TY - JOUR
T1 - HNO/NO conversion mechanisms of Cu-based HNO probes with implications for Cu,Zn-SOD
AU - Michael, Matthew A.
AU - Pizzella, Gianna
AU - Yang, Liu
AU - Shi, Yelu
AU - Evangelou, Tiffany
AU - Burke, Daniel T.
AU - Zhang, Yong
PY - 2014/3/20
Y1 - 2014/3/20
N2 - HNO has broad biological effects and pharmacological activities. Direct HNO probes for in vivo applications were recently reported, which are Cu II-based complexes having fluorescence reporters with reaction to HNO resulting in CuI systems and the release of NO. Their coordination environments are similar to that in Cu,Zn-superoxide dismutase (SOD), which plays a significant role in cellular HNO/NO conversion. However, none of these conversion mechanisms are known. A quantum chemical investigation was performed here to provide structural, energetic, and electronic profiles of HNO/NO conversion pathways via the first CuII-based direct HNO probe. Results not only are consistent with experimental observations but also provide numerous structural and mechanistic details unknown before. Results also suggest the first HNO/NO conversion mechanism for Cu,Zn-SOD, as well as useful guidelines for future design of metal-based HNO probes. These results shall facilitate development of direct HNO probes and studies of HNO/NO conversions via metal complexes and metalloproteins.
AB - HNO has broad biological effects and pharmacological activities. Direct HNO probes for in vivo applications were recently reported, which are Cu II-based complexes having fluorescence reporters with reaction to HNO resulting in CuI systems and the release of NO. Their coordination environments are similar to that in Cu,Zn-superoxide dismutase (SOD), which plays a significant role in cellular HNO/NO conversion. However, none of these conversion mechanisms are known. A quantum chemical investigation was performed here to provide structural, energetic, and electronic profiles of HNO/NO conversion pathways via the first CuII-based direct HNO probe. Results not only are consistent with experimental observations but also provide numerous structural and mechanistic details unknown before. Results also suggest the first HNO/NO conversion mechanism for Cu,Zn-SOD, as well as useful guidelines for future design of metal-based HNO probes. These results shall facilitate development of direct HNO probes and studies of HNO/NO conversions via metal complexes and metalloproteins.
KW - Cu,Zn-SOD
KW - HNO
KW - NO
KW - mechanism
KW - quantum chemical calculation
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U2 - 10.1021/jz5002902
DO - 10.1021/jz5002902
M3 - Article
AN - SCOPUS:84897903195
VL - 5
SP - 1022
EP - 1026
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 6
ER -