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Protonation-Triggered Conformational Changes to Möbius Aromatic [32]Heptaphyrins(1.1.1.1.1.1.1)
Saito, Shohei,Shin, Jae-Yoon,Lim, Jong Min,Kim, Kil Suk,Kim, Dongho,Osuka, Atsuhiro WILEY-VCH Verlag 2008 Angewandte Chemie Vol.47 No.50
<B>Graphic Abstract</B> <P>Switching Aromaticity: Conformations of [32]heptaphyrins(1.1.1.1.1.1.1) are dependent upon meso-aryl substituents, solvents, temperature, and protonation. Particularly, protonation of meso-pentafluorophenyl-substituted [32]heptaphyrin triggers conformational changes to form twisted aromatic Möbius structures (see picture), even at room temperature. <img src='wiley_img/14337851-2008-47-50-ANIE200804457-content.gif' alt='wiley_img/14337851-2008-47-50-ANIE200804457-content'> </P>
Saito, Shohei,Kim, Kil ,Suk,Yoon, Zin ,Seok,Kim, Dongho,Osuka, Atsuhiro WILEY-VCH Verlag 2007 Angewandte Chemie Vol.46 No.29
<B>Graphic Abstract</B> <P>An uneven split: Cooperative Cu<SUP>II</SUP> and B<SUP>III</SUP> metalation of meso-heptakis(pentafluorophenyl)[32]heptaphyrin (1) triggers an extrusion reaction to produce B<SUP>III</SUP> meso-tris(pentafluorophenyl)[14]subporphyrin (2) along with a Cu<SUP>II</SUP> porphyrin (3-Cu). Subporphyrin 2 exhibits unique optical properties that reflect the rotational restriction of its electron-withdrawing substituents. <img src='wiley_img/14337851-2007-46-29-ANIE200701682-content.gif' alt='wiley_img/14337851-2007-46-29-ANIE200701682-content'> </P>
Tanaka, Yasuo,Saito, Shohei,Mori, Shigeki,Aratani, Naoki,Shinokubo, Hiroshi,Shibata, Naoki,Higuchi, Yoshiki,Yoon, Zin Seok,Kim, Kil Suk,Noh, Su Bum,Park, Jong Kang,Kim, Dongho,Osuka, Atsuhiro WILEY-VCH Verlag 2008 Angewandte Chemie Vol.47 No.4
<B>Graphic Abstract</B> <P>Round the twist: Metalation of [36]octaphyrin 1 provided the Möbius aromatic Pd<SUB>2</SUB> complex 3 as well as the Hückel antiaromatic Pd<SUB>2</SUB> complex 2. This method can be applied to other expanded porphyrins and Group 10 metal ions. The aromatic/antiaromatic character was supported by NMR spectrscopy, NICS calculation, and two-photon absorption measurements. <img src='wiley_img/14337851-2008-47-4-ANIE200704407-content.gif' alt='wiley_img/14337851-2008-47-4-ANIE200704407-content'> </P>
Möbius Antiaromatic Bisphosphorus Complexes of [30]Hexaphyrins
Higashino, Tomohiro,Lim, Jong Min,Miura, Takahiro,Saito, Shohei,Shin, Jae-Yoon,Kim, Dongho,Osuka, Atsuhiro WILEY-VCH Verlag 2010 Angewandte Chemie Vol.122 No.29
<B>Graphic Abstract</B> <P>Aromatizität mit Dreh: Die Umkehr von Möbius-Aromatizität wurde in Mono-Phosphorkomplexen von [28]Hexaphyrinen und Bis-Phosphorkomplexen von [30]Hexaphyrinen durch eine Änderung der Anzahl der π-Elektronen zwischen [4n+2]π und [4n]π nachgewiesen. Bis-Phosphor[30]hexaphyrine (siehe Bild) sind die ersten strukturell charakterisierten Möbius-antiaromatischen Systeme, die formtreu, neutral und stabil sind. <img src='wiley_img_2010/00448249-2010-122-29-ANGE201001765-content.gif' alt='wiley_img_2010/00448249-2010-122-29-ANGE201001765-content'> </P>
Möbius Antiaromatic Bisphosphorus Complexes of [30]Hexaphyrins
Higashino, Tomohiro,Lim, Jong Min,Miura, Takahiro,Saito, Shohei,Shin, Jae-Yoon,Kim, Dongho,Osuka, Atsuhiro WILEY-VCH Verlag 2010 Angewandte Chemie Vol.49 No.29
<B>Graphic Abstract</B> <P>Aromaticity with a twist: The reversal of Möbius aromaticity occurs by changing the number of π electrons between [4n+2] and [4n] in monophosphorus complexes of [28]hexaphyrins and bisphosphorus complexes of [30]hexaphyrins. The 30π Möbius antiaromatic bisphosporus[30]hexaphyrins (see picture) were determined to be the first structurally characterized Möbius antiaromatic systems, which are rigid, neutral, and stable. <img src='wiley_img_2010/14337851-2010-49-29-ANIE201001765-content.gif' alt='wiley_img_2010/14337851-2010-49-29-ANIE201001765-content'> </P>
