Electrospray ionization mass spectrometry fingerprinting of beer

Thomson Mass Spectrometry Laboratory, Institute of Chemistry, State University of Campinas, UNICAMP, Campinas, SP 13083-970, Brazil.
The Analyst (Impact Factor: 4.11). 07/2005; 130(6):884-9. DOI: 10.1039/b415252b
Source: PubMed


After just simple degassing, dilution, pH adjustment and direct flow injection, characteristic fingerprint spectra of beer samples have been obtained by fast (few seconds) electrospray ionization mass spectrometry (ESI-MS) analysis in both the negative and positive ion modes. A total of 29 samples belonging to the two main beer types (lagers and ales) and several beer subtypes from USA, Europe and Brazil could be clearly divided into three groups both by simple visual inspection of their ESI(+)-MS and ESI(-)-MS fingerprints as well as by chemometric treatment of the MS data. Diagnostic ions with contrasting relative abundances in both the positive and negative ion modes allow classification of beers into three major types: P = pale (light) colored (pilsener, pale ale), D = dark colored (bock, stout, porter, mild ale) and M = malt beer. For M beers, samples of a dark and artificially sweetened caramel beer produced in Brazil and known as Malzbiers were used. ESI-MS/MS on these diagnostic beer cations and anions, most of which are characterized as arising from ionization of simple sugars, oligosaccharides, and iso-alpha-acids, yield characteristic tandem mass spectra adding a second and optional MS dimension for improved selectivity for beer characterization by fingerprinting. Direct ESI-MS or ESI-MS/MS analysis can therefore provide fast and reliable fingerprinting characterization of beers, distinguishing between types with different chemical compositions. Other unusual polar components, impurities or additives, as well as fermentation defects or degradation products, could eventually be detected, making the technique promising for beer quality control.

