-keyword=movable cross-link en-keyword=supramolecular materials kn-keyword=supramolecular materials en-keyword=polymericmaterials kn-keyword=polymericmaterials en-keyword=tough materials kn-keyword=tough materials en-keyword=upcycling kn-keyword=upcycling END start-ver=1.4 cd-journal=joma no-vol=8 cd-vols= no-issue=12 article-no= start-page=11213 end-page=11219 dt-received= dt-revised= dt-accepted= dt-pub-year=2023 dt-pub=20230317 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Development of Pipetteless Paper-Based Analytical Devices with a Volume Gauge en-subtitle= kn-subtitle= en-abstract= kn-abstract=In this work, we propose a new design for paper based analytical devices (PADs) that eliminate the need to use a micropipette for sample introduction. With this design, a PAD is equipped with a distance-based detection channel that is connected to a storage channel that indicates the volume of a sample introduced into the PAD. The analyte in the sample solution reacts with a colorimetric reagent deposited into the distance-based detection channel as the sample solution flows into the storage channel where the volume is measured. The ratio of the lengths of the detection channel and that of the storage channel (D/S ratio) are constant for a sample containing a certain concentration, which is independent of the introduced volume. Therefore, the PADs permit volume-independent quantification using a dropper instead of a micropipette because the length of the storage channel plays the role of a volume gauge to estimate the introduced sample volume. In this study, the D/S ratios obtained with a dropper were comparable to those obtained with a micropipette, which confirmed that precise volume control is unnecessary for this PAD system. The proposed PADs were applied to the determinations of iron and bovine serum albumin using bathophenanthroline and tetrabromophenol blue as colorimetric reagents, respectively. The calibration curves showed good linear relationships with coefficients of 0.989 for iron and 0.994 for bovine serum albumin, respectively. en-copyright= kn-copyright= en-aut-name=DanchanaKaewta en-aut-sei=Danchana en-aut-mei=Kaewta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=IwasakiHiroshi en-aut-sei=Iwasaki en-aut-mei=Hiroshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=ThayawutthikunYada en-aut-sei=Thayawutthikun en-aut-mei=Yada kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SaetearPhoonthawee en-aut-sei=Saetear en-aut-mei=Phoonthawee kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=KanetaTakashi en-aut-sei=Kaneta en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Department of Chemistry, Okayama University kn-affil= affil-num=2 en-affil=Department of Chemistry, Okayama University kn-affil= affil-num=3 en-affil=Flow Innovation-Research for Science and Technology Laboratories (FIRST Labs), Mahidol University kn-affil= affil-num=4 en-affil=Flow Innovation-Research for Science and Technology Laboratories (FIRST Labs), Mahidol University kn-affil= affil-num=5 en-affil=Department of Chemistry, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=8 cd-vols= no-issue= article-no= start-page=4826 end-page=4834 dt-received= dt-revised= dt-accepted= dt-pub-year=2023 dt-pub=20230125 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Detection of Membrane Potential-Dependent Rhodopsin Fluorescence Using Low-Intensity Light Emitting Diode for Long-Term Imaging en-subtitle= kn-subtitle= en-abstract= kn-abstract=Microbial rhodopsin is a family of photoreceptive membrane proteins that commonly consist of a seven-transmembrane domain and a derivative of vitamin-A, retinal, as a chromophore. In 2011, archaeorhodopsin-3 (AR3) was shown to exhibit voltage-dependent fluorescence changes in mammalian cells. Since then, AR3 and its variants have been used as genetically encoded voltage indicators, in which mostly intense laser stimulation (1-1000 W/cm(2)) is used for the detection of dim fluorescence of rhodopsin, leading to high spatiotemporal resolution. However, intense laser stimulation potentially causes serious cell damage, particularly during long-term imaging over minutes. In this study, we present the successful detection of voltage-sensitive fluorescence of AR3 and its high fluorescence mutant Archon1 in a variety of mammalian cell lines using low-intensity light emitting diode stimulation (0.15 W/cm2) with long exposure time (500 ms). The detection system enables real-time imaging of drug-induced slow changes in voltage within the cells for minutes harmlessly and without fluorescence bleaching. Therefore, we demonstrate a method to quantitatively understand the dynamics of slow changes in membrane voltage on long time scales. en-copyright= kn-copyright= en-aut-name=KawanishiShiho en-aut-sei=Kawanishi en-aut-mei=Shiho kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KojimaKeiichi en-aut-sei=Kojima en-aut-mei=Keiichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=ShibukawaAtsushi en-aut-sei=Shibukawa en-aut-mei=Atsushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SakamotoMasayuki en-aut-sei=Sakamoto en-aut-mei=Masayuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=SudoYuki en-aut-sei=Sudo en-aut-mei=Yuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences and Faculty of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University kn-affil= affil-num=4 en-affil=Department of Optical Neural and Molecular Physiology, Graduate School of Biostudies kn-affil= affil-num=5 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences and Faculty of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= END start-ver=1.4 cd-journal=joma no-vol=7 cd-vols= no-issue=50 article-no= start-page=46573 end-page=46582 dt-received= dt-revised= dt-accepted= dt-pub-year=2022 dt-pub=20221220 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Oligoarginine-Conjugated Peptide Foldamers Inhibiting Vitamin D Receptor-Mediated Transcription en-subtitle= kn-subtitle= en-abstract= kn-abstract=The vitamin D receptor (VDR) is a nuclear receptor, which is involved in several physiological processes, including differentiation and bone homeostasis. The VDR is a promising target for the development of drugs against cancer and bone-related diseases. To date, several VDR antagonists, which bind to the ligand binding domain of the VDR and compete with the endogenous agonist 1 alpha,25(OH)D3, have been reported. However, these ligands contain a secosteroidal skeleton, which is chemically unstable and complicated to synthesize. A few VDR antagonists with a nonsecosteroidal skeleton have been reported. Alternative inhibitors against VDR transactivation that act via different mechanisms are desirable. Here, we developed peptide-based VDR inhibitors capable of disrupting the VDR-coactivator interaction. It was reported that helical SRC2-3 peptides strongly bound to the VDR and competed with the coactivator in vitro. Therefore, we designed and synthesized a series of SRC2-3 derivatives by the introduction of nonproteinogenic amino acids, such as beta-amino acids, and by side-chain stapling to stabilize helical structures and provide resistance against digestive enzymes. In addition, conjugation with a cell-penetrating peptide increased the cell membrane permeability and was a promising strategy for intracellular VDR inhibition. The nona-arginine-conjugated peptides 24 with side-chain stapling and 25 with cyclic beta-amino acids showed strong intracellular VDR inhibitory activity, resulting in suppression of the target gene expression and inhibition of the cell differentiation of HL-60 cells. Herein, the peptide design, structure-activity relationship (SAR) study, and biological evaluation of the peptides are described. en-copyright= kn-copyright= en-aut-name=TakyoMami en-aut-sei=Takyo en-aut-mei=Mami kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SatoYumi en-aut-sei=Sato en-aut-mei=Yumi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=HirataNaoya en-aut-sei=Hirata en-aut-mei=Naoya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=TsuchiyaKeisuke en-aut-sei=Tsuchiya en-aut-mei=Keisuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=IshidaHiroaki en-aut-sei=Ishida en-aut-mei=Hiroaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=KuroharaTakashi en-aut-sei=Kurohara en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=YanaseYuta en-aut-sei=Yanase en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=ItoTakahito en-aut-sei=Ito en-aut-mei=Takahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=KandaYasunari en-aut-sei=Kanda en-aut-mei=Yasunari kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=YamamotoKeiko en-aut-sei=Yamamoto en-aut-mei=Keiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= en-aut-name=MisawaTakashi en-aut-sei=Misawa en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=11 ORCID= en-aut-name=DemizuYosuke en-aut-sei=Demizu en-aut-mei=Yosuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=12 ORCID= affil-num=1 en-affil=National Institute of Health Sciences kn-affil= affil-num=2 en-affil=National Institute of Health Sciences kn-affil= affil-num=3 en-affil=National Institute of Health Sciences kn-affil= affil-num=4 en-affil=National Institute of Health Sciences kn-affil= affil-num=5 en-affil=Laboratory of Drug Design and Medicinal Chemistry, Showa Pharmaceutical University kn-affil= affil-num=6 en-affil=National Institute of Health Sciences kn-affil= affil-num=7 en-affil=National Institute of Health Sciences kn-affil= affil-num=8 en-affil=National Institute of Health Sciences kn-affil= affil-num=9 en-affil=National Institute of Health Sciences kn-affil= affil-num=10 en-affil=Laboratory of Drug Design and Medicinal Chemistry, Showa Pharmaceutical University kn-affil= affil-num=11 en-affil=National Institute of Health Sciences kn-affil= affil-num=12 en-affil=National Institute of Health Sciences kn-affil= END start-ver=1.4 cd-journal=joma no-vol= cd-vols= no-issue= article-no= start-page=26021 end-page=26028 dt-received= dt-revised= dt-accepted= dt-pub-year=2022 dt-pub=20220722 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Characteristics of Vertical Ga2O3 Schottky Junctions with the Interfacial Hexagonal Boron Nitride Film en-subtitle= kn-subtitle= en-abstract= kn-abstract=We present the device properties of a nickel (Ni)- gallium oxide (Ga2O3) Schottky junction with an interfacial hexagonal boron nitride (hBN) layer. A vertical Schottky junction with the configuration Ni/hBN/Ga2O3/In was created using a chemical vapor-deposited hBN film on a Ga(2)O(3 )substrate. The current-voltage characteristics of the Schottky junction were investigated with and without the hBN interfacial layer. We observed that the turn-on voltage for the forward current of the Schottky junction was significantly enhanced with the hBN interfacial film. Furthermore, the Schottky junction was analyzed under the illumination of deep ultraviolet light (254 nm), obtaining a photoresponsivity of 95.11 mA/W under an applied bias voltage (-7.2 V). The hBN interfacial layer for the Ga2O3-based Schottky junction can serve as a barrier layer to control the turn-on voltage and optimize the device properties for deep-UV photosensor applications. Furthermore, the demonstrated vertical heterojunction with an hBN layer has the potential to be significant for temperature management at the junction interface to develop reliable Ga2O3-based Schottky junction devices. en-copyright= kn-copyright= en-aut-name=RamaVenkata Krishna Rao en-aut-sei=Rama en-aut-mei=Venkata Krishna Rao kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=RanadeAjinkya K. en-aut-sei=Ranade en-aut-mei=Ajinkya K. