| 1. |
Swelling behavior of super-absorbent polymer gels
We previously report development of a new class of ionic polymer gels having lipophilic ion-pairs that consist of a lipophilic tetraphenylborate anion and a quaternary ammonium cation with long alkyl chains. They swelled largely in the less polar solvents as 'super-absorbent' ionic polymer gels. The driving force of the large swelling was osmotic pressure induced by dissociation of lipophilic ion-pairs in these solvents. Here we wish to present discontinuous volume phase transition of 'super-absorbent' ionic polymer gels the by change of solvent polarity even in low dielectric media. Moreover, we investigated the effect of neutral comonomers to swelling behaviours in various organic solvents by changing the length of their alkyl chains. The ionic polymer gels with longer alkyl chain swelled in a large magnitude in the less polar solvents and those with shorter alkyl one did in more polar solvents.. |
| 2. |
Preparation and function of polymer gels with hydrophobic ion pairs
Molecular design of polymer gels with high swelling properties in non polar solvents lays on compatibility of the polymer chain with oil. In this study, we demonstrate new polymer gels based on the hydrophobic ion pairs in the polymer chain. They provided the high swelling degrees in polar solvents. In the mixtures of water and acetonitrile, the polymer gels exhibited volume phase transition.. |
| 3. |
Molecular design of super-absorbent polymer gels
Ionic polymer gels with the ability to absorb several hundreds times as much water as their dry weights have been used as 'super-absorbent polymers' in wide range of biomedical and agricultural applications. However, in the low dielectric media (ε < 10), common ions form tightly bound ion-pairs or multiplet aggregates, and incompatibilities between the polymer chain and the solvents greatly diminish the swelling power. Here we report development of a new class of ionic polymer gels having lipophilic ion-pairs that consist of a lipophilic tetraphenylborate anion and a quaternary ammonium cation with long alkyl chains. They swelled largely in the less polar solvents such as tetrahydrofuran and chloroform as 'super-absorbent' ionic polymer gels.. |
| 4. |
非金属ポルフィセン化学の開拓:新規リンポルフィセンの合成. |
| 5. |
非金属ポルフィセンの化学:新規リンポルフィセンの合成. |
| 6. |
長鎖アルキル修飾ルテニウム三核錯体の合成とその自己集合特性. |
| 7. |
軸位連結型ルテニウム(II)ポルフィリン‐ランタノイド(III)二核錯体の合成と発光特性. |
| 8. |
水素化ポルフィセン金属錯体の合成と酸化還元特性. |
| 9. |
可視光駆動型ビタミンB12高分子触媒の開発と物質変換反応への応用. |
| 10. |
メタロセン集積型金属クラスターの合成と電子特性. |
| 11. |
ポルフィリン環を含む多核箱形クラスターの合成と溶液内ホストゲスト相互作用. |
| 12. |
ポルフィリンとルテニウム三核錯体をユニットとする多核箱型クラスターの構築とホストゲスト相互作用. |
| 13. |
ホウ素‐窒素錯形成を利用した超分子複合体の固相合成法の構築と固体発光特性の評価. |
| 14. |
コバルト錯体とバイオマスを用いた光駆動型水素発生触媒系の構築. |
| 15. |
コバルトポルフィセンの配位子還元を利用したCo‐C結合の形成反応. |
| 16. |
コバルトポルフィセンの配位子レドックスを利用した酸化的付加反応. |
| 17. |
コバルトポルフィセンの配位子レドックスを利用した触媒的脱ハロゲン化反応. |
| 18. |
コバルトポルフィセン錯体類の酸化還元挙動と酸化的付加反応. |
| 19. |
非金属ポルフィセンの化学:新規リンポルフィセンの合成と発光挙動. |
| 20. |
重合部位を有する新規ポルフィセン金属錯体の合成. |
| 21. |
発光性包接結晶の分子設計:固相合成法の適用. |
| 22. |
発光性包接結晶の分子設計:多色,白色,室温リン光材料へのアプローチ. |
| 23. |
多核錯体を集積化したメタロ超分子ポリマーの創製とレドックス特性. |
| 24. |
多座配位子を末端に有する多核金属錯体の合成と物性. |
| 25. |
ルテニウムポルフィセン重合薄膜の合成及びそのエレクトロクロミック特性. |
| 26. |
