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As a material application of DNA double helix, a natural chiral source that is insoluble in anything other than water, we investigated the use of DNA double helix as an asymmetric catalyst for the Diels-Alder reaction by forming a complex with a porphyrin copper(II) complex in ionic liquids. In [N4444][Gly], the reaction substrates were phase-separated, and the reaction mixture gelled or solidified at low temperatures, resulting in ineffective asymmetric catalysis. In contrast, the reaction proceeded in a homogeneous system in 75 % [N1223][N(CN)2], which is not possible in water, and high yield, diastereoselectivity, and enantioselectivity were obtained at -20°C.

Metalation of porphyrins is usually carried out in a carefully chosen solvent that offers mutual solubility to both the metal salt and free-base porphyrin. However, these methods suffer from certain disadvantages, such as slow reaction rates, low yields, high boiling solvents. Recently, it has become clear that several ionic liquids dissolve both porphyrins and metal salts. Herein, we reported that metalation of TPP utilizing ionic liquids. In [C8mim][Br], Cu(Ⅱ)-TPP complex is obtained 79 % yields. In the presentation, we report detail reaction condition and effective ionic liquids structure for the metalation., Ⅲ.論文集

This is a report on the fabrication and characterization of a dye-sensitized solar cell (DSSC) containing non-carboxylated porphyrin (5,10,15,20-tetrakis-(4-aminophenyl)porphyrin,TAPP)and various cyclodextrins(CDs).The photoelectric conversion of DSSC resulted from light harvesting of TAPP. The open-circuit voltage (Voc) was 0.41 V for DSSC without CD. On the other hand, it increased to 0.47 V, 0.47 V, 0.45 V, 0.49 V containing α-CD, β-CD, CM-β-CD, and γ-CD respectively. The photovoltaic performance increased by electron recombination, which is induced by the formation of an incorporation complex of TAPP with CDs(TAPP/CDs).As a result, we concluded that the TAPP/CDs act as photosensitizer for a DSSC.These results indicate that our techniques can be used for future research on the fabrication of porphyrin-dye DSSC.

最終講義, ヘム蛋白質の機能は活性中心に存在するヘムの電子的,磁気的,および立体的構造により精密に制御されている.私はヘム蛋白質の触媒反応機構を理解するため,多様なヘムモデル錯体を合成し,それらをultraviolet-visible(UV-Vis),infrared(IR),proton nuclear magnetic resonance(1H NMR),13C NMR,electronparamagnetic resonance(EPR),Mossbauer,X 線結晶解析,およびsuperconducting quantum interferencedevice(SQUID)などにより詳細に検討した.その結果,下記に示すいくつかの新しい知見を得ることができた.1)ポルフィリン環がラッフル変形すると低スピン-鉄(III)の電子状態が通常の(dxy)2(dxz,dyz)3から異常な(dxz,dyz)4(dxy)1に変化する.2)電子状態の変化に伴いポルフィリン環はラジカル的性質を示す.3)非平面ポルフィリン環は中間スピンを安定化する.4)中間スピン錯体には2 種類の電子状態が存在する.5)いくつかのサドル型ポルフィリン錯体では前例のないスピンクロスオーバー現象が観測される.ヘムモデル錯体の研究により明らかになった上記の現象のいくつかは生体中のヘム蛋白質の機能に深く関わっていることが指摘されている.To elucidate the reaction mechanisms of heme proteins, we examined the physicochemical properties of a wide variety of iron porphyrin complexes by means of ultraviolet-visible, infrared, proton nuclear magnetic resonance, carbon-13 nuclear magnetic resonance, electron paramagnetic resonance, and Mossbauer spectroscopy, as well as X-ray crystallography and superconducting quantum interference device magnetometry. We found that some complexes exhibit previously unobserved properties both in naturally occurring heme proteins and synthetic model heme complexes. These properties were as follows: (1) the electronic ground state of low-spin complexes changes from the common (dxz, dyz)3(dxy)2 to the less common (dxz, dyz)4(dxy)1 if the porphyrin ring is ruffled, (2) the porphyrin ring of such low-spin complexes shows a strong radical character, (3) the deformed porphyrin ring greatly stabilizes in the intermediate-spin state, which is usually quite unstable, (4) 2 types of electronic ground state exist in the intermediate-spin state, and (5) some saddled complexes exhibit novel spin crossover phenomena involving the intermediate-spin state. Some of these properties have crucial roles in the enzymatic process of heme proteins.

22-23 May 1997 (58th). 27-28 Nov. 1997 (59th), 49種類の異なる調合の感圧塗料(PSP)サンプルについて系統的な試験を実施した。プローブ分子には、7種類のポルフィリン、2種類のルテニウム錯体、3種類の芳香化合物を選んだ。それぞれの化合物は、シリコンポリマ、シリコンゴム、ポリエチレン、シリカゲルをバインダとして用いてアルミニウム板上に塗布した。これらのサンプルを、10から100kPaの圧力、273から333Kの温度範囲で、較正チャンバ内で試験した。圧力に対する感度については、ポルフィリンはルテニウム錯体、芳香化合物よりもバインダに対する依存性が小さいことが分かった。幾つかのPSP調合は、PtOEP(白金オクタエチルポルフィリン)とGP197(酸素透過性シリコンポリマ)から成る基準塗料より高い感度を示した。しかし、これらの塗料の温度に対する感度も基準塗料と同程度であった。さらに、より低い温度感度をもつPSPを開発するための研究が必要である。, Systematic tests have been performed on samples of Pressure-Sensitive Pains (PSPs) with 49 different formulations. Seven porphyrins, two ruthenium complexes, and three aromatic compounds were selected as a probe molecule. Each compound was deposited onto aluminum plates using silicon polymer, silicon rubber, polystyrene, and silica gel as a binder. These sample plates were tested in a calibration chamber in the pressure range from 10 to 100 kPa and the temperature range of 273 to 333 K. In terms of pressure sensitivity, it was found that porphyrins were less dependent on binder type than ruthenium complexes and aromatic compounds. Several PSP formulations have been found, which have higher sensitivity than the baseline paint composed of PtOEP (Platinum Octaethyl Porphyrin) and GP197 (oxygen permeable silicon polymer). The temperature sensitivity of those paints, however, is as good as the baseline. Further study will be needed to develop a PSP having lower temperature sensitivity., 資料番号: AA0001434009, レポート番号: NAL SP-38