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=DesaiPradeep en-aut-sei=Desai en-aut-mei=Pradeep kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=TodankarBhagyashri en-aut-sei=Todankar en-aut-mei=Bhagyashri kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=KalitaGolap en-aut-sei=Kalita en-aut-mei=Golap kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=SuzukiHiroo en-aut-sei=Suzuki en-aut-mei=Hiroo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=TanemuraMasaki en-aut-sei=Tanemura en-aut-mei=Masaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=HayashiYasuhiko en-aut-sei=Hayashi en-aut-mei=Yasuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Department of Physical Science and Engineering, Nagoya Institute of Technology kn-affil= affil-num=3 en-affil=Department of Physical Science and Engineering, Nagoya Institute of Technology kn-affil= affil-num=4 en-affil=Department of Physical Science and Engineering, Nagoya Institute of Technology kn-affil= affil-num=5 en-affil=Department of Physical Science and Engineering, Nagoya Institute of Technology kn-affil= affil-num=6 en-affil=Graduate School of Natural Science and Technology kn-affil= affil-num=7 en-affil=Department of Physical Science and Engineering, Nagoya Institute of Technology kn-affil= affil-num=8 en-affil= kn-affil= END start-ver=1.4 cd-journal=joma no-vol=126 cd-vols= no-issue=22 article-no= start-page=9257 end-page=9263 dt-received= dt-revised= dt-accepted= dt-pub-year=2022 dt-pub=20220525 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Role of Oxygen Vacancy in the Photocarrier Dynamics of WO3 Photocatalysts: The Case of Recombination Centers en-subtitle= kn-subtitle= en-abstract= kn-abstract=Defects in powder photocatalysts determine the photocatalytic activity. The addition of defects sometimes enhances the activity, but sometimes decreases it. However, the factors determining the difference between these cases have not been fully elucidated yet. Herein, we investigated the effects of oxygen vacancies on photocarrier dynamics in WO3 powder using broadband transient absorption spectroscopy. It was found that the decay of deeply trapped electrons was accelerated when the number of oxygen vacancies was increased by H-2 reduction. This result suggests that oxygen vacancies in WO3 mainly act as recombination centers. This is in contrast to many other photocatalysts such as TiO2 and SrTiO3, where the carrier lifetime increases with increasing oxygen vacancy concentration. These differences can be attributed to the difference in the distance between oxygen vacancies. When defects are dispersed, trapped electrons need to travel over long distances by repeatedly hopping and tunneling between defects to combine with holes, resulting in decelerated recombination. In contrast, when the defects are connected or located close together, the trapped electrons can readily migrate among defects, leading to enhanced recombination. Control of the distance between defects is thus important for enhancing photocatalytic activity. en-copyright= kn-copyright= en-aut-name=KatoKosaku en-aut-sei=Kato en-aut-mei=Kosaku kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=UemuraYohei en-aut-sei=Uemura en-aut-mei=Yohei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=AsakuraKiyotaka en-aut-sei=Asakura en-aut-mei=Kiyotaka kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=YamakataAkira en-aut-sei=Yamakata en-aut-mei=Akira kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Institute for Molecular Science kn-affil= affil-num=3 en-affil=Institute for Catalysis, Hokkaido University kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=7 cd-vols= no-issue=15 article-no= start-page=12795 end-page=12802 dt-received= dt-revised= dt-accepted= dt-pub-year=2022 dt-pub=20220410 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Eco-Benign Orange-Hued Pigment Derived from Aluminum-Enriched Biogenous Iron Oxide Sheaths en-subtitle= kn-subtitle= en-abstract= kn-abstract=Inorganic pigments have been widely used due to their low cost of production, strong hiding power, and chemical resistance; nevertheless, they have limited hue width and chromaticity. To eliminate these disadvantages, we herein propose the use of an ingenious biotemplate technique to produce Al-enriched biogenic iron oxide (BIOX) materials. Spectrophotometric color analysis showed that high levels of Al inclusion on heat-treated BIOX samples produced heightened yellowish hues and lightness. The Al-enriched BIOX sheaths exhibited a stable tubular structure and excellent thermal stability of color tones after heating at high temperatures and repetitive heat treatments. Ultrastructural analysis and mechanical destruction experiments revealed that the highly chromatic orange-hue of these pigments are ascribed probably to an ingenious cylindrical nanocomposite architecture composed of putative Fe-included low crystalline Al oxide regions and hematite particles embedded therein. The present work therefore demonstrates that the bioengineered material can serve as an epochal orange-hued inorganic pigment with low toxicity and marked thermostability that should meet large industrial demand. en-copyright= kn-copyright= en-aut-name=TamuraKatsunori en-aut-sei=Tamura en-aut-mei=Katsunori kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=OshimaYuri en-aut-sei=Oshima en-aut-mei=Yuri kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=FuseYuta en-aut-sei=Fuse en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=NagaokaNoriyuki en-aut-sei=Nagaoka en-aut-mei=Noriyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=KunohTatsuki en-aut-sei=Kunoh en-aut-mei=Tatsuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=NakanishiMakoto en-aut-sei=Nakanishi en-aut-mei=Makoto kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=FujiiTatsuo en-aut-sei=Fujii en-aut-mei=Tatsuo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=NanbaTokuro en-aut-sei=Nanba en-aut-mei=Tokuro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=TakadaJun en-aut-sei=Takada en-aut-mei=Jun kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Advanced Research Center for Oral and Craniofacial Sciences, Okayama University kn-affil= affil-num=5 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=7 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=8 en-affil=Graduate School of Environmental and Life Science, Okayama University kn-affil= affil-num=9 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=7 cd-vols= no-issue=4 article-no= start-page=1194 end-page=1200 dt-received= dt-revised= dt-accepted= dt-pub-year=2022 dt-pub=2022411 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Dip-and-Read, Organic Solvent-Compatible, Paper-Based Analytical Devices Equipped with Chromatographic Separation for Indole Analysis in Shrimp en-subtitle= kn-subtitle= en-abstract= kn-abstract=We developed an organic solvent-compatible paper-based analytical device (PAD) for the quantitative analysis of indole, which is an indicator of shrimp freshness. Although indole is insoluble in water, ethyl acetate is a suitable solvent to dissolve and extract indole from shrimp. The PADs are fabricated using a cutting method that allows the use of an organic solvent because no hydrophobic barrier is needed to form fluidic channels. Ehrlich's reagent consists of 4-(dimethylamino)benzaldehyde and p-dimethylaminobenzaldehyde and was deposited onto the reaction zone of the PAD followed by lamination to prevent evaporation of the ethyl acetate. Samples are introduced into the PAD via immersion in organic sample solutions. When the PAD is immersed into an indole solution of ethyl acetate in a closed bottle, the sample solution penetrates the channel of the PAD and successively flows into the detection zone to form a hydrophilic colored product. The PADs provide a linear relationship between the logarithm of the indole concentration and the color intensity within a range of 1.0-20 ppm with correlation coefficients of r2 > 0.99. The limits of detection and quantification are 0.36 and 0.71 ppm, respectively. Relative standard deviations for both the intraday (n = 2) and interday (n = 3) precision were less than 2.5%. In the indole analysis of shrimp, the PADs separated the interfering orange-colored astaxanthin in the extract from the colored product of indole via the paper chromatographic principle. We used the PADs to investigate the degradation of shrimp, and the results showed a rapid increase in the indole level after 7 days. High-performance liquid chromatography verified the accuracy of the PADs by showing good agreement with the obtained indole levels. en-copyright= kn-copyright= en-aut-name=SeetasangSasikarn en-aut-sei=Seetasang en-aut-mei=Sasikarn kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KanetaTakashi en-aut-sei=Kaneta en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= affil-num=1 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=Ehrlich’s reagent kn-keyword=Ehrlich’s reagent en-keyword=astaxanthin kn-keyword=astaxanthin en-keyword=chromatography kn-keyword=chromatography en-keyword=indole kn-keyword=indole en-keyword=paper-based device kn-keyword=paper-based device en-keyword=shrimp kn-keyword=shrimp END start-ver=1.4 cd-journal=joma no-vol=7 cd-vols= no-issue=6 article-no= start-page=5495 end-page=5501 dt-received= dt-revised= dt-accepted= dt-pub-year=2022 dt-pub=20220131 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Evaluation of Effective Field-Effect Mobility in Thin-Film and Single-Crystal Transistors for Revisiting Various Phenacene-Type Molecules en-subtitle= kn-subtitle= en-abstract= kn-abstract=The magnitude of the field-effect mobility mu of organic thin-film and single-crystal field-effect transistors (FETs) has been over-estimated in certain recent studies. These reports set alarm bells ringing in the research field of organic electronics. Herein, we report a precise evaluation of the mu values using the effective field-effect mobility, mu(eff), a new indicator that is recently designed to prevent the FET performance of thin-film and single-crystal FETs based on various phenacene molecules from being overestimated. The transfer curves of a range of FETs based on phenacene are carefully categorized on the basis of a previous report. The exact evaluation of the value of mu(eff) depends on the exact classification of each transfer curve. The transfer curves of all our phenacene FETs could be successfully classified based on the method indicated in the aforementioned report, which made it possible to evaluate the exact value of mu(eff) for each FET. The FET performance based on the values of mu(eff) obtained in this study is discussed in detail. In particular, the mu(eff) values of single-crystal FETs are almost consistent with the mu values that were reported previously, but the mu(eff) values of thin-film FETs were much lower than those previously reported for mu, owing to a high absolute threshold voltage, vertical bar V-th vertical bar. The increase in the field-effect mobility as a function of the number of benzene rings, which was previously demonstrated based on the mu values of single-crystal FETs with phenacene molecules, is well reproduced from the mu(eff) values. The FET performance is discussed based on the newly evaluated mu(eff) values, and the future prospects of using phenacene molecules in FET devices are demonstrated. en-copyright= kn-copyright= en-aut-name=ZhangYanting en-aut-sei=Zhang en-aut-mei=Yanting kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=EguchiRitsuko en-aut-sei=Eguchi en-aut-mei=Ritsuko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=HamaoShino en-aut-sei=Hamao en-aut-mei=Shino kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=OkamotoHideki en-aut-sei=Okamoto en-aut-mei=Hideki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=GotoHidenori en-aut-sei=Goto en-aut-mei=Hidenori kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=KubozonoYoshihiro en-aut-sei=Kubozono en-aut-mei=Yoshihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= affil-num=1 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=2 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=3 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=4 en-affil=Department of Chemistry, Okayama University kn-affil= affil-num=5 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=6 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=6 cd-vols= no-issue=15 article-no= start-page=10030 end-page=10038 dt-received= dt-revised= dt-accepted= dt-pub-year=2021 dt-pub=20210409 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Design of Clickable Ionic Liquid Monomers to Enhance Ionic Conductivity for Main-Chain 1,2,3-Triazolium-Based Poly(Ionic Liquid)s en-subtitle= kn-subtitle= en-abstract= kn-abstract=A series of clickable alpha-azide-omega-alkyne ionic liquid (IL) monomers with an ethylene oxide spacer were developed and applied to the synthesis of 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) with high ionic conductivities via one-step thermal azide-alkyne cycloaddition click chemistry. Subsequently, the number of IL moieties in the resultant TPILs was further increased by N-alkylation of the 1,2,3-triazole-based backbones of the TPILs with a quarternizing reagent. This strategy affords the preparation of TPILs having either one or two 1,2,3-triazolium cations with bis(trifluoromethylsulfonyl)imide anions in a monomer unit. Synthesis of the TPILs was confirmed by H-1 and C-13 NMR spectroscopy and gel permeation chromatography. The effects of the length of the ethylene oxide spacer and the number of IL moieties in the IL monomer unit on the physicochemical properties of the TPILs were characterized by differential scanning calorimetry, thermogravimetric analysis, and impedance spectroscopy. The introduction of a longer ethylene oxide spacer or an increase in the number of IL moieties in the monomer unit resulted in TPILs with lower glass-transition temperatures and higher ionic conductivities. The highest ionic conductivity achieved in this study was 2.0 x 10(-5) S cm(-1) at 30 degrees C. These results suggest that the design of the IL monomer provides the resultant polymer with high chain flexibility and a high IL density, and so it is effective for preparing TPILs with high ionic conductivities. en-copyright= kn-copyright= en-aut-name=HiraiRuka en-aut-sei=Hirai en-aut-mei=Ruka kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=WatanabeTakaichi en-aut-sei=Watanabe en-aut-mei=Takaichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=OnoTsutomu en-aut-sei=Ono en-aut-mei=Tsutomu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Department of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Department of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Department of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=5 cd-vols= no-issue=42 article-no= start-page=27287 end-page=27294 dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=20201016 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Preparation and Characterization of Additional Metallic