ポルフィリン環を含むRu十二核箱型クラスターの合成,構造および溶液内挙動. |
| 27. |
ビタミンB12‐Ru光増感剤系への電子メディエーターの導入とその応用. |
| 28. |
ビタミンB12誘導体を用いた有機ハロゲン化合物からの電気化学的物質変換反応. |
| 29. |
ビタミンB12誘導体を触媒とするラジカル的トリフルオロメチル化反応の開発. |
| 30. |
ビタミンB12誘導体を触媒とするトリフルオロメチル化反応. |
| 31. |
トリフルオロメチル基を軸配位子とするビタミンB12誘導体の合成と性質. |
| 32. |
コバルトポルフィセン錯体の配位子還元体を活性種とした反応とその機構. |
| 33. |
Ru三核錯体とポルフィリンを含む多核箱形クラスターの合成とホストゲスト相互作用. |
| 34. |
自己組織化を利用した多核金属錯体のメゾスコピック超分子構造体形成とその特性. |
| 35. |
自己組織化を利用した多核金属錯体のメゾスコピック超分子構造体形成とその特性. |
| 36. |
自己組織化を利用した多核金属錯体のメゾスコピック超分子構造体形成とその特性. |
| 37. |
新規オキシム型二核コバルト錯体の合成とその性質. |
| 38. |
新規イミダゾール修飾ポルフィセンの合成. |
| 39. |
多核錯体を集積化した環状構造体への修飾基導入法の開拓. |
| 40. |
多核クラスターユニットの事前修飾による機能性高分子錯体の合成. |
| 41. |
多核クラスターユニットの事前修飾による機能性高分子錯体の合成. |
| 42. |
多孔性有機結晶のナノ空間を利用した強発光性室温リン光材料の創製. |
| 43. |
多孔性有機結晶のナノ空間を利用した芳香族炭化水素の高感度蛍光検出. |
| 44. |
ポルフィリン構造異性体を集積化した電解重合薄膜の作製とそのエレクトロクロミック特性. |
| 45. |
ポルフィリン構造異性体を集積化した電解重合薄膜の作製とそのエレクトロクロミック特性. |
| 46. |
ポルフィリン構造異性体を集積化した電解重合薄膜の作製とそのエレクトロクロミック特性. |
| 47. |
ポルフィリン構造異性体を集積化した電解重合薄膜の創製及びそのエレクトロクロミック特性. |
| 48. |
ビタミンB12誘導体を触媒とした電解トリフルオロメチル化触媒反応. |
| 49. |
ビタミンB12誘導体のコバルト‐ヒドリド錯体を用いた有機合成反応の開拓. |
| 50. |
新規なリンポルフィセン錯体の合成と構造および酸化還元挙動. |
| 51. |
新規なポルフィセン15族元素錯体の合成とその物性. |
| 52. |
新規なポルフィセン15族元素錯体の合成とその電気化学的特性について. |
| 53. |
ポルフィセンリン錯体の合成と光・電気化学物性. |
| 54. |
新規なポルフィセンリン錯体の合成とその酸化還元挙動. |
| 55. |
新規なアンチモンポルフィセン錯体の合成と性質. |
| 56. |
Visible-Light-Driven, One-pot Amide Synthesis Catalyzed by the B 12 Model Complex under Aerobic Conditions
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Invited for this month's cover is the group of Prof. Dr. Hisashi Shimakoshi at Kyushu University, Japan. The front cover shows “le mariage” of an iridium complex and a vitamin B 12 derivative with two wedding rings in the background. This collaboration of two complexes is induced by visible light in the presence of air to achieve green molecular transformations. This protocol was applied to the synthesis of amides from a wide range of trichlorinated organic compounds. Read the full text of the article at 10.1002/cplu.201800522.. |
| 57. |
Toshikazu Ono, Hyuga Shinjo, Daiki Koga, Yoshio Hisaeda, Synthesis of a meso-Tetraalkylporphycene Bearing Reactive Sites: Toward Porphycene–Polydimethylsiloxane Hybrids with Enhanced Photophysical Properties, European Journal of Organic Chemistry, 10.1002/ejoc.201901497, Vol.2019, No.46, pp.7578-7583, 2019.12, © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim meso-Tetraalkyl porphycenes exhibit unique optical properties with wide potential applications. The very fact that incorporation of porphycenes into polymeric materials is rare, make this approach a particularly attractive one. In this work, meso-tetrakis(3-butenyl)porphycene bearing four terminal olefin groups is prepared via two synthetic strategies: 1) the McMurry reaction using 5,5′-diacyl-2,2′-bipyrroles as precursors and 2) the oxidative coupling of dipyrroethenes. The newly obtained porphycene has been characterized by single X-ray crystallography. A porphycene–polydimethylsiloxane hybrid film is successfully prepared by a platinum-catalyzed hydrosilylation reaction. The hybrid film can be anchored with tweezers, showing a weak red emission with a quantum yield of 0.4 % at room temperature, whose intensity drastically increases reaching a quantum yield of 6.7 % in liquid nitrogen (77 K). This report represents the first example of porphycene-containing elastomeric films for potential application in various fields.. |
