ニトロシリロン (III) ポルフィリネート:ポルフィリン核の形状とFeNOの幾何学. 関連性はあるのか?
Mary K Ellison1, Charles E Schulz, W Robert Scheidt
1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
Journal of the American Chemical Society
|November 15, 2002
まとめ
ニトロシリロン (III) 複合体の非平面のポルフィリン核の形状は,FeNO群の幾何学を変えない. これらの発見は,タンパク質によって引き起こされる歪みが,ヘムタンパク質のFeNO部分の曲解を引き起こす可能性が低いことを示唆しています.
科学分野:
- 協調化化学について
- 有機金属化学 有機金属化学
- 生物物理化学 生物物理化学
背景:
- ニトロフォリンのようなヘムタンパク質は,ニトロシリロン (FeNO) グループを使用し,その幾何学はポルフィリン核構造によって潜在的に影響を受けます.
- ポルフィリン構造とFeNO幾何学の関係を理解することは,生物学的メカニズムを解明し,合成アナログの設計に不可欠です.
研究 の 目的:
- 設計された非平面のポルフィリンコアを持つニトロシリロン (III) ポルフィリナート複合体を合成し,特徴づけること.
- FeNO群の幾何学に対するポルフィリン核の歪み (平面,,ラッフル) の影響を調査する.
- ポルフィリン核の歪みが,ニトロフォリンで提案されたように,曲げられたFeNO幾何学につながる可能性があるという仮説を検証する.
主な方法:
- ニトロシリロン (III) ポルフィリナート複合体の合成,ポルフィリン核の形状が異なる (オクタエチルテトラフェニルポルフィリンとオクタエチルポルフィリンリガンド).
- 精密な結合長と角度を決定するために,X線結晶学を用いた構造的特徴付け.
- ニトロシル伸縮周波数を含むスペクトル解析と,電子構造と結合を確認するためのモースバウアースペクトル検査.
主要な成果:
- 平面的および重度の非平面的 (サドルとラッフル) の両方のポルフィリンコアを持つ複合体は,成功裏に合成され,特徴づけられました.
- レントゲン結晶学では,サドルまたはラッフルされたポルフィリンコアの歪みがFe-N(p),Fe-N(NO),Fe-N(L) 結合長,またはFe-N-Oの角度を大幅に変化させなかったことが明らかになりました.
- 顕微鏡データ (ニトロシル伸縮周波数とMössbauerパラメータ) は,線形Fe-N-O群と鉄中心の二磁性基底状態を確認した.
結論:
- 合成ニトロシリロン (III) 複合体におけるポルフィリン核の歪みは,FeNO群の曲解を誘導しない.
- 観測された線形FeNO幾何学は,ポルフィリン核の平面性に関係なく維持されます.
- ニトロフォリンなどのヘムタンパク質におけるタンパク質誘発のポルフィリン核変形が,FeNO部分の曲解を引き起こす可能性は低い.
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