Element-Containing Tubular Iron Oxides of Bacterial Origin en-subtitle= kn-subtitle= en-abstract= kn-abstract=Biogenic microtubular iron oxides (BIOXs) derived from Leptothrix spp. are known as promising multifunctional materials for industrial applications such as ceramic pigments and catalyst carriers. Here, we report unprecedented BIOX products with additive depositions of various metallic elements prepared by a newly devised "two-step" method using an artificial culture system of Leptothrix cholodnii strain OUMS1; the method comprises a biotic formation of immature organic sheaths and subsequent abiotic deposition of Fe and intended elements on the sheaths. Chemical composition ratios of the additional elements Al, Zr, and Ti in the respective BIOXs were arbitrarily controllable depending on initial concentrations of metallic salts added to reaction solutions. Raman spectroscopy exemplified an existence of Fe-O-Al linkage in the Al-containing BIOX matrices. Time-course analyses revealed the underlying physiological mechanism for the BIOX formation. These results indicate that our advanced method can contribute greatly to creations of innovative bioderived materials with improved functionalities. en-copyright= kn-copyright= en-aut-name=TamuraKatsunori en-aut-sei=Tamura en-aut-mei=Katsunori kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KunohTatsuki en-aut-sei=Kunoh en-aut-mei=Tatsuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NakanishiMakoto en-aut-sei=Nakanishi en-aut-mei=Makoto kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=KusanoYoshihiro en-aut-sei=Kusano en-aut-mei=Yoshihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=TakadaJun en-aut-sei=Takada en-aut-mei=Jun kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Department of Applied Chemistry and Biotechnology, Okayama University of Science kn-affil= affil-num=5 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=35 cd-vols= no-issue=6 article-no= start-page=2358 end-page=2367 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190110 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Microfluidic Formation of Hydrogel Microcapsules with a Single Aqueous Core by en-subtitle= kn-subtitle= en-abstract= kn-abstract=We report a simple process to fabricate monodisperse tetra-arm poly(ethylene glycol) (tetra-PEG) hydrogel microcapsules with an aqueous core and a semipermeable hydrogel shell through the formation of aqueous two-phase system (ATPS) droplets consisting of a dextran-rich core and a tetra-PEG macromonomer-rich shell, followed by a spontaneous cross-end coupling reaction of tetra-PEG macromonomers in the shell. Different from conventional techniques, this process enables for the continuous production of hydrogel microcapsules from water-in-oil emulsion droplets under mild conditions in the absence of radical initiators and external stimuli such as heating and ultraviolet light irradiation. We find that rapid cross-end coupling reaction of tetra-PEG macromonomers in ATPS droplets in the range of pH from 7.4 to 7.8 gives hydrogel microcapsules with a kinetically arrested core–shell structure. The diameter and core–shell ratio of the microcapsules can be easily controlled by adjusting flow rates and ATPS compositions. On the other hand, the slow cross-end coupling reaction of tetra-PEG macromonomers in ATPS droplets at pH 7.0 and lower induces structural change from core–shell to Janus during the reaction, which eventually forms hydrogel microparticles with a thermodynamically stable crescent structure. We believe that these hydrogel microparticles with controlled structures can be used in biomedical fields such as cell encapsulation, biosensors, and drug delivery carriers for sensitive biomolecules. en-copyright= kn-copyright= en-aut-name=WatanabeTakaichi en-aut-sei=Watanabe en-aut-mei=Takaichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=MotohiroIbuki en-aut-sei=Motohiro en-aut-mei=Ibuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=OnoTsutomu en-aut-sei=Ono en-aut-mei=Tsutomu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=30 cd-vols= no-issue=9 article-no= start-page=2470 end-page=2479 dt-received= dt-revised= dt-accepted= dt-pub-year=2014 dt-pub=2014029 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Microfluidic Approach to the Formation of Internally Porous Polymer Particles by Solvent Extraction en-subtitle= kn-subtitle= en-abstract= kn-abstract=We report the controlled formation of internally porous polyelectrolyte particles with diameters ranging from tens to hundreds of micrometers through selective solvent extraction using microfluidics. Solvent-resistant microdevices, fabricated by frontal photopolymerization, encapsulate binary polymer (P)/solvent (S1) mixtures by a carrier solvent phase (C) to form plugs with well-defined radii and low polydispersity; the suspension is then brought into contact with a selective extraction solvent (S2) that is miscible with C and S1 but not P, leading to the extraction of S1 from the droplets. The ensuing phase inversion yields polymer capsules with a smooth surface but highly porous internal structure. Depending on the liquid extraction time scale, this stage can be carried out in situ, within the chip, or ex situ, in an external S2 bath. Bimodal polymer plugs are achieved using asymmetrically inverted T junctions. For this demonstration, we form sodium poly(styrenesulfonate) (P) particles using water (S1), hexadecane (C), and methyl ethyl ketone (S2). We measure droplet extraction rates as a function of drop size and polymer concentration and propose a simple scaling model to guide particle formation. We find that the extraction time required to form particles from liquid droplets does not depend on the initial polymer concentration but is rather proportional to the initial droplet size. The resulting particle size follows a linear relationship with the initial droplet size for all polymer concentrations, allowing for the precise control of particle size. The internal particle porous structure exhibits a polymer density gradient ranging from a dense surface skin toward an essentially hollow core. Average particle porosities between 10 and 50% are achieved by varying the initial droplet compositions up to 15 wt % polymer. Such particles have potential applications in functional, optical, and coating materials. en-copyright= kn-copyright= en-aut-name=WatanabeTakaichi en-aut-sei=Watanabe en-aut-mei=Takaichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=LopezCarlos G. en-aut-sei=Lopez en-aut-mei=Carlos G. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=DouglasJack F. en-aut-sei=Douglas en-aut-mei=Jack F. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=OnoTsutomu en-aut-sei=Ono en-aut-mei=Tsutomu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=CabralJoão T. en-aut-sei=Cabral en-aut-mei=João T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Department of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil= Department of Chemical Engineering, Imperial College London kn-affil= affil-num=3 en-affil= Materials Science and Engineering Division, National Institute of Standards and Technology kn-affil= affil-num=4 en-affil=Department of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Department of Chemical Engineering, Imperial College London kn-affil= END start-ver=1.4 cd-journal=joma no-vol=29 cd-vols= no-issue=46 article-no= start-page=14082 end-page=14088 dt-received= dt-revised= dt-accepted= dt-pub-year=2013 dt-pub=20131029 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Microfluidic Fabrication of Monodisperse Polylactide Microcapsules with Tunable Structures through Rapid Precipitation en-subtitle= kn-subtitle= en-abstract= kn-abstract=We describe a versatile and facile route to the continuous production of monodisperse polylactide (PLA) microcapsules with controllable structures. With the combination of microfluidic emulsification, solvent diffusion, and internal phase separation, uniform PLA microcapsules with a perfluorooctyl bromide (PFOB) core were successfully obtained by simply diluting monodisperse ethyl acetate (EA)-in-water emulsion with pure water. Rapid extraction of EA from the droplets into the aqueous phase enabled the solidification of the polymer droplets in a nonequilibrium state during internal phase separation between a concentrated PLA/EA phase and a PFOB phase. Higher-molecular-weight PLA generated structural complexity of the microcapsules, yielding core–shell microcapsules with covered with small PFOB droplets. Removal of the PFOB via freeze drying gave hollow microcapsules with dimpled surfaces. The core–shell ratios and the diameter of these microcapsules could be finely tuned by just adjusting the concentration of PFOB and flow rates on emulsification, respectively. These biocompatible microcapsules with controllable size and structures are potentially applicable in biomedical fields such as drug delivery carriers of many functional molecules. en-copyright= kn-copyright= en-aut-name=WatanabeTakaichi en-aut-sei=Watanabe en-aut-mei=Takaichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KimuraYukitaka en-aut-sei=Kimura en-aut-mei=Yukitaka kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=OnoTsutomu en-aut-sei=Ono en-aut-mei=Tsutomu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Department of Chemistry and Biotechnology, Graduate School of Natural Science and Technolog kn-affil= affil-num=2 en-affil=Department of Material and Energy Science, Graduate School of Environmental and Life Science, Okayama University kn-affil= affil-num=3 en-affil=Department of Chemistry and Biotechnology, Graduate School of Natural Science and Technology kn-affil= END start-ver=1.4 cd-journal=joma no-vol=11 cd-vols= no-issue=11 article-no= start-page=4536 end-page=4541 dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=20200522 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Application of First-Principles-Based Artificial Neural Network Potentials to Multiscale-Shock Dynamics Simulations on Solid Materials en-subtitle= kn-subtitle= en-abstract= kn-abstract=The use of artificial neural network (ANN) potentials trained with first-principles calculations has emerged as a promising approach for molecular dynamics (MD) simulations encompassing large space and time scales while retaining first-principles accuracy. To date, however, the application of ANN-MD has been limited to near-equilibrium processes. Here we combine first-principles-trained ANN-MD with multiscale shock theory (MSST) to successfully describe far-from-equilibrium shock phenomena. Our ANN-MSST-MD approach describes shock-wave propagation in solids with first-principles accuracy but a 5000 times shorter computing time. Accordingly, ANN-MD-MSST was able to resolve fine, long-time elastic deformation at low shock speed, which was impossible with first-principles MD because of the high computational cost. This work thus lays a foundation of ANN-MD simulation to study a wide range of far-from-equilibrium processes. en-copyright= kn-copyright= en-aut-name=MisawaMasaaki en-aut-sei=Misawa en-aut-mei=Masaaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=FukushimaShogo en-aut-sei=Fukushima en-aut-mei=Shogo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=KouraAkihide en-aut-sei=Koura en-aut-mei=Akihide kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=ShimamuraKohei en-aut-sei=Shimamura en-aut-mei=Kohei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=ShimojoFuyuki en-aut-sei=Shimojo en-aut-mei=Fuyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=TiwariSubodh en-aut-sei=Tiwari en-aut-mei=Subodh kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=NomuraKen-ichi en-aut-sei=Nomura en-aut-mei=Ken-ichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=KaliaRajiv K. en-aut-sei=Kalia en-aut-mei=Rajiv K. