金属离子能否用作气相二硫键裂解试剂？对含有分子间二硫键的模型肽的铜族金属配合物的研究。
Can metal ions be used as gas-phase disulfide bond cleavage reagents? A survey of coinage metal complexes of model peptides containing an intermolecular disulfide bond.
作者信息
Lioe Hadi, Duan Mubing, O'Hair Richard A J
机构信息
School of Chemistry, University of Melbourne, Victoria 3010, Australia.
出版信息
Rapid Commun Mass Spectrom. 2007;21(16):2727-33. doi: 10.1002/rcm.3122.
The role that a metal ion can have in promoting disulfide bond cleavage has been assessed by surveying the tandem mass spectra of the following metal complexes of model peptides containing an intermolecular disulfide bond: M--H+Cu(II); M--H+Cu(II)(bipy); M+Ag(I); and M+Au(I)(PMe(3)). In comparison to previously studied protonated peptides, these binary and ternary metal complexes generally yield more abundant S--S and/or C--S bond cleavage. In general, M--H+Cu(II) ions cleave the adjacent C--S bond more readily, while the M+Au(I)(PMe(3)) ion cleaves the S--S bond more readily. The ternary metal complex M--H+Cu(II)(bipy), on the other hand, fragments by exclusive loss of the bipyridyl ligand for the larger model peptides studied. Of all coinage metal systems studied, Me(3)PAu(+) is superior in promoting disulfide bond cleavage.
通过研究含有分子间二硫键的模型肽的以下金属配合物的串联质谱，评估了金属离子在促进二硫键断裂中可能发挥的作用：[M–H+Cu(II)]⁺；[M–H+Cu(II)(bipy)]⁺；[M+Ag(I)]⁺；以及[M+Au(I)(PMe₃)]⁺。与之前研究的质子化肽相比，这些二元和三元金属配合物通常会产生更丰富的S-S和/或C-S键断裂。一般来说，[M–H+Cu(II)]⁺离子更容易断裂相邻的C-S键，而[M+Au(I)(PMe₃)]⁺离子更容易断裂S-S键。另一方面，对于所研究的较大模型肽，三元金属配合物[M–H+Cu(II)(bipy)]⁺通过唯一失去联吡啶配体而发生碎片化。在所研究的所有铸币金属体系中，Me₃PAu⁺在促进二硫键断裂方面表现出色。
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