| 58. |
Learning From Vitamin B12-Mediated Reactions: Cobalt(III)–Carbon-Assisted Catalytic C−H Difluoroacylation of (Hetero)Arenes through Controlled-Potential Electrolysis
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Invited for this month's cover picture is the group of Yoshio Hisaeda at Kyushu University (Japan). The cover picture shows the electrochemical activation of a vitamin B12 derivative and the obtained difluoroacylated products. Read the full text of the Article at 10.1002/celc.201900164.. |
| 59. |
Learning From Vitamin B 12 -Mediated Reactions: Cobalt(III)−Carbon-Assisted Catalytic C−H Difluoroacylation of (Hetero)Arenes through Controlled-Potential Electrolysis
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The synthesis of difluoromethylated (CF 2 R) (R=H, alkyl/aryl, CO 2 R, etc.) compounds has received considerable attention in recent years. In this study, the cobalt(III)−carbon-mediated catalytic C−H difluoroacylation of unactivated arenes and heteroarenes using BrCF 2 CO 2 Et is reported. This catalytic cycle is based on a valence change of the cobalt catalyst, a naturally derived vitamin B 12 derivative, driven by controlled-potential electrolysis at −0.8 V vs. Ag/AgCl under visible-light irradiation in dimethyl sulfoxide. A broad substrate scope is demonstrated, and two compounds were characterized according to their X-ray crystal structures. Mechanistic studies showed that the reaction proceeds through a radical pathway mediated by homolytic cleavage of the cobalt(III)–carbon bond. A turnover number of more than 100 was observed, owing to the inherent stability of the vitamin B 12 framework. This naturally derived catalytic system has potential applications in medicinal chemistry and materials science.. |
| 60. |
Keishiro Tahara, Ling Pan, Toshikazu Ono, Yoshio Hisaeda, Learning from b12 enzymes
Biomimetic and bioinspired catalysts for eco-friendly organic synthesis, Beilstein Journal of Organic Chemistry, 10.3762/bjoc.14.232, 2018.10, Cobalamins (B12) play various important roles in vivo. Most B12-dependent enzymes are divided into three main subfamilies: adenosylcobalamin-dependent isomerases, methylcobalamin-dependent methyltransferases, and dehalogenases. Mimicking these B12 enzyme functions under non-enzymatic conditions offers good understanding of their elaborate reaction mechanisms. Furthermore, bio-inspiration offers a new approach to catalytic design for green and eco-friendly molecular transformations. As part of a study based on vitamin B12 derivatives including heptamethyl cobyrinate perchlorate, we describe biomimetic and bioinspired catalytic reactions with B12 enzyme functions. The reactions are classified according to the corresponding three B12 enzyme subfamilies, with a focus on our recent development on electrochemical and photochemical catalytic systems. Other important reactions are also described, with a focus on radical-involved reactions in terms of organic synthesis.. |