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=NakanoAiichiro en-aut-sei=Nakano en-aut-mei=Aiichiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=VashishtaPriya en-aut-sei=Vashishta en-aut-mei=Priya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Department of Physics, Kumamoto University kn-affil= affil-num=3 en-affil=Department of Physics, Kumamoto University kn-affil= affil-num=4 en-affil=Department of Physics, Kumamoto University kn-affil= affil-num=5 en-affil=Department of Physics, Kumamoto University kn-affil= affil-num=6 en-affil=Collaboratory for Advanced Computing and Simulations, University of Southern California kn-affil= affil-num=7 en-affil=Collaboratory for Advanced Computing and Simulations, University of Southern California kn-affil= affil-num=8 en-affil=Collaboratory for Advanced Computing and Simulations, University of Southern California kn-affil= affil-num=9 en-affil=Collaboratory for Advanced Computing and Simulations, University of Southern California kn-affil= affil-num=10 en-affil=Collaboratory for Advanced Computing and Simulations, University of Southern California kn-affil= END start-ver=1.4 cd-journal=joma no-vol=5 cd-vols= no-issue=17 article-no= start-page=10207 end-page=10216 dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=20200420 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Minimization of Amounts of Catalyst and Solvent in NHC-Catalyzed Benzoin Reactions of Solid Aldehydes: Mechanistic Consideration of Solid-to-Solid Conversion and Total Synthesis of Isodarparvinol B en-subtitle= kn-subtitle= en-abstract= kn-abstract=Attempts were made to minimize the amounts of catalyst and solvent in the NHC-catalyzed benzoin reactions of solid aldehydes. In some case, solid-to-solid conversions proceeded in the solvent-free NHC-catalyzed benzoin reactions. Even if a mixture of the substrate, N-heterocyclic carbene (NHC) precursor, and inorganic base was initially a powdery solid, the reaction did proceed at reaction temperature lower than the melting points of each compound. The solid mixture partially melted or became a slurry or suspension in the meantime. We call this solid/liquid mixture a semisolid state. The reaction giving an optically active product was faster than that giving a racemic mixture of the same product. Melting-point depression was observed for a series of mixtures of the substrate and product in different substrate/product ratios. Solvent-free solid-to-solid conversions were accelerated by the formation of a semisolid state resulting from the melting-point depression of the solid substrate accompanied by the product formation. In the case of solid substrates with high melting points, melting-point depression was useless, and the addition of a small amount of solvent was needed. The first total synthesis of isodarparvinol B was achieved via the NHC-catalyzed intramolecular benzoin reaction using a small amount of solvent as an additive. en-copyright= kn-copyright= en-aut-name=IwaiKenta en-aut-sei=Iwai en-aut-mei=Kenta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=OnoMasakazu en-aut-sei=Ono en-aut-mei=Masakazu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NanjoYoshiko en-aut-sei=Nanjo en-aut-mei=Yoshiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=EmaTadashi en-aut-sei=Ema en-aut-mei=Tadashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=22 cd-vols= no-issue=6 article-no= start-page=2350 end-page=2353 dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=20200505 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Palladium-Catalyzed Decarbonylative Alkylation of Acyl Fluorides en-subtitle= kn-subtitle= en-abstract= kn-abstract=Palladium-catalyzed decarbonylative alkylation reactions of acyl fluorides have been developed using alkylboranes having β-hydrogens. A wide range of functional groups were well tolerated, even at the high temperature required for decarbonylation. This protocol provides a diverse C(sp2)–C(sp3) bond formation via a highly efficient decarbonylative process. The hemilabile bidentate ligand DPPE plays a crucial role for retardation of the undesired β-hydride elimination. en-copyright= kn-copyright= en-aut-name=FuLiyan en-aut-sei=Fu en-aut-mei=Liyan kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=ChenQiang en-aut-sei=Chen en-aut-mei=Qiang kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=WangZhenhua en-aut-sei=Wang en-aut-mei=Zhenhua kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=NishiharaYasushi en-aut-sei=Nishihara en-aut-mei=Yasushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=59 cd-vols= no-issue=17 article-no= start-page=1701 end-page=1710 dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=20200416 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Development and Characterization of Novel Molecular Probes for Ca2+/Calmodulin-Dependent Protein Kinase Kinase, Derived from STO-609 en-subtitle= kn-subtitle= en-abstract= kn-abstract=Ca2+/calmodulin-dependent protein kinase kinase (CaMKK) activates particular multifunctional kinases, including CaMKI, CaMKIV, and 5′AMP-activated protein kinase (AMPK), resulting in the regulation of various Ca2+-dependent cellular processes, including neuronal, metabolic, and pathophysiological pathways. We developed and characterized a novel pan-CaMKK inhibitor, TIM-063 (2-hydroxy-3-nitro-7H-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one) derived from STO-609 (7H-benzimidazo[2,1-a]benz[de]isoquinoline-7-one-3-carboxylic acid), and an inactive analogue (TIM-062) as molecular probes for the analysis of CaMKK-mediated cellular responses. Unlike STO-609, TIM-063 had an inhibitory activity against CaMKK isoforms (CaMKKα and CaMKKβ) with a similar potency (Ki = 0.35 μM for CaMKKα, and Ki = 0.2 μM for CaMKKβ) in vitro. Two TIM-063 analogues lacking a nitro group (TIM-062) or a hydroxy group (TIM-064) completely impaired CaMKK inhibitory activities, indicating that both substituents are necessary for the CaMKK inhibitory activity of TIM-063. Enzymatic analysis revealed that TIM-063 is an ATP-competitive inhibitor that directly targets the catalytic domain of CaMKK, similar to STO-609. TIM-063 suppressed the ionomycin-induced phosphorylation of exogenously expressed CaMKI, CaMKIV, and endogenous AMPKα in HeLa cells with an IC50 of ∼0.3 μM, and it suppressed CaMKK isoform-mediated CaMKIV phosphorylation in transfected COS-7 cells. Thus, TIM-063, but not the inactive analogue (TIM-062), displayed cell permeability and the ability to inhibit CaMKK activity in cells. Taken together, these results indicate that TIM-063 could be a useful tool for the precise analysis of CaMKK-mediated signaling pathways and may be a promising lead compound for the development of therapeutic agents for the treatment of CaMKK-related diseases. en-copyright= kn-copyright= en-aut-name=OhtsukaSatomi en-aut-sei=Ohtsuka en-aut-mei=Satomi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=OzekiYui en-aut-sei=Ozeki en-aut-mei=Yui kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=FujiwaraMoeno en-aut-sei=Fujiwara en-aut-mei=Moeno kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=MiyagawaTomoyuki en-aut-sei=Miyagawa en-aut-mei=Tomoyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=KanayamaKanayamaNaoki en-aut-sei=Kanayama en-aut-mei=KanayamaNaoki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=MagariMasaki en-aut-sei=Magari en-aut-mei=Masaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=HatanoNaoya en-aut-sei=Hatano en-aut-mei=Naoya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=SuizuFutoshi en-aut-sei=Suizu en-aut-mei=Futoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=IshikawaTeruhiko en-aut-sei=Ishikawa en-aut-mei=Teruhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=TokumitsuHiroshi en-aut-sei=Tokumitsu en-aut-mei=Hiroshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= affil-num=1 en-affil=Graduate School of Interdisciplinary Science & Engineering in Health Systems, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Education, Okayama University kn-affil= affil-num=3 en-affil=Faculty of Education, Okayama Universit kn-affil= affil-num=4 en-affil= Graduate School of Education, Okayama University kn-affil= affil-num=5 en-affil=Graduate School of Interdisciplinary Science & Engineering in Health Systems, Okayama University kn-affil= affil-num=6 en-affil=Graduate School of Interdisciplinary Science & Engineering in Health Systems, Okayama Universityayama University kn-affil= affil-num=7 en-affil=Graduate School of Interdisciplinary Science & Engineering in Health Systems, Okayama University kn-affil= affil-num=8 en-affil= Institute for Genetic Medicine, Hokkaido University kn-affil= affil-num=9 en-affil=Graduate School of Education, Okayama University kn-affil= affil-num=10 en-affil=Graduate School of Interdisciplinary Science & Engineering in Health Systems, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=141 cd-vols= no-issue=25 article-no= start-page=9832 end-page=9836 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=2019611 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Deoxygenative Insertion of Carbonyl Carbon into a C(sp3)–H Bond: Synthesis of Indolines and Indoles en-subtitle= kn-subtitle= en-abstract= kn-abstract=A simple deoxygenation reagent prepared in situ from commercially available Mo(CO)6 and ortho-quinone has been developed for the synthesis of indoline and indole derivatives. The Mo/quinone complex efficiently deoxygenates carbonyl compounds bearing a neighboring dialkylamino group and effects intramolecular cyclizations with the insertion of a deoxygenated carbonyl carbon into a C(sp3)–H bond, in which a carbonyl group acts as a carbene equivalent. The reaction also proceeds with a catalytic amount of Mo/quinone in the presence of disilane as an oxygen atom acceptor. en-copyright= kn-copyright= en-aut-name=AsakoSobi en-aut-sei=Asako en-aut-mei=Sobi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=IshiharaSeina en-aut-sei=Ishihara en-aut-mei=Seina kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=HirataKeiya en-aut-sei=Hirata en-aut-mei=Keiya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=TakaiKazuhiko en-aut-sei=Takai en-aut-mei=Kazuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=C-H activation kn-keyword=C-H activation en-keyword=Oxidative addition kn-keyword=Oxidative addition en-keyword=Structural-characterization kn-keyword=Structural-characterization en-keyword=Ditungsten hexaalkoxides kn-keyword=Ditungsten hexaalkoxides en-keyword=Direct functionalization kn-keyword=Direct functionalization en-keyword=Organic-synthesis kn-keyword=Organic-synthesis en-keyword=Tertiary-amines kn-keyword=Tertiary-amines en-keyword=Oxo-alkylidene kn-keyword=Oxo-alkylidene en-keyword=Ketones kn-keyword=Ketones en-keyword=Chemistry kn-keyword=Chemistry END start-ver=1.4 cd-journal=joma no-vol=21 cd-vols= no-issue=17 article-no= start-page=6756 end-page=6760 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190808 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Rhenium-Catalyzed Cyclization via 1,2-Iodine and 1,5-Hydrogen Migration for the Synthesis of 2-Iodo-1H-indenes en-subtitle= kn-subtitle= en-abstract= kn-abstract=A rhenium complex catalyzed the formation of 2-iodo-1H-indene derivatives through iodine and hydrogen migration of 3-iodopropargyl ethers. The reaction proceeded via generation of 1-iodoalkenylrhenium carbene species by sequential 1,2-iodine and 1,5-hydrogen shifts with readily available precursors under neutral conditions. The reaction mechanism and the reactivity of the generated alkenylcarbene species were also investigated. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=TakaiKazuhiko en-aut-sei=Takai en-aut-mei=Kazuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=anti-markovnikov addition kn-keyword=anti-markovnikov addition en-keyword=silyl enol ethers kn-keyword=silyl enol ethers en-keyword=terminal alkynes kn-keyword=terminal alkynes en-keyword=metal vinylidenes kn-keyword=metal vinylidenes en-keyword=cycloisomerization kn-keyword=cycloisomerization en-keyword=ruthenium kn-keyword=ruthenium en-keyword=complexes kn-keyword=complexes en-keyword=derivatives kn-keyword=derivatives en-keyword=carbene kn-keyword=carbene en-keyword=functionalization kn-keyword=functionalization END start-ver=1.4 cd-journal=joma no-vol=21 cd-vols= no-issue=9 article-no= start-page=3441 end-page=3445 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190418 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Rhenium-Catalyzed Regioselective ortho-Alkenylation and [3 + 2 + 1] Cycloaddition of Phenols with Internal Alkynes en-subtitle= kn-subtitle= en-abstract= kn-abstract=An operationally simple and direct rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes was developed. The protocol provided ortho-alkenylphenols exclusively, and formation of para- or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products were not observed. The [3 + 2 + 1] cycloaddition of phenols and two alkynes via ortho-alkenylation was also demonstrated, in which the alkynes functioned as both two- and one-carbon units. These reactions proceeded with readily available starting materials under neutral conditions without additional ligands. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=YamamotoMasaki en-aut-sei=Yamamoto en-aut-mei=Masaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TakaiKazuhiko en-aut-sei=Takai en-aut-mei=Kazuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=anti-markovnikov addition kn-keyword=anti-markovnikov addition en-keyword=intramolecular hydroarylation kn-keyword=intramolecular hydroarylation en-keyword=oxidative annulation kn-keyword=oxidative annulation en-keyword=gold kn-keyword=gold en-keyword=hydrophenoxylation kn-keyword=hydrophenoxylation en-keyword=construction kn-keyword=construction en-keyword=cyclization kn-keyword=cyclization en-keyword=vinylation kn-keyword=vinylation en-keyword=alkenes kn-keyword=alkenes END start-ver=1.4 cd-journal=joma no-vol=21 cd-vols= no-issue=8 article-no= start-page=2668 end-page=2672 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190404 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Chromium-Mediated Stannylcyclopropanation of Alkenes with (Diiodomethyl)stannanes en-subtitle= kn-subtitle= en-abstract= kn-abstract=A stannyl-group-substituted gem-dichromiomethane species, generated in situ from CrCl2, TMEDA, and tributyl(diiodomethyl)stannane, worked as an efficient stannylcarbene equivalent to promote cyclopropanation of alkenes. The reaction provided synthetically useful stannylcyclopropanes directly from commercially available unactivated alkenes without using potentially flammable alkylzinc and diazo compounds. Structural characterization of stannyl- and germyl-group-substituted gem-dichromiomethane complexes and the effect of group 14 elements containing substituents for cyclopropanation are also described. