Electrospray ionization mass spectrometry fingerprinting of whisky: immediate proof of origin and authenticity

Abstract

Authentic samples of whisky produced in Scotland and USA and counterfeit whisky samples commercialized in Brazil have been directly submitted to electrospray ionization mass spectrometry (ESI-MS) analysis in both the negative and positive ion modes to assess the potential of this technique for simple and rapid quality control and proof of authenticity of whisky samples. ESI in the negative ion mode yields the most characteristic whisky fingerprinting mass spectra in just a few seconds by direct infusion of the samples, detecting the most polar or acidic components of each sample in their deprotonated anionic forms. No pre-treatment of the sample, such as extraction or derivatization or even dilution, is required. The analysis of the ESI(-)-MS data both by simple visual inspection but more particularly by chemometric data treatment enables separation of the whisky samples into three unequivocally distinct groups: Scotch, American and counterfeit whisky, whereas single malt and blended Scotch whiskies are also distinguished to some extent. As indicated by ESI-MS/MS analysis, the diagnostic anions are simple sugars, disaccharides and phenolic compounds. Direct infusion ESI-MS therefore provides immediate chemical fingerprinting of whisky samples for type, origin and quality control, as demonstrated herein for American, Scottish and counterfeit samples, whereas ESI-MS/MS analysis of diagnostic ions adds a second dimension of fingerprinting characterization when improved selectivity is desired.

Fingerprinting of propolis by easy ambient sonic-spray ionization mass spectrometry

“…We performed the first systematic study applying ESI-MS fingerprinting to propolis [19], analyzing over 40 propolis samples, mainly from Brazil. Since then, ESI-MS fingerprinting has been applied to a wide variety of food and beverage samples [20][21][22] as well as natural products [23].…”

Electrospray ionization mass spectrometry fingerprinting of propolis of native Brazilian stingless bees

“…Therefore ESI-MS and its tandem version ESI-MS/MS with direct infusion (no previous separation) has been applied to the analysis of a variety of complex natural mixtures such as those found in plant extracts (Mauri and Pieta, 2000;Möller et al, 2007), beer (Araújo et al, 2005), vegetable oils Wu et al, 2004) wine (Catharino et al, 2006;Cooper and Marshal, 2001), whisky (Möller et al, 2005), and even the most complex chemical mixture: petroleum (Hughey et al, 2002).…”

Extracting homologous series from mass spectrometry data by projection on predefined vectors

“…High resolution measurements have also been attempted and the knowledge of the elemental composition of the single analysed components gives further information [19]. These findings are frequently supported by complementary analytics, which do not necessarily require to be directly tied into the chemometric evaluation [20].…”