資料番号: AA0063158008, レポート番号: JAXA-SP-06-017

金属イオンとボルフィリンが水溶液中で錯形成する際, 錯体形成前に両化学種間の会合体が存在していることを疎水性樹脂(AmberliteXAD-2)カラムを用いて確認した.金属イオン溶液の連続的な流れの中にポルフィリン溶液を注入すると, ボルフィリンはインジェクタ-の下流に設けたXADカラムに吸着する.その際, 会合及び錯形成した分の金属イオンも伴われて吸着し, その分金属イオン濃度が-時的に減少する.この減少分から算出すると, Cu^及びZn^とα, β, γ, δ-tetrakis(4-N-methylpyridyl)porphine(TMPyP)との会合定数は, それぞれ32(10℃)及び57(25℃)M^であった.ボルフィリンの金属錯体がCu^と金属置換反応する際も, 錯形成時と同様に会合体が生成していることが分かった.亜鉛錯体とCu^との置換反応の場合, 大きな会合定数が得られた.本研究により, 配位子あるいはその金属錯体が疎水性樹脂に吸着される現象を利用して, 金属イオンと配位子あるいはその金属錯体との間の相互作用を調べることができた.その結果は錯形成の反応速度論の実験より算出した値とほぼ一致した., The existence of intermediate species during complex formation between metal ions and porphyrin in aqueous solution was confirmed using an Amberlite XAD-2 resin column. When porphyrin solution is injected into the metal ion solution stream, the porphyrin adsorbed to the XAD column with the metal ions associated or complexed with it, and the decrease of the metal ion in solution is observed in the column eluant. Calculated from the decrease, the association constants of Cu^ and Zn^ with α, β, γ, δ-tetrakis(4- N-methylpyridyl)porphine (TMPyP) are 32 (l0℃) and 57 M^ (25℃), respectively. It was also confirmed that the intermediate exists before the metal replacement reaction between Cu^ and the metalloporphyrin complex. The association constant in the Cu^ /Zn-TMPyP system was especially large. As mentioned above, the interaction of the metal ion and the ligand before complex formation can be investigated by separating the ligand with the attached metal ion from the free metal ion using the hydrophobic interaction between the column and the ligand. These results were in good agreement with the values obtained by the kinetic method.

雑誌掲載版

雑誌掲載版

学際領域における分子イメージングフォーラム 宇宙航空研究開発機構 20061116 東京 日本, Interdisciplinary Forum on Molecular Imaging Japan Aerospace Exploration Agency 20061116 Tokyo Japan, 資料番号: AA0063158000, レポート番号: JAXA-SP-06-017

資料番号: AA0063158010, レポート番号: JAXA-SP-06-017

資料番号: AA0063158014, レポート番号: JAXA-SP-06-017

資料番号: AA0063158013, レポート番号: JAXA-SP-06-017

This is a report on the fabrication and characterization of a dye-sensitized solar cell (DSSC) containing non-carboxylated porphyrin (5,10,15,20-tetrakis-(4-aminophenyl)porphyrin,TAPP)and various cyclodextrins(CDs).The photoelectric conversion of DSSC resulted from light harvesting of TAPP. The open-circuit voltage (Voc) was 0.41 V for DSSC without CD. On the other hand, it increased to 0.47 V, 0.47 V, 0.45 V, 0.49 V containing α-CD, β-CD, CM-β-CD, and γ-CD respectively. The photovoltaic performance increased by electron recombination, which is induced by the formation of an incorporation complex of TAPP with CDs(TAPP/CDs).As a result, we concluded that the TAPP/CDs act as photosensitizer for a DSSC.These results indicate that our techniques can be used for future research on the fabrication of porphyrin-dye DSSC.

本研究では分子の構造を系統的に変化させて合成したポルフィリン発色団をもつ種々のアルコールを用いて、シリケートガラス表面にポルフィリンの単分子膜を作製し、縮合反応やシリルエステル結合の化学的安定性を検討し、安定な有機/無機界面の構築に必要な分子設計の指針を示すことに成功した。また、リニアテトラピロールであるビリンジオンのソルバトクロミズムについても述べている。, Doctor of Philosophy in Engineering, Doshisha University

ピリジン配位子を持つメチル化シクロデキストリン二量体と水溶性鉄ポルフィリンから構成される超分子ヘムタンパク質モデル化合物"hemoCD"を用いて、過酸化水素などのヒドロペルオキシドとの反応から、ペルオキシダーゼなどの酸化酵素における反応中間体および酸化活性種の捕捉とそれら反応性について検討を行った。, Doctor of Philosophy in Engineering, Doshisha University