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Available from: Alexandra C H F Sawaya,
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    • "Mass spectrometry (MS) is currently the gold standard technique for the analysis of complex chemical mixtures due mainly to its unmatched ability to detect, count and characterise atoms and molecules of many types, compositions and sizes (Marshall and Rodgers, 2004). Although previous separation is needed, particularly for precise quantitation, direct MS analysis using soft ionisation techniques performed at atmospheric conditions, such as electrospray ionisation (ESI–MS) of complex mixtures, has been shown to provide fast and reliable characterisation of complex mixtures via distinctive chemical profiles (Araújo et al., 2005a; Catharino et al., 2007; Roesler et al., 2007). We have used the MS fingerprinting approach to characterise numerous samples and have shown it to provide reliable qualitative distinction (see for instance: Sawaya et al., 2004; Araújo et al., 2005b; Catharino et al., 2005; Marques et al., 2006; de Souza et al., 2007). "
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    ABSTRACT: INTRODUCTION: The oil obtained from Pterodon pubescens (Leguminosae) seeds are known to display anti-cancer, anti-dermatogenic and anti-nociceptive activitiy. Phytochemical studies have demonstrated that its main constituents are diterpenoids with voucapan skeletons. Considering the potential biological activities of the oil, rapid and efficient methods for assessing its quality would facilitate certification and quality control. OBJECTIVE: To develop a direct mass spectrometric fingerprinting method for the P. pubescens seed oil that would focus on the major diterpenoids constituents, enabling quality control, origin certification and recognition of marker species in commercially available products. METHOD: Two techniques were used: (i) direct infusion electrospray ionisation (ESI) mass spectrometry after solvent extraction and dilution and (ii) ambient desorption/ionisation via easy ambient sonic-spray ionisation, EASI(+)-MS, performed directly on the seed surface or at a paper surface imprinted with the oil. RESULTS: From a combination of ESI-MS, HRESI-MS and ESI-MS/MS data, 12 diterpenes were characterised, and typical profiles were obtained for the oil extract or the crude oil via both ESI-MS and EASI-MS. These techniques require no or very simple sample preparation protocols and the whole analytical processes with spectra acquisition take just a few minutes. CONCLUSION: Both techniques, but particularly EASI-MS, provide simple, fast and efficient MS fingerprinting methodologies to characterise the P. pubescens oil with typical (di)terpene profiles being applicable to quality control and certification of authenticity and origin. Copyright © 2012 John Wiley & Sons, Ltd.
    Phytochemical Analysis 02/2013; 24(2). DOI:10.1002/pca.2404 · 2.34 Impact Factor
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    • "Up to now, only a few studies have focused on the authenticity of beer products. The methods employed in these studies were gas chromatography–isotope ratio mass spectrometry (GC–IRMS–– 13 C/ 12 C ratio of CO 2 ), gas chromatography–flame-ionization detection (GC–FID––amino acids), high-performance liquid chromatography–fluorescence detection (HPLC–FLD––amino acids), HPLC–UV–Vis (phenolic substances), LC–MS (metabolite profiles), head-space solid-phase microextraction coupled to GC–FID or GC–MS (volatile compounds), nuclear magnetic resonance spectroscopy (D/H ratio of the methylene group of ethanol and d 18 O measurement of water; organic and amino acids), and Fourier transform infrared spectroscopy (da Silva et al. 2008; Calderone et al. 2007; Erbe and Bruckner 2000; Kabelova et al. 2008; Obruca et al. 2009; Rossmann 2001; Lachenmeier et al. 2005; Lachenmeier 2007; Cajka et al. 2010b; Araujo et al. 2005; Mattarucchi et al. 2010). Since highly complex data matrices are generated by these fingerprint and profiling techniques and require to be processed, powerful chemometric tools are needed to fully utilize this comprehensive information. "
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    ABSTRACT: A metabolomic fingerprinting/profiling generated by ambient mass spectrometry (MS) employing a direct analysis in real time (DART) ion source coupled to high-resolution time-of-flight mass spectrometry (TOFMS) was employed as a tool for beer origin recognition. In a first step, the DART–TOFMS instrumental conditions were optimized to obtain the broadest possible representation of ionizable compounds occurring in beer samples (direct measurement, no sample preparation). In the next step, metabolomic profiles (mass spectra) of a large set of different beer brands (Trappist and non-Trappist specialty beers) were acquired. In the final phase, the experimental data were analyzed using partial least squares discriminant analysis (PLS-DA), linear discriminant analysis (LDA), and artificial neural networks with multilayer perceptrons (ANN-MLP) with the aim of distinguishing (i) the beers labeled as Rochefort 8; (ii) a group consisting of Rochefort 6, 8, 10 beers; and (iii) Trappist beers. The best prediction ability was obtained for the model that distinguished the group of Rochefort 6, 8, 10 beers from the rest of beers. In this case, all chemometric tools employed provided≥95% correct classification. The current study showed that DART–TOFMS metabolomic fingerprinting/profiling is a powerful analytical strategy enabling quality monitoring/authenticity assessment to be conducted in real time. KeywordsBeer–Authenticity–Traceability–Direct analysis in real time–Mass spectrometry–Multivariate analysis–Metabolomic fingerprinting/profiling
    Metabolomics 12/2011; 7(4):500-508. DOI:10.1007/s11306-010-0266-z · 3.86 Impact Factor
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    • "It establishes a chemical fingerprinting for the composition of major polar compounds. ESI-MS fingerprinting has been used for a variety of samples such as vegetable oil (Catharino et al. 2005; Riccio et al. 2011; Saraiva et al. 2009; Simas et al. 2010; Wu, Rodgers and Marshall 2004), fruits (Roesler et al. 2007), beer (Araujo et al. 2005), wine (Biasoto et al. 2010; Catharino et al. 2006; Cooper and Marshall 2001), whisky (Moller, Catharino, and Eberlin 2005), soybeans (Santos et al. 2006), yerba mate  green tea constituents (Bastos et al. 2007), and biodiesel (Catharino et al. 2007). Herein, we investigate the ability of ESI-MS fingerprinting to characterize Amazonian Rosewood essential oil either from crude wood or leaf and to detect adulteration with the addition of synthetic linalool. "
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    ABSTRACT: Direct infusion of samples via electrospray ionization mass spectrometry (ESI-MS) is shown to characterize unequivocally genuine samples of Amazonian Aniba rosaeodora Ducke (Rosewood) essential oils obtained either from the wood or leafs. The ESI-MS also distinguishes the essential oils from synthetic linalool; hence, adulteration by the synthetic oil is also clearly detected. The analysis requires no pretreatment or preseparation, and the most polar components of the essential oil are extracted with an acidified 1:1 methanol/water solution. This simple extract is then analyzed by direct infusion ESI-MS in the positive ion mode, which provides characteristic fingerprintings of the sample composition. The ESI-MS fingerprinting can be used therefore as a simple and fast (few minutes) method for authenticity and quality control of this famous Amazonian essential oil.
    Analytical Letters 10/2011; 44(15):2417. · 1.03 Impact Factor
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