アザマクロサイクルの銅複合体のリガンド環境を調節することによって,リバーシブルなニトロキシル検出を達成する
Sunghee Kim1, Mikael A Minier1, Andrei Loas1
1Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|February 3, 2016
まとめ
研究者は他の分子よりも選択的にニトロキシル (HNO) を検出するために銅複合体を探索しました. 一つの複合体はHNOによる選択的還元を示し,新しい光探査機への道を開いた.
科学分野:
- 協調化学
- 化学センサー
- バイオ有機化学
背景:
- ニトロキシル (HNO) は寿命が短い重要なシグナリング分子です.
- HNOの選択的光探査機の開発は,その反応性および他の反応性窒素種との類似性のために困難です.
- 金属ベースの探査機は,センシングアプリケーションにユニークなリドックス特性を提供します.
研究 の 目的:
- ニトロキシル (HNO) の検出のためのCu (II) -サイクラム (14-N4) 誘導体の選択性に影響を与える要因を調査する.
- HNO,酸化窒素 (NO),チオール,硫化水素 (H2S) との銅複合体の反応性を理解する.
- 新しいHNO光探知器の設計におけるアザマクロサイクル銅複合体の可能性を調査する.
主な方法:
- 5つのCu (II) -サイクラム (14-N4) 誘導体の合成と特徴付け
- アンジェリー塩から生成されたNOとHNOとの反応をモニターするスペクトル解析 (UV-vis)
- 還元電位を測定する電気化学的測定
- Cu (II) 混合のチア/アザ (14-N2S2) リガンド複合体の製造と試験.
主要な成果:
- Cu (II) -サイクラム複合体は,NOガスと反応しなかった.
- [Cu ((II) ((14-N4-Ts)) ((OTf)) ]は,HNO曝露時に選択的なCu ((II)) 減少を示し,その高い減少の可能性と相関しています.
- Cu (II) -14-N2S2複合体はHNOと逆向きに反応したが,チオールとH2Sに対する選択性が欠けていた.
- 反応性パターンは,HNOの選択性を支配する要因の洞察を提供した.
結論:
- Cu (II) 複合体の還元能力は,HNOの選択性を達成する上で重要な要因である.
- アザマクロサイクルの銅複合体は,HNOを繰り返し検出する可能性がある.
- この研究は,HNOのための新世代の選択的金属ベースの光探査機の開発のための基礎を築きます.
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