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991.
Dr. Tsuyoshi Murata Kenta Yoshida Dr. Shuichi Suzuki Dr. Akira Ueda Dr. Shinsuke Nishida Dr. Junya Kawai Dr. Kozo Fukui Prof. Dr. Kazunobu Sato Prof. Dr. Takeji Takui Prof. Dr. Kazuhiro Nakasuji Prof. Dr. Yasushi Morita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(52):e202201426
A novel neutral diradical of π-extended phenalenyl derivative having three oxo-groups, tri-tert-butyl-1,4,7-trioxophenalenyl, and two types of the corresponding σ-dimers were investigated. Quantum chemical calculations showed that the neutral diradical is in triplet ground state having doubly degenerate singly occupied molecular orbitals. The neutral diradical undergoes a σ-dimerization, generating two types of σ-dimers immediately after the preparation. One of the σ-dimers, which was selectively generated in the crystalline state, was a close-shell dimer linked through double-σ-bonds on the phenalenyl skeleton with a long C−C bond length of 1.66 Å. The other σ-dimer, which existed only in the solution state, was a peroxy-linked open-shell dimer in which one σ-bond was formed between two oxygen atoms. Furthermore, the temperature-dependent 1H NMR and ESR spectra revealed that these σ-dimers are in equilibrium in the solution state by the reversible σ-bond formation/cleavage via the neutral diradical as a key intermediate. 相似文献
992.
Iori Morita Takahiro Mori Takaaki Mitsuhashi Shotaro Hoshino Yoshimasa Taniguchi Takashi Kikuchi Kei Nagae Norihiro Nasu Makoto Fujita Tomohiko Ohwada Ikuro Abe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):4017-4022
C–S bond formation reactions are widely distributed in the biosynthesis of biologically active molecules, and thus have received much attention over the past decades. Herein, we report intramolecular C–S bond formation by a P450 monooxygenase, TleB, which normally catalyzes a C−N bond formation in teleocidin biosynthesis. Based on the proposed reaction mechanism of TleB, a thiol-substituted substrate analogue was synthesized and tested in the enzyme reaction, which afforded the unprecedented sulfur-containing thio-indolactam V, in addition to an unusual indole-fused 6/5/8-tricyclic product whose structure was determined by the crystalline sponge method. Interestingly, conformational analysis revealed that the SOFA conformation is stable in thio-indolactam V, in sharp contrast to the major TWIST form in indolactam V, resulting in differences in their biological activities. 相似文献
993.
Takanori Kondo Chihiro Yasui Ikkei Miyajima Dr. Taisuke Banno Prof. Dr. Kouichi Asakura Dr. Tokuma Fukuoka Dr. Kazunori Ushimaru Dr. Maito Koga Dr. Azusa Saika Dr. Tomotake Morita Dr. Yoshiaki Takahashi Chigusa Hayashi Dr. Masayuki Igarashi Prof. Dr. Daisuke Takahashi Prof. Dr. Kazunobu Toshima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(55):e202201733
Synthesis of three types of purpose-designed mannosylerythritol lipid (MEL)-D analogues with decanoyl groups, β-GlcEL-D, α-GlcEL-D, and α-MEL-D, was accomplished utilizing our boron-mediated aglycon delivery (BMAD) methods. Their self-assembling properties, recovery effects on damaged skin cells, and antibacterial activity were evaluated. It was revealed, for the first time, that α-GlcEL-D and α-MEL-D only generated giant vesicles, indicating that slight differences in the steric configuration of an erythritol moiety and fatty acyl chains affect the ability to form vesicles. Analogue α-MEL-D exhibited significant recovery effects on damaged skin cells. Furthermore, α-MEL-D exhibited antibacterial activity as high as that for MEL-D, indicating that α-MEL-D is a promising artificial sugar-based material candidate for enhancing the barrier function of the stratum corneum, superior to a known cosmetic ingredient, and possesses antibacterial activity. 相似文献
994.
