title: HNO/NO Conversion Mechanisms of Cu-Based HNO Probes with Implications for Cu,Zn-SOD.
abstract: HNO has broad biological effects and pharmacological activities. Direct HNO probes for in vivo applications were recently reported, which are CuII-based complexes having fluorescence reporters with reaction to HNO resulting in CuIsystems 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.
authors.affiliation: Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology , Castle Point on Hudson, Hoboken, New Jersey 07030, Unites States.
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Michael
authors.affiliation: Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology , Castle Point on Hudson, Hoboken, New Jersey 07030, Unites States.
authors.forename: Gianna
authors.initials: G
authors.lastname: Pizzella
authors.affiliation: Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology , Castle Point on Hudson, Hoboken, New Jersey 07030, Unites States.
authors.forename: Liu
authors.initials: L
authors.lastname: Yang
authors.affiliation: Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology , Castle Point on Hudson, Hoboken, New Jersey 07030, Unites States.
authors.forename: Yelu
authors.initials: Y
authors.lastname: Shi
authors.affiliation: Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology , Castle Point on Hudson, Hoboken, New Jersey 07030, Unites States.
authors.forename: Tiffany
authors.initials: T
authors.lastname: Evangelou
authors.affiliation: Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology , Castle Point on Hudson, Hoboken, New Jersey 07030, Unites States.
authors.forename: Daniel T
authors.initials: DT
authors.lastname: Burke
authors.affiliation: Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology , Castle Point on Hudson, Hoboken, New Jersey 07030, Unites States.
authors.forename: Yong
authors.initials: Y
authors.lastname: Zhang