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=TaniguchiRyuji en-aut-sei=Taniguchi en-aut-mei=Ryuji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=MizutaChisato en-aut-sei=Mizuta en-aut-mei=Chisato kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=TakaiKazuhiko en-aut-sei=Takai en-aut-mei=Kazuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=chromium(II)-mediate synthesis kn-keyword=chromium(II)-mediate synthesis en-keyword=stereoselective-synthesis kn-keyword=stereoselective-synthesis en-keyword=e-alkenylstannanes kn-keyword=e-alkenylstannanes en-keyword=redox system kn-keyword=redox system en-keyword=cyclopropanation kn-keyword=cyclopropanation en-keyword=aldehydes kn-keyword=aldehydes en-keyword=reagents kn-keyword=reagents en-keyword=cyclopropenes kn-keyword=cyclopropenes en-keyword=reactivity kn-keyword=reactivity en-keyword=reduction kn-keyword=reduction END start-ver=1.4 cd-journal=joma no-vol=140 cd-vols= no-issue=45 article-no= start-page=15425 end-page=15429 dt-received= dt-revised= dt-accepted= dt-pub-year=2018 dt-pub=20181022 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Use of Cyclopropane as C1 Synthetic Unit by Directed Retro- Cyclopropanation with Ethylene Release en-subtitle= kn-subtitle= en-abstract= kn-abstract=Cyclopropanation of alkenes is a well-established textbook reaction for the synthesis of cyclopropanes, where a “high-energy” carbene species is exploited to drive the reaction forward. However, little attention has been focused toward molecular transformations involving the reverse reaction, retro-cyclopropanation (RC). This is because of difficulties associated with both cleaving the two geminal C–C single bonds and exploiting the generated carbenes for further transformations in an efficient and selective manner. Here, we report that a molybdenum-based catalytic system overcomes the above challenges and effects the RC of cyclopropanes bearing a pyridyl group with the release of ethylene (alkene) and the subsequent intramolecular cyclization leading to pyrido[2,1-a]isoindoles. The reaction allows for the uncommon use of cyclopropanes as C1 synthetic units in contrast to most conventional reactions in which cyclopropanes are used as C3 synthetic units. We anticipate that this new strategy will pave the way for C1 cyclopropane chemistry. en-copyright= kn-copyright= en-aut-name=SobiAsako en-aut-sei=Sobi en-aut-mei=Asako kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name= KobashiTakaaki en-aut-sei= Kobashi en-aut-mei=Takaaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TakaiKazuhiko en-aut-sei=Takai en-aut-mei=Kazuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=8 cd-vols= no-issue=6 article-no= start-page=5454 end-page=5459 dt-received= dt-revised= dt-accepted= dt-pub-year=2018 dt-pub=20180504 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Amine-Promoted anti-Markovnikov Addition of 1,3-Dicarbonyl Compounds with Terminal Alkynes under Rhenium Catalysis en-subtitle= kn-subtitle= en-abstract= kn-abstract=Amines have been identified to greatly accelerate the intermolecular anti-Markovnikov addition of carbon nucleophiles to unactivated terminal alkynes. Using a combination of [ReBr(CO)3(thf)]2 and iPr2NEt, construction of cyclic all-carbon quaternary centers was achieved with various 1,3-ketoesters, diketones, and diesters with lower catalyst loading under milder conditions. The type of addition could be easily controlled by choice of additive, highlighting the unique features of rhenium catalysis en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=UemuraErika en-aut-sei=Uemura en-aut-mei=Erika kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TakaiKazuhiko en-aut-sei=Takai en-aut-mei=Kazuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=rhenium kn-keyword=rhenium en-keyword=anti-Markovnikov addition kn-keyword=anti-Markovnikov addition en-keyword=1,3-dicarbonyl compound kn-keyword=1,3-dicarbonyl compound en-keyword=vinylidene kn-keyword=vinylidene en-keyword=amine kn-keyword=amine END start-ver=1.4 cd-journal=joma no-vol=59 cd-vols= no-issue=3 article-no= start-page=218 end-page=229 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20191209 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=The Unlimited Potential of Microbial Rhodopsins as Optical Tools en-subtitle= kn-subtitle= en-abstract= kn-abstract= Microbial rhodopsins, a photoactive membrane protein family, serve as fundamental tools for optogenetics, an innovative technology for controlling biological activities with light. Microbial rhodopsins are widely distributed in nature and have a wide variety of biological functions. Regardless of the many different known types of microbial rhodopsins, only a few of them have been used in optogenetics to control neural activity to understand neural networks. The efforts of our group have been aimed at identifying and characterizing novel rhodopsins from nature and also at engineering novel variant rhodopsins by rational design. On the basis of the molecular and functional characteristics of those novel rhodopsins, we have proposed new rhodopsin-based optogenetics tools to control not only neural activities but also "non-neural" activities. In this Perspective, we introduce the achievements and summarize future challenges in creating optogenetics tools using rhodopsins. The implementation of optogenetics deep inside an in vivo brain is the well-known challenge for existing rhodopsins. As a perspective to address this challenge, we introduce innovative optical illumination techniques using wavefront shaping that can reinforce the low light sensitivity of the rhodopsins and realize deep-brain optogenetics. The applications of our optogenetics tools could be extended to manipulate non-neural biological activities such as gene expression, apoptosis, energy production, and muscle contraction. We also discuss the potentially unlimited biotechnological applications of microbial rhodopsins in the future such as in photovoltaic devices and in drug delivery systems. We believe that advances in the field will greatly expand the potential uses of microbial rhodopsins as optical tools. en-copyright= kn-copyright= en-aut-name=KojimaKeiichi en-aut-sei=Kojima en-aut-mei=Keiichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=ShibukawaAtsushi en-aut-sei=Shibukawa en-aut-mei=Atsushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=SudoYuki en-aut-sei=Sudo en-aut-mei=Yuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University, kn-affil= affil-num=2 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University, kn-affil= affil-num=3 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=85 cd-vols= no-issue=2 article-no= start-page=798 end-page=805 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20191218 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Formal Total Synthesis of Manzacidin B via Sequential Diastereodivergent Henry Reaction en-subtitle= kn-subtitle= en-abstract= kn-abstract=A formal total synthesis of manzacidin B is described. beta,beta-Disubstituted gamma-hydroxy-beta-aminoalcohol, the key structure of manzacidin B, is stereoselectively constructed via sequential Henry reactions. By taking advantage of noncovalent interactions, such as intramolecular hydrogen bonding and chelation, we could diastereodivergently control the stereoselectivity of the Henry reaction. en-copyright= kn-copyright= en-aut-name=ArakiYuya en-aut-sei=Araki en-aut-mei=Yuya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=MiyoshiNatsumi en-aut-sei=Miyoshi en-aut-mei=Natsumi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=MorimotoKazuki en-aut-sei=Morimoto en-aut-mei=Kazuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=KudohTakayuki en-aut-sei=Kudoh en-aut-mei=Takayuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=MizoguchiHaruki en-aut-sei=Mizoguchi en-aut-mei=Haruki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=SakakuraAkira en-aut-sei=Sakakura en-aut-mei=Akira kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=84 cd-vols= no-issue=23 article-no= start-page=15373 end-page=15379 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20191104 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Copper-Catalyzed Regioselective Aminothiolation of Aromatic and Aliphatic Alkenes with N-Fluorobenzenesulfonimide and Thiols through Three-Component Radical Coupling en-subtitle= kn-subtitle= en-abstract= kn-abstract= Copper-catalyzed regioselective aminothiolation of terminal and internal alkenes with N-fluorobenzenesulfonimide and thiols has been developed. The three-component reaction is promoted by the addition of dimethyl sulfide. In addition to aromatic alkenes, aliphatic alkenes are subjected to the reaction, affording various aminothiolation adducts as single regioisomers. The radical process is proposed by preliminary mechanistic studies, involving radical trap and radical clock experiments. en-copyright= kn-copyright= en-aut-name=IwasakiMasayuki en-aut-sei=Iwasaki en-aut-mei=Masayuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=NonakaKosei en-aut-sei=Nonaka en-aut-mei=Kosei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=ZouSong en-aut-sei=Zou en-aut-mei=Song kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SawanakaYuta en-aut-sei=Sawanaka en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=ShinozakiTakaaki en-aut-sei=Shinozaki en-aut-mei=Takaaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=FujiiTomoya en-aut-sei=Fujii en-aut-mei=Tomoya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=NakajimaKiyohiko en-aut-sei=Nakajima en-aut-mei=Kiyohiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=NishiharaYasushi en-aut-sei=Nishihara en-aut-mei=Yasushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= affil-num=1 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil= kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=7 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=8 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=21 cd-vols= no-issue=7 article-no= start-page=2073 end-page=2076 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190312 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Thioureas as Highly Active Catalysts for Biomimetic Bromocyclization of Geranyl Derivatives en-subtitle= kn-subtitle= en-abstract= kn-abstract= Thioureas bearing electron-deficient aryl groups show high catalytic activity in the biomimetic bromocyclization of geranyl derivatives. The reaction of geranyl derivatives with N-bromosuccinimide (NBS) proceeds rapidly in CH2Cl2 to give the corresponding bromocyclization products in high yields as a ca. 1:1 mixture of endo- and exo-isomers. The reactivity of geranyl derivatives highly depends on the terminal substituent: electron-donating substituents increase the reactivity, while electron-withdrawing substituents decrease the reactivity. en-copyright= kn-copyright= en-aut-name=TerazakiMiyuki en-aut-sei=Terazaki en-aut-mei=Miyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=ShiomotoKei-ichi en-aut-sei=Shiomoto en-aut-mei=Kei-ichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=MizoguchiHaruki en-aut-sei=Mizoguchi en-aut-mei=Haruki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SakakuraAkira en-aut-sei=Sakakura en-aut-mei=Akira kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=19 cd-vols= no-issue=9 article-no= start-page=5915 end-page=5919 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190802 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Asymmetric Phosphorus Incorporation in Homoepitaxial P-Doped (111) Diamond Revealed by Photoelectron Holography en-subtitle= kn-subtitle= en-abstract= kn-abstract= Diamond has two crystallographically inequivalent sites in the unit cell. In doped diamond, dopant occupation in the two sites is expected to be equal. Nevertheless, preferential dopant occupation during growth under nonequilibrium conditions is of fundamental importance, for example, to enhance the properties of nitrogen-vacancy (N-V) centers; therefore, this is a promising candidate for a qubit. However, the lack of suitable experimental techniques has made it difficult to study the crystal- and chemical-site-resolved local structures of dopants. Here, we confirm the identity of two chemical sites with asymmetric dopant incorporation in the diamond structure, via the photoelectron holography (PEH) of heavily phosphorus (P)-doped diamond prepared by chemical vapor deposition. One is substitutionally incorporated P with preferential site occupations and the other can be attributed to a PV split vacancy complex with preferential orientation. The present study shows that PEH is a valuable technique to study the local structures around dopants with a resolution of crystallographically inequivalent but energetically equivalent sites/orientations. Such information provides strategies to improve the properties of dopant related-complexes in which alignment is crucial for sensing of magnetic field or quantum spin register using N-V centers in diamond. en-copyright= kn-copyright= en-aut-name=YokoyaT. en-aut-sei=Yokoya en-aut-mei=T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=TerashimaK. en-aut-sei=Terashima en-aut-mei=K. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TakedaA. en-aut-sei=Takeda en-aut-mei=A. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=FukuraT. en-aut-sei=Fukura en-aut-mei=T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=FujiwaraH. en-aut-sei=Fujiwara en-aut-mei=H. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=MuroT. en-aut-sei=Muro en-aut-mei=T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=KinoshitaT. en-aut-sei=Kinoshita en-aut-mei=T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=KatoH. en-aut-sei=Kato en-aut-mei=H. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=YamasakiS. en-aut-sei=Yamasaki en-aut-mei=S. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=OguchiT. en-aut-sei=Oguchi en-aut-mei=T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= en-aut-name=WakitaT. en-aut-sei=Wakita en-aut-mei=T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=11 ORCID= en-aut-name=MuraokaY. en-aut-sei=Muraoka en-aut-mei=Y. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=12 ORCID= en-aut-name=MatsushitaT. en-aut-sei=Matsushita en-aut-mei=T. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=13 ORCID= affil-num=1 en-affil=Research Institute for Interdisciplinary Science (RIIS), Okayama University kn-affil= affil-num=2 en-affil=Research Institute for Interdisciplinary Science (RIIS), Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Graduate School of Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Graduate School of Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8 kn-affil= affil-num=7 en-affil=Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8 kn-affil= affil-num=8 en-affil=Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST) kn-affil= affil-num=9 en-affil=Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST) kn-affil= affil-num=10 en-affil=Institute of Scientific and Industrial Research, Osaka University kn-affil= affil-num=11 en-affil=Research Institute for Interdisciplinary Science (RIIS), Okayama University kn-affil= affil-num=12 en-affil=Research Institute for Interdisciplinary Science (RIIS), Okayama University kn-affil= affil-num=13 en-affil=Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8 kn-affil= en-keyword=Dopant local structure kn-keyword=Dopant local structure en-keyword=asymmetric dopant incorporation kn-keyword=asymmetric dopant incorporation en-keyword=diamond kn-keyword=diamond en-keyword=dopant-vacancy complex kn-keyword=dopant-vacancy complex en-keyword=photoelectron holography kn-keyword=photoelectron holography en-keyword=substitutional doping kn-keyword=substitutional doping END start-ver=1.4 cd-journal=joma no-vol=62 cd-vols= no-issue=19 article-no= start-page=8809 end-page=8818 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190904 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Competitive Binding Assay with an Umbelliferone-Based Fluorescent Rexinoid for Retinoid X Receptor Ligand Screening en-subtitle= kn-subtitle= en-abstract= kn-abstract= Ligands for retinoid X receptors (RXRs), "rexinoids", are attracting interest as candidates for therapy of type 2 diabetes and Alzheimer's and Parkinson's diseases. However, current screening methods for rexinoids are slow and require special apparatus or facilities. Here, we created 7-hydroxy-2-oxo-6-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2H-chromene-3-carboxylic acid (10, CU-6PMN) as a new fluorescent RXR agonist and developed a screening system of rexinoids using 10. Compound 10 was designed based on the fact that umbelliferone emits strong fluorescence in a hydrophilic environment, but the fluorescence intensity decreases in hydrophobic environments such as the interior of proteins. The developed assay using 10 enabled screening of rexinoids to be performed easily within a few hours by monitoring changes of fluorescence intensity with widely available fluorescence microplate readers, without the need for processes such as filtration. en-copyright= kn-copyright= en-aut-name=YamadaShoya en-aut-sei=Yamada en-aut-mei=Shoya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KawasakiMayu en-aut-sei=Kawasaki en-aut-mei=Mayu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=FujiharaMichiko en-aut-sei=Fujihara en-aut-mei=Michiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=WatanabeMasaki en-aut-sei=Watanabe en-aut-mei=Masaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=TakamuraYuta en-aut-sei=Takamura en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=TakiokuMaho en-aut-sei=Takioku en-aut-mei=Maho kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=NishiokaHiromi en-aut-sei=Nishioka en-aut-mei=Hiromi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=TakeuchiYasuo en-aut-sei=Takeuchi en-aut-mei=Yasuo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=MakishimaMakoto en-aut-sei=Makishima en-aut-mei=Makoto kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=MotoyamaTomoharu en-aut-sei=Motoyama en-aut-mei=Tomoharu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= en-aut-name=ItoSohei en-aut-sei=Ito en-aut-mei=Sohei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=11 ORCID= en-aut-name=TokiwaHiroaki en-aut-sei=Tokiwa en-aut-mei=Hiroaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=12 ORCID= en-aut-name=NakanoShogo en-aut-sei=Nakano en-aut-mei=Shogo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=13 ORCID= en-aut-name=KakutaHiroki en-aut-sei=Kakuta en-aut-mei=Hiroki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=14 ORCID= affil-num=1 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= affil-num=2 en-affil= kn-affil= affil-num=3 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= affil-num=4 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= affil-num=5 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= affil-num=6 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= affil-num=7 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= affil-num=8 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= affil-num=9 en-affil=Division of Biochemistry, Department of Biomedical Sciences, Nihon University School of Medicine kn-affil= affil-num=10 en-affil=Graduate School of Integrated Pharmaceutical and Nutritional Sciences, University of Shizuoka kn-affil= affil-num=11 en-affil=Graduate School of Integrated Pharmaceutical and Nutritional Sciences, University of Shizuoka kn-affil= affil-num=12 en-affil=Department of Chemistry and Research Center of Smart Molecules, Rikkyo University kn-affil= affil-num=13 en-affil=Graduate School of Integrated Pharmaceutical and Nutritional Sciences, University of Shizuoka kn-affil= affil-num=14 en-affil=Division of Pharmaceutical Sciences, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences kn-affil= END start-ver=1.4 cd-journal=joma no-vol=20 cd-vols= no-issue=22 article-no= start-page=7336 end-page=7340 dt-received= dt-revised= dt-accepted= dt-pub-year=2018 dt-pub=20181029 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Synthesis and Properties of Dithieno-Fused 1,4-Azaborine Derivatives. en-subtitle= kn-subtitle= en-abstract= kn-abstract= The first synthesis of dithieno[3,2- b:2',3'- e][1,4]azaborinine (DTAB) derivatives has been achieved by Buchwald-Hartwig coupling and subsequent Friedel-Crafts-type C-H borylation. A facile method for further π-extension of DTAB was also developed via stannylation and subsequent Kosugi-Migita-Stille cross-coupling reaction. The fundamental properties of DTAB derivatives were also investigated. en-copyright= kn-copyright= en-aut-name=MitsudoKoichi en-aut-sei=Mitsudo en-aut-mei=Koichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=ShigemoriKeisuke en-aut-sei=Shigemori en-aut-mei=Keisuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=MandaiHiroki en-aut-sei=Mandai en-aut-mei=Hiroki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=WakamiyaAtsushi en-aut-sei=Wakamiya en-aut-mei=Atsushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=SugaSeiji en-aut-sei=Suga en-aut-mei=Seiji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Institute for Chemical Research, Kyoto University kn-affil= affil-num=5 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=19 cd-vols= no-issue=11 article-no= start-page=2821 end-page=2824 dt-received= dt-revised= dt-accepted= dt-pub-year=2017 dt-pub=20170518 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Synthesis of 3-Benzo[b]thienyl 3-Thienyl Ether via an Addition-Elimination Reaction and Its Transformation to an Oxygen-Fused Dithiophene Skeleton: Synthesis and Properties of Benzodithienofuran and Its π-Extended Derivatives en-subtitle= kn-subtitle= en-abstract= kn-abstract= The synthesis of 3-benzo[b]thienyl 3-thienyl ether and its dehydrogenative cyclization leading to benzodithienofuran (BDTF; [1]benzothieno[3,2-b]thieno[2,3-d]furan) are described for the first time. Further transformation of BDTF to more π-extended BDTF derivatives and their fundamental physical properties are also studied. en-copyright= kn-copyright= en-aut-name=MitsudoKoichi en-aut-sei=Mitsudo en-aut-mei=Koichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KurimotoYuji en-aut-sei=Kurimoto en-aut-mei=Yuji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=MandaiHiroki en-aut-sei=Mandai en-aut-mei=Hiroki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SugaSeiji en-aut-sei=Suga en-aut-mei=Seiji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=21 cd-vols= no-issue=7 article-no= start-page=2171 end-page=2175 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190307 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Iodide-Mediated or Iodide-Catalyzed Demethylation and Friedel-Crafts C-H Borylative Cyclization Leading to Thiophene-Fused 1,2-Oxaborine Derivatives en-subtitle= kn-subtitle= en-abstract= kn-abstract= The first synthesis of dithieno-1,2-oxaborine derivatives was achieved via iodide-mediated or iodide-catalyzed demethylation of 3-methoxy-2,2'-bithiophene and subsequent C-H borylation. A wide variety of thiophene-fused oxaborines could be synthesized by the procedure. en-copyright= kn-copyright= en-aut-name=ShigemoriKeisuke en-aut-sei=Shigemori en-aut-mei=Keisuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=WatanabeMomoka en-aut-sei=Watanabe en-aut-mei=Momoka kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=KongJulie en-aut-sei=Kong en-aut-mei=Julie kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=MitsudoKoichi en-aut-sei=Mitsudo en-aut-mei=Koichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=WakamiyaAtsushi en-aut-sei=Wakamiya en-aut-mei=Atsushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=MandaiHiroki en-aut-sei=Mandai en-aut-mei=Hiroki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=SugaSeiji en-aut-sei=Suga en-aut-mei=Seiji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Institute for Chemical Research, Kyoto University kn-affil= affil-num=6 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=7 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=19 cd-vols= no-issue=5 article-no= start-page=3370 end-page=3378 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190424 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Is F-1-ATPase a Rotary Motor with Nearly 100% Efficiency? Quantitative Analysis of Chemomechanical Coupling and Mechanical Slip en-subtitle= kn-subtitle= en-abstract= kn-abstract= We present a chemomechanical network model of the rotary molecular motor F1-ATPase which quantitatively describes not only the rotary motor dynamics driven by ATP hydrolysis but also the ATP synthesis caused by forced reverse rotations. We observe a high reversibility of F1-ATPase, that is, the main cycle of ATP synthesis corresponds to the reversal of the main cycle in the hydrolysis-driven motor rotation. However, our quantitative analysis indicates that torque-induced mechanical slip without chemomechanical coupling occurs under high external torque and reduces the maximal efficiency of the free energy transduction to 40–80% below the optimal efficiency. Heat irreversibly dissipates not only through the viscous friction of the probe but also directly from the motor due to torque-induced mechanical slip. Such irreversible heat dissipation is a crucial limitation for achieving a 100% free-energy transduction efficiency with biological nanomachines because biomolecules are easily deformed by external torque. en-copyright= kn-copyright= en-aut-name=SumiTomonari en-aut-sei=Sumi en-aut-mei=Tomonari kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KlumppStefan en-aut-sei=Klumpp en-aut-mei=Stefan kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= affil-num=1 en-affil=Research Institute for Interdisciplinary Science, Department of Chemistry, Faculty of Science, Okayama University kn-affil= affil-num=2 en-affil=Department Theory and Bio-Systems, Max Planck Institute of Colloids and Interfaces kn-affil= en-keyword=F-1-ATPase kn-keyword=F-1-ATPase en-keyword=rotary molecular motor kn-keyword=rotary molecular motor en-keyword=chemomechanical network model kn-keyword=chemomechanical network model en-keyword=free-energy transduction efficiency kn-keyword=free-energy transduction efficiency en-keyword=ATP synthesis kn-keyword=ATP synthesis en-keyword=torque-induced mechanical slip kn-keyword=torque-induced mechanical slip END start-ver=1.4 cd-journal=joma no-vol=58 cd-vols= no-issue=26 article-no= start-page=2934 end-page=2943 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190531 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Photochemical Characterization of a New