This paper is intended as a tutorial review on the use of inductively coupled plasma – tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio ...analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H2, O2 and NH3, also the use of promising alternative gases, such as CH3F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis.
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•First review on tandem ICP-mass spectrometry (ICP-MS/MS).•Clear description of operating principles of ICP-MS/MS.•Description on how to make use of product ion scans, precursor ion scans and neutral gain scans in method development.•Overview of applications published so far.
•A method was developed for the determination of 7 bisphenols in environment.•This universal analytical method is available for varied environmental samples.•Real sample analysis indicated all target ...analytes except BPB were detected.
This article presents a simple and universal analytical method for the simultaneous analysis of bisphenol S (BPS), bisphenol F (BPF), bisphenol A (BPA), bisphenol B (BPB), bisphenol AF (BPAF), tetrachlorobisphenol A (TCBPA), and tetrabromobisphenol A (TBBPA) in environmental water (river water, sewage) and solid samples (sediment, sludge) based on liquid chromatography–electrospray tandem mass spectrometry (LC–MS/MS). Analytes were extracted from water samples using hydrophilic lipophilic balanced (HLB) solid-phase extraction (SPE) cartridges, and the extracts were further purified using MAX SPE cartridges. For the solid samples, a combination of ultrasonic extraction with the same SPE clean-up procedures used for the water samples was employed. The absolute recoveries for all analytes in the water and solid samples ranged from 57.1 to 114.3%. Good method reproducibility was achieved in terms of intra- and inter-day precision, yielding relative standard deviations (RSDs) less than 16.9 and 18.1%, respectively. The method limits of quantitation (MLOQ) for the seven compounds in environmental water and solid samples ranged from 0.05 to 4.35ng/L and from 0.06 to 2.83ng/g (dry weight, d.w.), respectively. Finally, this method was successfully applied to real environmental sample analysis, which revealed that all of the tested BPs were present, with the exception of BPB.
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► New LC–MS method for the analysis of reduced and oxidised glutathione and methionine. ► Improved quantification of free varietal thiols by means of GC–MS/MS. ► Improved ...quantification of bound varietal thiols by means of UPLC–MS/MS. ► Free and bound varietal thiols identified for the first time in Lugana wines. ► Developed methods effective in evaluating the process of winemaking of Lugana wine.
This paper presents methods for the definition of important analytical tools, such as the development of sensitive and rapid methods for analysing reduced and oxidised glutathione (GSH and GSSG), hydroxycinnamic acids (HCA), bound thiols (GSH-3MH and Cys-3MH) and free thiols (3MH and 3MHA), and their first application to evaluate the effect of reductive winemaking on the composition of Lugana juices and wines.
Lugana is a traditional white wine from the Lake Garda region (Italy), produced using a local grape variety, Trebbiano di Lugana. An innovative winemaking procedure based on preliminary cooling of grape berries followed by crushing in an inert environment was implemented and explored on a winery scale.
The effects of these procedures on hydroxycinnamic acids, GSH, GSSG, free and bound thiols and flavanols content were investigated. The juices and wines produced using different protocols were examined. Moreover, wines aged in tanks for 1, 2 and 3 months were analysed.
The high level of GSH found in Lugana grapes, which can act as a natural antioxidant and be preserved in must and young wines, thus reducing the need of exogenous antioxidants, was particularly interesting. Moreover, it was clear that polyphenol concentrations (hydroxycinnamic acids and catechins) were strongly influenced by winemaking and pressing conditions, which required fine tuning of pressing.
Above-threshold levels of 3-mercaptohexan-1-ol (3MH) and 3-mercaptohexyl acetate (3MHA) were found in the wines and changed according to the winemaking procedure applied. Interestingly, the evolution during the first three months also varied depending on the procedure adopted. Organic synthesis of cysteine and glutathione conjugates was carried out and juices and wines were subjected to LC–MS/MS analysis. These two molecules appeared to be strongly affected by the winemaking procedure, but did not show any significant change during the first 3 months of post-bottling ageing. This supports the theory, already proposed in the literature, that there are other synthetic pathways for free thiol formation.
Integrating the governing chemistry with the genomics and phenotypes of microbial colonies has been a “holy grail” in microbiology. This work describes a highly sensitive, broadly applicable, and ...cost-effective approach that allows metabolic profiling of live microbial colonies directly from a Petri dish without any sample preparation. Nanospray desorption electrospray ionization mass spectrometry (MS), combined with alignment of MS data and molecular networking, enabled monitoring of metabolite production from live microbial colonies from diverse bacterial genera, including Bacillus subtilis, Streptomyces coelicolor, Mycobacterium smegmatis , and Pseudomonas aeruginosa . This work demonstrates that, by using these tools to visualize small molecular changes within bacterial interactions, insights can be gained into bacterial developmental processes as a result of the improved organization of MS/MS data. To validate this experimental platform, metabolic profiling was performed on Pseudomonas sp. SH-C52, which protects sugar beet plants from infections by specific soil-borne fungi R. Mendes et al. (2011) Science 332:1097–1100. The antifungal effect of strain SH-C52 was attributed to thanamycin, a predicted lipopeptide encoded by a nonribosomal peptide synthetase gene cluster. Our technology, in combination with our recently developed peptidogenomics strategy, enabled the detection and partial characterization of thanamycin and showed that it is a monochlorinated lipopeptide that belongs to the syringomycin family of antifungal agents. In conclusion, the platform presented here provides a significant advancement in our ability to understand the spatiotemporal dynamics of metabolite production in live microbial colonies and communities.