Dr. Ryu Yamasaki Kento Morita Hiromi Iizumi Dr. Ai Ito Dr. Kazuo Fukuda Prof. Dr. Iwao Okamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10118-10122
Activated amide bonds have been attracting intense attention; however, most of the studied moieties have twisted amide character. To add a new strategy to activate amide bonds while maintaining its planarity, we envisioned the introduction of an alkynyl group on the amide nitrogen to disrupt amide resonance by nN→Csp conjugation. In this context, the conformations and properties of N-ethynyl-substituted aromatic amides were investigated by DFT calculations, crystallography, and NMR spectroscopic analysis. In contrast to the cis conformational preference of N-ethyl- and vinyl-substituted acetanilides, N-ethynyl-substituted acetanilide favors the trans conformation in the crystal and in solution. It also has a decreased double bond character of the C(O)−N bond, without twisting of the amide. N-Ethynyl-substituted acetanilides undergo selective C(O)−N bond or N−C(sp) bond cleavage reactions and have potential applications as activated amides for coupling reactions or easily cleavable tethers. 相似文献
995.
Dr. Tsuyoshi Murata Dr. Noriaki Asakura Dr. Ryotaro Tsuji Dr. Yuki Kanzaki Prof. Kazunobu Sato Prof. Takeji Takui Prof. Yasushi Morita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(12):e202104447
A new silyl-substituted trioxotriangulene ( TOT ) neutral radical and corresponding porous organosiloxanes (POSs) were synthesized. The neutral radical exhibited a peculiarly high stability and formed a diamagnetic π-dimer characteristic to TOT neutral radicals stabilized by the strong multiple SOMO-SOMO interaction in both solution and solid states. POSs including TOT units within the organosiloxane-wall were prepared by polycondensation of the silyl groups and formed microporous structures with ∼1 nm-size diameters. Redox ability of TOT units in the POS was demonstrated by the treatment of oxidant/reductant in heterogeneous suspension condition, where the TOT units were reversibly converted between reduced and neutral radical species. Furthermore, the solid-state electrochemical measurements of the POS revealed the reversible multi-stage redox ability of TOT units involving polyanionic species within the organosiloxane-wall. 相似文献
996.
997.
998.
Aryan Morita Felipe P. Perona Martinez Mayeul Chipaux Nicolas Jamot Simon R. Hemelaar Kiran J. van der Laan Romana Schirhagl 《Particle & Particle Systems Characterization》2019,36(8)
Fluorescent nanodiamonds (FNDs) can be used as nanoscale magnetic resonance sensors and stable optical labels. As a first step for using FNDs as nanosensors inside cells, they have to be ingested. Several techniques that improve particle uptake have been used. A simple approach based on commercially available liposomes is used to improve uptake. Uptake into colon cancer cells (HT‐29 cells) is demonstrated. Additionally, it is shown for the first time that one can facilitate diamond uptake into yeast cells by removing the cell wall and creating a so‐called spheroplast. Finally, the characteristics of FNDs coated with lipids and their behavior inside the cells are evaluated. 相似文献
999.
Kazunari Naka Hirofumi Sato Akihiro Morita Fumio Hirata Shigeki Kato 《Theoretical chemistry accounts》1999,102(1-6):165-169
The free-energy profile for the Menshutkin-type reaction NH3 + CH3Cl → NH3CH3
+ + Cl− in aqueous solution is studied using the RISM-SCF method. The effect of electron correlation on the free-energy profile is
estimated by the RISM-MP2 method at the HF optimized geometries along the reaction coordinate. Solvation was found to have
a large influence on the vibrational frequencies at the reactant, transition state and product; these vibrational frequencies
are utilized to calculate the zero-point energy correction of the free-energy profile. The computed barrier height and reaction
exothermicity are in reasonable agreement with those of experiment and previous calculations. The change of solvation structure
along the reaction path is represented by radial distribution functions between solute-solvent atomic sites. The mechanisms
of the reaction are discussed from the view points of solute electronic and solvation structures.
Received: 26 June 1998/Accepted: 28 August 1998 / Published online: 2 November 1998 相似文献
1000.