Heliorhodopsin from the Gram-Negative Eubacterium Bellilinea caldifistulae (BcHeR) and Comparison with Heliorhodopsin-48C12 en-subtitle= kn-subtitle= en-abstract= kn-abstract= Many microorganisms express rhodopsins, pigmented membrane proteins capable of absorbing sunlight and harnessing that energy for important biological functions such as ATP synthesis and phototaxis. Microbial rhodopsins that have been discovered to date are categorized as type-1 rhodopsins. Interestingly, researchers have very recently unveiled a new microbial rhodopsin family named the heliorhodopsins, which are phylogenetically distant from type-1 rhodopsins. Among them, only heliorhodopsin-48C12 (HeR-48C12) from a Gram-positive eubacterium has been photochemically characterized [Pushkarev, A., et al. (2018) Nature 558, 595-599]. In this study, we photochemically characterize a purple-colored heliorhodopsin from Gram-negative eubacterium Bellilinea caldifistulae (BcHeR) as a second example and identify which properties are or are not conserved between BcHeR and HeR-48C12. A series of photochemical measurements revealed several conserved properties between them, including a visible absorption spectrum with a maximum at around 550 nm, the lack of ion-transport activity, and the existence of a second-order O-like intermediate during the photocycle that may activate an unidentified biological function. In contrast, as a property that is not conserved, although HeR-48C12 shows the light adaptation state of retinal, BcHeR showed the same retinal configuration under both dark- and light-adapted conditions. These comparisons of photochemical properties between BcHeR and HeR-48C12 are an important first step toward understanding the nature and functional role of heliorhodopsins. en-copyright= kn-copyright= en-aut-name=ShibukawaAtsushi en-aut-sei=Shibukawa en-aut-mei=Atsushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KojimaKeiichi en-aut-sei=Kojima en-aut-mei=Keiichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NakajimaYu en-aut-sei=Nakajima en-aut-mei=Yu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=NishimuraYosuke en-aut-sei=Nishimura en-aut-mei=Yosuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=YoshizawaSusumu en-aut-sei=Yoshizawa en-aut-mei=Susumu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=SudoYuki en-aut-sei=Sudo en-aut-mei=Yuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= affil-num=1 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences , Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences , Okayama University kn-affil= affil-num=3 en-affil=Atmosphere and Ocean Research Institute , The University of Tokyo kn-affil= affil-num=4 en-affil=Atmosphere and Ocean Research Institute , The University of Tokyo kn-affil= affil-num=5 en-affil=Atmosphere and Ocean Research Institute , The University of Tokyo kn-affil= affil-num=6 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences , Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=4 cd-vols= no-issue=12 article-no= start-page=15249 end-page=15254 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190703 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Characterization of Pieces of Paper That Form Reagent Containers for Use as Portable Analytical Devices en-subtitle= kn-subtitle= en-abstract= kn-abstract= Reagent-deposited pieces of paper were characterized by the use of a compact conductometer, a compact pH sensor, and a conventional spectrophotometer to assess their suitability for use as reagent containers. The pieces of paper were fabricated by wax printing to form a limited hydrophilic area to which a consistent volume of an aqueous reagent could be added. The pieces of paper without the reagent increased the conductivity of water gradually because of the release of sodium salts, whereas pH of NaOH decreased because of the acidity of the functional groups in the paper. Three reagents, sulfamic acid as an acid, Na2CO3 as a base, and BaCl2 as a metal salt, were deposited on the pieces of paper to evaluate their ability to release from the pieces of paper. Sulfamic acid and Na2CO3 were released in quantities of 58 and 73% into water after 420 s, whereas 100% of BaCl2 was released after 480 s. The conductometric titrations of NaOH, HCl, and Na2SO4, and the spectrophotometry of Fe2+ were examined using the pieces of paper that contained sulfamic acid, Na2CO3, BaCl2, and 1,10-phenanthroline. Titrations using the pieces of paper suggested that the reagents were quantitatively released into the titrant, which resulted in a linear relationship between the endpoints and the equivalent points. In 120 s of soaking time, 60-70% of the reagents were released. The spectrophotometric measurements of Fe2+ indicated that when an excess amount of the reagents was deposited onto the pieces of paper, they nonetheless sufficiently fulfilled the role of a reagent container. en-copyright= kn-copyright= en-aut-name=BukingSupatana en-aut-sei=Buking en-aut-mei=Supatana kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SuedomiYusuke en-aut-sei=Suedomi en-aut-mei=Yusuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NacaprichaDuangjai en-aut-sei=Nacapricha en-aut-mei=Duangjai kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=KanetaTakashi en-aut-sei=Kaneta en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Flow Innovation-Research for Science and Technology Laboratories (FIRST Labs) and Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University kn-affil= affil-num=2 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Flow Innovation-Research for Science and Technology Laboratories (FIRST Labs) and Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University kn-affil= affil-num=4 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=83 cd-vols= no-issue=18 article-no= start-page=11028 end-page=11056 dt-received= dt-revised= dt-accepted= dt-pub-year=2018 dt-pub=20180809 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Unified Total Synthesis, Stereostructural Elucidation, and Biological Evaluation of Sarcophytonolides en-subtitle= kn-subtitle= en-abstract= kn-abstract= Sarcophytonolides are cembranolide diterpenes isolated from the soft corals of genus Sarcophyton. Unified total synthesis of sarcophytonolides C, E, F, G, H, and J and isosarcophytonolide D was achieved. The synthetic routes feature NaHMDS- or SmI2-mediated fragment coupling, alkoxycarbonylallylation, macrolactonization, and transannular ring-closing metathesis. These total syntheses led to the absolute configurational confirmation of sarcophytonolide H, elucidation of sarcophytonolides C, E, F, and G, and revision of sarcophytonolide J and isosarcophytonolide D. We also evaluated the antifouling activity and toxicity of the synthetic sarcophytonolides H and J and their analogues as well as the cytotoxicity of the synthetic sarcophytonolides and the key synthetic intermediates. en-copyright= kn-copyright= en-aut-name=TakamuraHiroyoshi en-aut-sei=Takamura en-aut-mei=Hiroyoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KikuchiTakahiro en-aut-sei=Kikuchi en-aut-mei=Takahiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=IwamotoKohei en-aut-sei=Iwamoto en-aut-mei=Kohei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=NakaoEiji en-aut-sei=Nakao en-aut-mei=Eiji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=HaradaNaoki en-aut-sei=Harada en-aut-mei=Naoki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=OtsuTaichi en-aut-sei=Otsu en-aut-mei=Taichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=EndoNoriyuki en-aut-sei=Endo en-aut-mei=Noriyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=FukudaYuji en-aut-sei=Fukuda en-aut-mei=Yuji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=OhnoOsamu en-aut-sei=Ohno en-aut-mei=Osamu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=SuenagaKiyotake en-aut-sei=Suenaga en-aut-mei=Kiyotake kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= en-aut-name=GuoYue-Wei en-aut-sei=Guo en-aut-mei=Yue-Wei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=11 ORCID= en-aut-name=KadotaIsao en-aut-sei=Kadota en-aut-mei=Isao kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=12 ORCID= affil-num=1 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology , Okayama University kn-affil= affil-num=2 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology , Okayama University kn-affil= affil-num=3 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology , Okayama University kn-affil= affil-num=4 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology , Okayama University kn-affil= affil-num=5 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology , Okayama University kn-affil= affil-num=6 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology , Okayama University kn-affil= affil-num=7 en-affil=Himeji EcoTech Co., Ltd. kn-affil= affil-num=8 en-affil=Himeji EcoTech Co., Ltd. kn-affil= affil-num=9 en-affil= Department of Chemistry and Life Science, School of Advanced Engineering , Kogakuin University kn-affil= affil-num=10 en-affil= Department of Chemistry, Faculty of Science and Technology , Keio University kn-affil= affil-num=11 en-affil=Shanghai Institute of Materia Medica , Chinese Academy of Sciences kn-affil= affil-num=12 en-affil=Department of Chemistry, Graduate School of Natural Science and Technology , Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=80 cd-vols= no-issue=6 article-no= start-page=3111 end-page=3123 dt-received= dt-revised= dt-accepted= dt-pub-year=2015 dt-pub=20150227 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Stereodivergent synthesis and relative stereostructure of the C1-C13 fragment of symbiodinolide en-subtitle= kn-subtitle= en-abstract= kn-abstract= Four possible diastereomers of the C1-C13 fragment of symbiodinolide, which were proposed by the stereostructural analysis of the degraded product, were synthesized in a stereodivergent and stereoselective manner. The key transformations were aldol reaction of methyl acetoacetate with the aldehyde, diastereoselective reduction of the resulting β-hydroxy ketone, and the stereoinversion at the C6 position. Comparison of the (1)H NMR data between the four synthetic products and the degraded product revealed the relative stereostructure of the C1-C13 fragment of symbiodinolide. en-copyright= kn-copyright= en-aut-name=TakamuraHiroyoshi en-aut-sei=Takamura en-aut-mei=Hiroyoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=WadaHiroko en-aut-sei=Wada en-aut-mei=Hiroko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=OginoMao en-aut-sei=Ogino en-aut-mei=Mao kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=KikuchiTakahiro en-aut-sei=Kikuchi en-aut-mei=Takahiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=KadotaIsao en-aut-sei=Kadota en-aut-mei=Isao kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=UemuraDaisuke en-aut-sei=Uemura en-aut-mei=Daisuke kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= affil-num=1 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Department of Chemistry, Faculty of Science, Kanagawa University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=18 cd-vols= no-issue=9 article-no= start-page=2110 end-page=2113 dt-received= dt-revised= dt-accepted= dt-pub-year=2016 dt-pub=20160506 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Total Synthesis of Sarcophytonolide H and Isosarcophytonolide D: Structural Revision of Isosarcophytonolide D and Structure-Antifouling Activity Relationship of Sarcophytonolide H en-subtitle= kn-subtitle= en-abstract= kn-abstract= The first total syntheses of sarcophytonolide H and the originally proposed and correct structures of isosarcophytonolide D have been achieved via transannular ring-closing metathesis (RCM). These total syntheses culminated in the stereostructural confirmation of sarcophytonolide H and the reassignment of isosarcophytonolide D, respectively. The antifouling activity of the synthetic sarcophytonolide H and its analogues was also evaluated. en-copyright= kn-copyright= en-aut-name=TakamuraHiroyoshi en-aut-sei=Takamura en-aut-mei=Hiroyoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KikuchiTakahiro en-aut-sei=Kikuchi en-aut-mei=Takahiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=EndoNoriyuki en-aut-sei=Endo en-aut-mei=Noriyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=FukudaYuji en-aut-sei=Fukuda en-aut-mei=Yuji kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=KadotaIsao en-aut-sei=Kadota en-aut-mei=Isao kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Himeji EcoTech Co., Ltd. kn-affil= affil-num=4 en-affil=Himeji EcoTech Co., Ltd. kn-affil= affil-num=5 en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=18 cd-vols= no-issue=17 article-no= start-page=4380 end-page=4383 dt-received= dt-revised= dt-accepted= dt-pub-year=2016 dt-pub=20160811 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Synthesis and Properties of Sila[n]helicenes via Dehydrogenative Silylation of C-H Bonds under Rhodium Catalysis en-subtitle= kn-subtitle= en-abstract= kn-abstract= Use of a rhodium catalyst with (R)-(S)-BPPFA ligand allows efficient synthesis of sila[n]helicenes via dehydrogenative silylation of C-H bonds. By selecting the proper ligands, the current method provides the ability to prepare unsymmetrical sila[n]helicene derivatives without any oxidants. The resulting sila[6]helicene