Lim, Jong Min,Shin, Jae-Yoon,Tanaka, Yasuo,Saito, Shohei,Osuka, Atsuhiro,Kim, Dongho American Chemical Society 2010 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.132 No.9
<P>Protonation-triggered conformational changes of <I>meso</I>-octakis(pentafluorophenyl) [36]octaphyrin and [38]octaphyrin have been investigated. The X-ray crystal structures and <SUP>1</SUP>H NMR analyses revealed that the protonation process cuts off intramolecular hydrogen bonds between aminic and iminic pyrrole units and, at the same time, produces intermolecular hydrogen-bond network between aminic pyrrole unit and counter-anions. Such a replacement induces some pyrrole inversion, leading to Möbius aromatic conformation for [36]octaphyrin and to Hückel aromatic conformation for [38]octaphyrin. These protonated octaphyrins show similar structures only with a subtle difference in tilted pyrrole angles, which results in their different topologies. This feature strongly suggests that the macrocycles control their topologies by pyrrole rotation to gain [4<I>n</I>]π Möbius or [4<I>n</I>+2]π Hückel aromatic stabilization, depending on the number of π-electrons. Detailed photophysical properties such as absorption/fluorescence, excited singlet/triplet state lifetimes, and two-photon absorption cross-section values have been presented for both protonated [36] and [38]octaphyrins in conjunction with their Möbius or Hückel aromaticity.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2010/jacsat.2010.132.issue-9/ja909744z/production/images/medium/ja-2009-09744z_0005.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja909744z'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja909744z'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja909744z'>ACS Electronic Supporting Info</A></P>
Ayako Uchinaka,Yoshinosuke Hamada,Seiji Mori,Shigeru Miyagawa,Atsuhiro Saito,Yoshiki Sawa,Nariaki Matsuura,Naomasa Kawaguchi 한국조직공학과 재생의학회 2015 조직공학과 재생의학 Vol.12 No.3
In ischemic heart disease, cardiomyocyte death results from both necrosis and apoptosis, and the area of infarction gradually increases. The induction of therapeutic angiogenesis is a promising therapy for this condition. In the present study, we investigated the actions of SV peptide—a 7-amino-acid sequence with angiogenic properties derived from osteopontin in the extracellular matrix—in a rat model of myocardial ischemia. We examined the angiogenesis activity of SV ex vivo using ring assay and dorsal air sac assay and in ischemic myocardium. We also conducted histological evaluations of left-ventricle remodeling and evaluated left ventricular (LV) function by echocardiography. The SV peptide had strong angiogenic effects both ex vivo and in vivo. In the experimental rats, this peptide stimulated the formation of new blood vessels in ischemic myocardium. Histological evaluation of the left ventricle in the SV-treated group showed a significant decrease in the size of the infarction, rate of myocardial fibrosis, and cardiomyocyte hypertrophy. Moreover, administration of the SV peptide significantly improved LV function. These results indicate that SV peptide induced angiogenesis in ischemic myocardium and improved cardiac function. Thus, it could serve as a potentially useful new therapy for ischemic heart disease.
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>
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>