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Facile Formation of a Benzopyrane-Fused [28]Hexaphyrin That Exhibits Distinct Möbius Aromaticity
Tokuji, Sumito,Shin, Jae-Yoon,Kim, Kil Suk,Lim, Jong Min,Youfu, Katsuyuki,Saito, Shohei,Kim, Dongho,Osuka, Atsuhiro American Chemical Society 2009 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.131 No.21
<P>A benzopyrane-fused [28]hexaphyrin, 2, was prepared by simple heating of [26]hexaphyrin 1 in acetic acid. Fused [28]hexaphyrin 2 features a molecular twist, a distinct diatropic ring current, a large HOMA value, a large negative NICS value, and a large two-photon absorption (TPA) cross section even at room temperature, all of which support the Möbius aromaticity of 2. To the best of our knowledge, 2 is the first macrocycle that acquires distinct Möbius aromaticity without any assistance from metal coordination, temperature control, or protonation.</P>
Shota Kanno,Sumito Kashihara,Seonghee Jeong 제어로봇시스템학회 2014 제어로봇시스템학회 국제학술대회 논문집 Vol.2014 No.10
In a pHRI, physical contact between humans and robots may happen occasionally or on purpose. Extensive efforts have been made to develop safety measures reducing human injury and improving human safety. Contact sensor is a fundamental requirement for those robots to sense the contact with humans and to take appropriate safety measures. In this paper, we propose a safety confirmation type wide-range detectable contact sensor that detects an ultrasonic wave propagating through a viscoelastic tube. The proposed sensor generates ultrasonic waves from a transmitter installed at the end of a long and slender viscoelastic tube, and detects the waves as safety monitoring signals by a receiver located at the other end. For all cases where safety monitoring signals is not detected, such as an abnormal state of ultrasonic wave and sensor elements failure, it does not transmit safety. An estimation equation related to the propagating sound pressure and time of an ultrasonic wave in the silicon tube was derived through experimental investigation on the propagation characteristics in a straight and a curved tube. It was confirmed that a safety monitoring signal was successively generated in an arbitrary curved tube by setting an appropriate safety threshold which was calculated using the estimation equation.
Rath, Harapriya,Tokuji, Sumito,Aratani, Naoki,Furukawa, Ko,Lim, Jong Min,Kim, Dongho,Shinokubo, Hiroshi,Osuka, Atsuhiro WILEY-VCH Verlag 2010 Angewandte Chemie Vol.122 No.8
<B>Graphic Abstract</B> <P>Ein neuer Dreh bei Porphyrinen: Die Metallierung von Möbius-aromatischem Hexakis(pentafluorphenyl)[28]hexaphyrin ergibt ein stabiles organisches Radikal, das über ein zweifach verdrehtes π-System delokalisiert ist. Der Zweiphotonenabsorptionsquerschnitt ist deutlich höher als bei nichtaromatischen expandierten Porphyrinen (Pd rosa, Cl grün, N blau; ohne Phenylringe). <img src='wiley_img/00448249-2010-122-8-ANGE200906017-content.gif' alt='wiley_img/00448249-2010-122-8-ANGE200906017-content'> </P>
Son, Minjung,Sung, Young Mo,Tokuji, Sumito,Fukui, Norihito,Yorimitsu, Hideki,Osuka, Atsuhiro,Kim, Dongho The Royal Society of Chemistry 2014 Chemical communications Vol.50 No.23
<P>Two meso-meso vinylene-bridged Zn(II) porphyrin dimers 1 and 2 were analyzed in terms of the control of their conformational dynamics induced by the rotation around the double bond bridge. The dihedral angles between the two porphyrin rings were modulated through coordination with alpha,omega-diaminoalkanes of varying chain lengths.</P>
Yoon, Min-Chul,Kim, Pyosang,Yoo, Hyejin,Shimizu, Soji,Koide, Taro,Tokuji, Sumito,Saito, Shohei,Osuka, Atsuhiro,Kim, Dongho American Chemical Society 2011 The Journal of physical chemistry B Vol.115 No.50
