Elemental and molecular analysis of metal containing biomolecules using laser induced breakdown spectroscopy and sonic spray ionization mass spectrometry: A step towards full integration and simultaneous analysis

A novel methodology is proposed that combines sonic spray ionization (SSI) mass spectrometry (MS) with laser induced breakdown spectroscopy (LIBS) for analyzing metal-containing biomolecules and complexes. Focusing pulses from a nanosecond laser (Nd:YAG, λ = 1064 nm) in the microdroplet ensemble produced by a pneumatic nebulizer yielded LIBS spectra that enabled highly sensitive detection of several metal ions in aqueous and aqueous methanolic solutions. Based on the calibration curve method, LOD values at the ng/mL level were achieved for Ca (15 ng/mL), Ba (27 ng/mL), Cu (67 ng/mL) and Fe (650 ng/mL) with accuracy > 90%. LIBS measurements were performed for the first time on aerosols of solutions of known biomolecules such as superoxide dismutase and alpha-lactalbumin, which led to the reliable determination of the concentration of Cu and Ca, respectively, both in the range of a few μg/mL. In parallel, the relative molecular mass of the metalloproteins was determined by separate SSI-MS measurements performed using an identical pneumatic nebulizer based sample introduction system. This is a first step towards the ultimate aim of integrating the two analytical techniques by use of a single pneumatic nebulization system for simultaneous sample introduction for both LIBS and SSI-MS. Such a system is expected to greatly enhance our capabilities to simultaneously acquire molecular and atomic data.