Electrospray ionization mass spectrometry combined with the ultra high performance liquid chromatography in the analysis of in vitro formation of chlorophyll complexes with copper and zinc

Abstract

The aim of this work was to give more accurate insight in the interaction of major photosynthesis pigment, chlorophyll (Chl), with copper (II) and zinc (II) in solution by flow injection analysis with electrospray ionization mass spectrometry (FIA-ESI-MS) method, as well as combined with ultra high performance liquid chromatography with DAD detection (UHPLC-DAD). These interactions may potentially, but not necessarily lead to formation of Cu-Chl and Zn-Chl complexes of two different types, which has a lot of - at least - disfunctional implications in plant world. The results based on analysis of full-scan and MS/MS spectra - with or without the UHPLC chromatograms - confirm formation of ?central type? Cu-Chl complex, and ?central type? Zn-Chl complex as well, along with a proof for formation of ?peripheral? Zn-Chl complex, the latter one originating from a very week coordinative interaction at the edge of Chl structure. The used techniques appeared to be an efficient and reliable tool for studying formation and stability of heavy metals complexes with chlorophyll, at least in vitro, with a considerable possibility for assessment of real bio-environmental behavior.