オキシコボグロビンモデルによる酸化窒素酸化反応: 協調ペロキシニトリートの低温FTIR特性をin-situで表した
Tigran S Kurtikyan1, Shahane R Eksuzyan, Vardan A Hayrapetyan
1Molecule Structure Research Centre (MSRC) of the Scientific and Technological Centre of Organic and Pharmaceutical Chemistry NAS, 0014, Yerevan, Armenia. kurto@netsys.am
Journal of the American Chemical Society
|August 14, 2012
まとめ
コボグロビンのモデルは酸化窒素と酸化酸素と反応し,ペロキシニトリートとニトラット複合体を形成します. これらの発見は,コボグロビンモデルがオキシヘム反応を模倣し,窒素製品を形成する能力を示しています.
科学分野:
- バイオ・オーガニック化学 バイオ・オーガニック化学
- 協調化化学について
- スペクトロスコーピーは,スペクトロスコーピーを用います.
背景:
- コボグロビンモデルは,天然のヘムタンパク質の機能を真似して合成されます.
- 酸化窒素や酸化酸素のような小分子とのこれらのモデルの反応性を理解することは,生物無機化学にとって極めて重要です.
研究 の 目的:
- 酸化窒素とオキシコボグロビンモデルの反応経路を調査する.
- 反応中に形成される中間および最終製品を特徴付けるため.
主な方法:
- ポルフィリンリガンドによるオキシコボグロビンモデルの合成.
- 低温スペクトロスコーピー (FTIRおよびUV可視) で,反応をモニターする.
- 同位体ラベリング実験では, (18) O, (2) (15) NO,およびN, (18) O.
- 密度関数理論 (DFT) による計算.
主要な成果:
- 6座標ペロキシニート複合体の形成 ((NH(3)) Co(Por ((OONO)) 80から120Kまで加熱すると.
- 140〜170Kの間のペロキシニトリート複合物の分解と二酸化窒素 (NO2) の形成.
- 180~210Kで6座標のニトラート複合体 ((NH(3)) の形成 ((Co(Por) (((η(1) -ONO(2))) は,酸化窒素酸化 (NOD) を示す.
結論:
- オキシコボグロビンのモデルは,オキシヘムと同様に,酸化窒素酸化酸化反応 (NOD) を促進します.
- 6座標のニトラト複合体は室温では不安定で,ニトラット複合体と酸化コバルト複合体に分解する.
- この研究は,小さな分子を持つコバルト-ポルフィリン複合体の反応機構の洞察を提供します.
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