Sensitive analysis of metal cations in positive ion mode electrospray ionization mass spectrometry using commercial chelating agents and cationic ion‐pairing reagents

Metals play a very important role in many scientific and environmental fields, and thus their detection and analysis is of great necessity. A simple and very sensitive method has been developed herein for the detection of metals in positive ion mode ESI‐MS. Metal ions are positively charged, and as such they can potentially be detected in positive ion mode ESI‐MS; however, their small mass‐to‐charge (m/z) ratio makes them fall in the low‐mass region of the mass spectrum, which has the largest background noise. Therefore, their detection can become extremely difficult. A better and well‐known way to detect metals by ESI‐MS is by chelating them with complexation agents. In this study eleven different metals, Fe(II), Fe(III), Mg(II), Cu(II), Ru(III), Co(II), Ca(II), Ni(II), Mn(II), Sn(II), and Ag(I), were paired with two commercially available chelating agents: ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS). Since negative ion mode ESI‐MS has many disadvantages compared to positive ion mode ESI‐MS, it would be very beneficial if these negatively charged complex ions could be detected in the positive mode. Such a method is described in this paper and it is shown to achieve much lower sensitivities. Each of the negatively charged metal complexes is paired with six cationic ion‐pairing reagents. The new positively charged ternary complexes are then analyzed by ESI‐MS in the positive single ion monitoring (SIM) and single reaction monitoring (SRM) modes. The results clearly revealed that the presence of the cationic reagents significantly improved the sensitivity for these analytes, often by several orders of magnitude. This novel method developed herein for the detection of metals improved the limits of detection (LODs) significantly when compared to negative ion mode ESI‐MS and shows great potential in future trace studies of these and many other species. Copyright © 2012 John Wiley & Sons, Ltd.