is a rare example of a five-membered ring-fused [6]helicene, which was isolated as a single pure enantiomer without substituents on the terminal benzene rings. en-copyright= kn-copyright= en-aut-name=MuraiMasahito en-aut-sei=Murai en-aut-mei=Masahito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=OkadaRyo en-aut-sei=Okada en-aut-mei=Ryo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NishiyamaAtsushi en-aut-sei=Nishiyama en-aut-mei=Atsushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=TakaiKazuhiko en-aut-sei=Takai en-aut-mei=Kazuhiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=18 cd-vols= no-issue=7 article-no= start-page=1642 end-page=1645 dt-received= dt-revised= dt-accepted= dt-pub-year=2016 dt-pub=20160321 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Palladium-Catalyzed Regio- and Stereoselective Carbothiolation of Terminal Alkynes with Azolyl Sulfides en-subtitle= kn-subtitle= en-abstract= kn-abstract= Palladium-catalyzed carbothiolation of terminal alkynes with azolyl sulfides affords various 2-(azolyl)alkenyl sulfides with perfect regio- and stereoselectivities. The present addition reaction proceeded through a direct cleavage of carbon-sulfur bonds in azolyl sulfides. The resulting adducts that are useful intermediates in organic synthesis are further transformed to multisubstituted olefins containing azolyl moieties. en-copyright= kn-copyright= en-aut-name=IwasakiMasayuki en-aut-sei=Iwasaki en-aut-mei=Masayuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=TopolovčanNikola en-aut-sei=Topolovčan en-aut-mei=Nikola kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=HuHao en-aut-sei=Hu en-aut-mei=Hao kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=NishimuraYugo en-aut-sei=Nishimura en-aut-mei=Yugo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=GagnotGlwadys en-aut-sei=Gagnot en-aut-mei=Glwadys kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=nakornRungsaeng Na en-aut-sei=nakorn en-aut-mei=Rungsaeng Na kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=YuvacharaskulRamida en-aut-sei=Yuvacharaskul en-aut-mei=Ramida kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=NakajimaKiyohiko en-aut-sei=Nakajima en-aut-mei=Kiyohiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=NishiharaYasushi en-aut-sei=Nishihara en-aut-mei=Yasushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= affil-num=1 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=7 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=8 en-affil=Department of Chemistry, Aichi University of Education kn-affil= affil-num=9 en-affil=Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=18 cd-vols= no-issue=9 article-no= start-page=2020 end-page=2023 dt-received= dt-revised= dt-accepted= dt-pub-year=2016 dt-pub=20160427 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Lewis Acid and Fluoroalcohol Mediated Nucleophilic Addition to the C2 Position of Indoles en-subtitle= kn-subtitle= en-abstract= kn-abstract= Indole readily undergoes nucleophilic substitution at the C3 site, and many indole derivatives have been functionalized using this property. Indole also forms indolium, which allows electrophilic addition in acidic conditions, but current examples have been limited to intramolecular reactions. C2 site-selective nucleophilic addition to indole derivatives using fluoroalcohol and a Lewis acid was developed. en-copyright= kn-copyright= en-aut-name=MorimotoNaoki en-aut-sei=Morimoto en-aut-mei=Naoki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=MoriokuKumika en-aut-sei=Morioku en-aut-mei=Kumika kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=SuzukiHideyuki en-aut-sei=Suzuki en-aut-mei=Hideyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=TakeuchiYasuo en-aut-sei=Takeuchi en-aut-mei=Yasuo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=NishinaYuta en-aut-sei=Nishina en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Okayama Univ, Grad Sch Med Dent & Pharmaceut Sci, Div Pharmaceut Sci kn-affil= affil-num=2 en-affil= Okayama Univ, Fac Engn, Dept Appl Chem & Biotechnol kn-affil= affil-num=3 en-affil=Okayama Univ, Res Core Interdisciplinary Sci kn-affil= affil-num=4 en-affil=Okayama Univ, Grad Sch Med Dent & Pharmaceut Sci, Div Pharmaceut Sci kn-affil= affil-num=5 en-affil=Okayama Univ, Res Core Interdisciplinary Sci kn-affil= END start-ver=1.4 cd-journal=joma no-vol=19 cd-vols= no-issue=5 article-no= start-page=1092 end-page=1095 dt-received= dt-revised= dt-accepted= dt-pub-year=2017 dt-pub=20170217 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Synthesis of Benzoisoselenazolone Derivatives by Nickel-Catalyzed Dehydrogenative Direct Selenation of C(sp2)-H Bonds with Elemental Selenium in Air en-subtitle= kn-subtitle= en-abstract= kn-abstract= Nickel-catalyzed direct selenation of benzamides bearing an 8-quinolyl auxiliary with elemental selenium provides benzoisoselenazolones in good yield via carbon-selenium and nitrogen-selenium bond formation under aerobic conditions. In addition to aryl C-H bonds, the method can also be applied to alkenyl C-H bonds, constructing an isoselenazolone skeleton. Simple mechanistic analysis shows that the reaction proceeds through a rate-determining C-H bond cleavage. The obtained benzoisoselenazolones are transformed into various organoselenium compounds and utilized as the catalyst for bromolactonization of alkenoic acids. en-copyright= kn-copyright= en-aut-name=IwasakiMasayuki en-aut-sei=Iwasaki en-aut-mei=Masayuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=MikiNatsumi en-aut-sei=Miki en-aut-mei=Natsumi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TsuchiyaYuta en-aut-sei=Tsuchiya en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=NakajimaKiyohiko en-aut-sei=Nakajima en-aut-mei=Kiyohiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=NishiharaYasushi en-aut-sei=Nishihara en-aut-mei=Yasushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil= Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Department of Chemistry, Aichi University of Education kn-affil= affil-num=5 en-affil= Research Institute for Interdisciplinary Science, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=29 cd-vols= no-issue=5 article-no= start-page=2150 end-page=2156 dt-received= dt-revised= dt-accepted= dt-pub-year=2017 dt-pub=20170302 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Real-Time, in Situ Monitoring of the Oxidation of Graphite: Lessons Learned en-subtitle= kn-subtitle= en-abstract= kn-abstract= Graphite oxide (GO) and its constituent layers (i.e., graphene oxide) display a broad range of functional groups and, as such, have attracted significant attention for use in numerous applications. GO is commonly prepared using the “Hummers method” or a variant thereof in which graphite is treated with KMnO4 and various additives in H2SO4. Despite its omnipresence, the underlying chemistry of such oxidation reactions is not well understood and typically affords results that are irreproducible and, in some cases, unsafe. To overcome these limitations, the oxidation of graphite under Hummers-type conditions was monitored over time using in situ X-ray diffraction and in situ X-ray absorption near edge structure analyses with synchrotron radiation. In conjunction with other atomic absorption spectroscopy, UV–vis spectroscopy and elemental analysis measurements, the underlying mechanism of the oxidation reaction was elucidated, and the reaction conditions were optimized. Ultimately, the methodology for reproducibly preparing GO on large scales using only graphite, H2SO4, and KMnO4 was developed and successfully adapted for use in continuous flow systems. en-copyright= kn-copyright= en-aut-name=MorimotoNaoki en-aut-sei=Morimoto en-aut-mei=Naoki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SuzukiHideyuki en-aut-sei=Suzuki en-aut-mei=Hideyuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TakeuchiYasuo en-aut-sei=Takeuchi en-aut-mei=Yasuo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=KawaguchiShogo en-aut-sei=Kawaguchi en-aut-mei=Shogo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=KunisuMasahiro en-aut-sei=Kunisu en-aut-mei=Masahiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=BielawskiChristopher W. en-aut-sei=Bielawski en-aut-mei=Christopher W. kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=NishinaYuta en-aut-sei=Nishina en-aut-mei=Yuta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= affil-num=1 en-affil=Graduate School of Medicine, Dentistry, and Pharmaceutical Sciences, Division of Pharmaceutical Sciences, Okayama University kn-affil= affil-num=2 en-affil=Research Core for Interdisciplinary Sciences, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Medicine, Dentistry, and Pharmaceutical Sciences, Division of Pharmaceutical Sciences, Okayama Universit kn-affil= affil-num=4 en-affil=Japan Synchrotron Radiation Research Institute (JASRI), SPring-8 kn-affil= affil-num=5 en-affil=Toray Research Center, Inc., Surface Science Laboratories kn-affil= affil-num=6 en-affil=Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS) kn-affil= affil-num=7 en-affil=Research Core for Interdisciplinary Sciences, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=139 cd-vols= no-issue=12 article-no= start-page=4376 end-page=4389 dt-received= dt-revised= dt-accepted= dt-pub-year=2017 dt-pub=20170329 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Demonstration of a Light-Driven SO42- Transporter and Its Spectroscopic Characteristics. en-subtitle= kn-subtitle= en-abstract= kn-abstract= In organisms, ion transporters play essential roles in the generation and dissipation of ion gradients across cell membranes. Microbial rhodopsins selectively transport cognate ions using solar energy, in which the substrate ions identified to date have been confined to monovalent ions such as H+, Na+, and Cl-. Here we report a novel rhodopsin from the cyanobacterium Synechocystis sp. PCC 7509, which inwardly transports a polyatomic divalent sulfate ion, SO42-, with changes of its spectroscopic properties in both unphotolyzed and photolyzed states. Upon illumination, cells expressing the novel rhodopsin, named Synechocystis halorhodopsin (SyHR), showed alkalization of the medium only in the presence of Cl- or SO42-. That alkalization signal was enhanced by addition of a protonophore, indicating an inward transport of Cl- and SO42- with a subsequent secondary inward H+ movement across the membrane. The anion binding to SyHR was suggested by absorption spectral shifts from 542 to 536 nm for Cl- and from 542 to 556 nm for SO42-, and the affinities of Cl- and SO42- were estimated as 0.112 and 5.81 mM, respectively. We then performed time-resolved spectroscopic measurements ranging from femtosecond to millisecond time domains to elucidate the structure and structural changes of SyHR during the photoreaction. Based on the results, we propose a photocycle model for SyHR in the absence or presence of substrate ions with the timing of their uptake and release. Thus, we demonstrate SyHR as the first light-driven polyatomic divalent anion (SO42-) transporter and report its spectroscopic characteristics. en-copyright= kn-copyright= en-aut-name=NihoAkiko en-aut-sei=Niho en-aut-mei=Akiko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=YoshizawaSusumu en-aut-sei=Yoshizawa en-aut-mei=Susumu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TsukamotoTakashi en-aut-sei=Tsukamoto en-aut-mei=Takashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=KuriharaMarie en-aut-sei=Kurihara en-aut-mei=Marie kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=TaharaShinya en-aut-sei=Tahara en-aut-mei=Shinya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=NakajimaYu en-aut-sei=Nakajima en-aut-mei=Yu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=MizunoMisao en-aut-sei=Mizuno en-aut-mei=Misao kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=KuramochiHikaru en-aut-sei=Kuramochi en-aut-mei=Hikaru kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=TaharaTahei en-aut-sei=Tahara en-aut-mei=Tahei kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= en-aut-name=MizutaniYasuhisa en-aut-sei=Mizutani en-aut-mei=Yasuhisa kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=10 ORCID= en-aut-name=SudoYuki en-aut-sei=Sudo en-aut-mei=Yuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=11 ORCID= affil-num=1 en-affil=Faculty of Pharmaceutical Sciences, Okayama University kn-affil= affil-num=2 en-affil=Atmosphere and Ocean Research Institute, The University of Tokyo kn-affil= affil-num=3 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University kn-affil= affil-num=4 en-affil= Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University kn-affil= affil-num=5 en-affil= Molecular Spectroscopy Laboratory, RIKEN kn-affil= affil-num=6 en-affil= Atmosphere and Ocean Research Institute, The University of Tokyo kn-affil= affil-num=7 en-affil=Department of Chemistry, Graduate School of Science, Osaka University kn-affil= affil-num=8 en-affil=Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics kn-affil= affil-num=9 en-affil=Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics kn-affil= affil-num=10 en-affil=Department of Chemistry, Graduate School of Science, Osaka University kn-affil= affil-num=11 en-affil=Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University kn-affil= END