The widespread occurrence of antibiotics as contaminants in the aquatic environment has increased attention in the last years. The concern over the release of antibiotics into the environment is ...related primarily to the potential for the development of antimicrobial resistance among microorganisms. This article presents an overview of analytical methodologies for the determination of quinolone (Qs) and fluoroquinolone (FQs), macrolide (MLs), tetracycline (TCs), sulfonamide (SAs) antibiotics and trimethoprim (TMP) in different environmental waters. The analysis of these antibiotics has usually been carried out by high-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) or tandem mass spectrometry (MS/MS) and to a lesser extent by ultraviolet (UV) or fluorescence detection (FD). A very important step before LC analysis is sample preparation and extraction leading to elimination of interferences and prevention of matrix effect and preconcentration of target analytes.
In recent years, metabolomics and lipidomics approaches have become increasingly popular for use in the analysis of human heath, molecular mechanisms, and disease progression. Despite the growth in ...applications and advances in instrumentation, metabolomics and lipidomics are limited by factors including interference from matrix effects, the need for lengthy for chromatographic analysis, and structural diversity of metabolites and lipids creating interference of isomers and isobars, which can confound identification. Ion mobility spectrometry (IMS) provides a method to enhance throughput, enhance isomeric separation, and reduce chemical noise. This review focuses on (i) the use of IMS and subsequent advancements in global metabolomics and lipidomics, (ii) the application and benefits of IMS in targeted metabolomics studies, and (iii) the use of IMS for non-chromatographic methods such as direct analysis, desorption ionization methods, and imaging.
•Integration of ion mobility spectrometry (IMS) enhances isomeric separation.•IMS improves metabolome coverage.•IMS mass spectrometry imaging enhances spatial characterization of tissues.•Addition of collision cross sections to metabolite databases are needed.
Metabolomics and lipidomics are new drivers of the omics era as molecular signatures and selected analytes allow phenotypic characterization and serve as biomarkers, respectively. The growing ...capabilities of untargeted and targeted workflows, which primarily rely on mass spectrometric platforms, enable extensive charting or identification of bioactive metabolites and lipids. Structural annotation of these compounds is key in order to link specific molecular entities to defined biochemical functions or phenotypes. Tandem mass spectrometry (MS), first and foremost collision-induced dissociation (CID), is the method of choice to unveil structural details of metabolites and lipids. But CID fragment ions are often not sufficient to fully characterize analytes. Therefore, recent years have seen a surge in alternative tandem MS methodologies that aim to offer full structural characterization of metabolites and lipids. In this article, principles, capabilities, drawbacks, and first applications of these “advanced tandem mass spectrometry” strategies will be critically reviewed. This includes tandem MS methods that are based on electrons, photons, and ion/molecule, as well as ion/ion reactions, combining tandem MS with concepts from optical spectroscopy and making use of derivatization strategies. In the final sections of this review, the first applications of these methodologies in combination with liquid chromatography or mass spectrometry imaging are highlighted and future perspectives for research in metabolomics and lipidomics are discussed.
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Over several millennia, various native plant species in South America have been used for their healing and psychoactive properties. Chemical analysis of archaeological artifacts provides an ...opportunity to study the use of psychoactive plants in the past and to better understand ancient botanical knowledge systems. Liquid chromatography tandem mass spectrometry (LC-MS/MS) was used to analyze organic residues from a ritual bundle, radiocarbon dated to approximately 1,000 C.E., recovered from archaeological excavations in a rock shelter located in the Lípez Altiplano of southwestern Bolivia. The site is located at an elevation of ∼3,900 m above sea level and contains evidence of intermittent human occupations during the last 4,000 years. Chemical traces of bufotenine, dimethyltryptamine, harmine, and cocaine, including its degradation product benzoylecgonine, were identified, suggesting that at least three plants containing these compounds were part of the shamanic paraphernalia dating back 1,000 years ago, the largest number of compounds recovered from a single artifact from this area of the world, to date. This is also a documented case of a ritual bundle containing both harmine and dimethyltryptamine, the two primary ingredients of ayahuasca. The presence of multiple plants that come from disparate and distant ecological areas in South America suggests that hallucinogenic plants moved across significant distances and that an intricate botanical knowledge was intrinsic to pre-Columbian ritual practices.
Liquid chromatography tandem mass spectrometry (LC-MS/MS) assays are considered the reference standard for serum steroid hormone analyses, while full urinary steroid profiles are only achievable by ...gas chromatography (GC–MS). Both LC-MS/MS and GC–MS have well documented strengths and limitations. Recently, commercial ultra-high performance supercritical fluid chromatography–tandem mass spectrometry (UHPSFC-MS/MS) systems have been developed. These systems combine the resolution of GC with the high-throughput capabilities of UHPLC. Uptake of this new technology into research and clinical labs has been slow, possibly due to the perceived increase in complexity. Here we therefore present fundamental principles of UHPSFC-MS/MS and the likely applications for this technology in the clinical research setting, while commenting on potential hurdles based on our experience to date.
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