<P>We investigated the photophysical properties of figure-eight-like meso-hexakis(trifluoromethyl) [26]- and [28]hexaphyrins(1.1.1.1.1.1) denoted as TFM26H and TFM28H, respectively, using steady-state and time-resolved spectroscopy along with theoretical calculations to explore their electronic and magnetic natures depending on their molecular aromaticity. TFM26H exhibited a well-resolved absorption feature and intense fluorescence, both of which were neither solvent- nor temperature-dependent. These optical properties were in agreement with its H?ckel's [4n + 2] aromaticity as observed in typical aromatic porphyrinoids. The S(1)-state lifetime of ~50 ps for TFM26H in solution was shorter than those in planar aromatic hexaphyrins (>100 ps) presumably due to nonplanar figure-eight geometry of TFM26H. However, TFM28H exhibited remarkable changes in solvent- and temperature-dependent absorption spectra as well as excited-state lifetimes indicating that a dynamic equilibrium occurs between the two conformational species. With the help of quantum mechanical geometry optimization and vertical excitation energy calculations, we found that the figure-eight double-sided conformer observed in the solid-state and single-sided distorted one could be the best candidates for the two conformers, which should be H?ckel antiaromatic and M?bius aromatic species, respectively, based on their optical characteristics, molecular orbital structures, and excited-state lifetimes. Conformational dynamics between these two conformers of TFM28H was scrutinized in detail by temperature-dependent (1)H NMR spectra in various solvents, which showed that the conformational equilibrium was quite sensitive to solvents and that a conformational change faster than the NMR time-scale occurs even at 173 K.</P>
Sou N. Matsunaga,Kojiro Shimada,Tatsuhiko Masuda,Junya Hoshi,Sumito Sato,Hiroki Nagashima,Hiroyuki Ueno 한국대기환경학회 2017 Asian Journal of Atmospheric Environment (AJAE) Vol.11 No.1
Ozone concentration in Tokyo Metropolitan area is one of the most serious issues of the local air quality. Tropospheric ozone is formed by radical reaction including volatile organic compound (VOC) and nitrogen oxides (NOx). Reduction of the emission of reactive VOC is a key to reducing ozone concentrations. VOC is emitted from anthropogenic sources and also from vegetation (biogenic VOC or BVOC). BVOC also forms ozone through NOx and radical reactions. Especially, in urban area, the BVOC is emitted into the atmosphere with high NOx concentration. Therefore, trees bordering streets and green spaces in urban area may contribute to tropospheric ozone. On the other hand, not all trees emit BVOC which will produce ozone locally. In this study, BVOC emissions have been investigated (terpenoids: isoprene, monoterpenes, sesquiterpenes) for 29 tree species. Eleven in the 29 species were tree species that did not emit BVOCs. Three in 12 cultivars for future planting (25 %) were found to emit no terpenoid BVOCs. Eight in 17 commonly planted trees (47%) were found to emit no terpenoid BVOC. Lower-emitting species have many advantages for urban planting. Therefore, further investigation is required to find the species which do not emit terpenoid BVOC. Emission of reactive BVOC should be added into guideline for the urban planting to prevent the creation of sources of ozone. It is desirable that species with no reactive BVOC emission are planted along urban streets and green areas in urban areas, such as Tokyo.
Soichiro Kondo,Kazufumi Takada,Taro Kojima,Kosuke Tanaka,Mitsutaka Yakabe,Eisuke Shibata,Yumi Umeda-Kamayama,Hidemasa Takao,Sumito Ogawa,Masahiro Akishita 대한노인병학회 2022 Annals of geriatric medicine and research Vol.26 No.3
A 91-year-old man with chronic cognitive impairment underwent shunt embolization for portosystemic encephalopathy (PSE). He experienced intermittent episodes of impaired consciousness and decreased cognitive function and activities of daily living (ADL), for which Alzheimer disease was suspected. On admission, he was in a coma and PSE was diagnosed based on his high ammonia level and the computed tomography findings. After shunt embolization, the patient fully recovered from the impaired consciousness and experienced no recurrence. The patient’s Revised Hasegawa Dementia Scale and Mini-Mental State Examination scores improved significantly from 12 and 17 to 30 and 29 points, respectively. The Barthel Index score also improved from 55/100 to 85/100, suggesting a marked improvement in ADL. PSE progresses slowly in very old patients and may mimic the clinical course of Alzheimer disease but without liver enzyme abnormalities. Therefore, it should be distinguished in every dementia case.