Identification, characterization and quantitation of pyrogenic polycylic aromatic hydrocarbons and other organic compounds in tire fire products

On 15 August 2001, a tire fire took place at the Pneu Lavoie Facility in Gatineau, Quebec, in which 4000 to 6000 new and recycled tires were stored along with other potentially hazardous materials. Comprehensive gas chromatography-mass spectrometry (GC-MS) analyses were performed on the tire fire samples to facilitate detailed chemical composition characterization of toxic polycyclic aromatic hydrocarbons (PAHs) and other organic compounds in samples. It is found that significant amounts of PAHs, particularly the high-ring-number PAHs, were generated during the fire. In total, 165 PAH compounds including 13 isomers of molecular weight (MW) 302, 10 isomers of MW 278, 10 isomers of MW 276, 7 isomers of MW 252, 7 isomers of MW 228, and 8 isomers of MW 216 PAHs were positively identified in the tire fire wipe samples for the first time. Numerous S-, O-, and N-containing PAH compounds were also detected. The identification and characterization of the PAH isomers was mainly based on: (1) a positive match of mass spectral data of the PAH isomers with the NIST authentic mass spectra database; (2) a positive match of the GC retention indices (I) of PAHs with authentic standards and with those reported in the literature; (3) agreement of the PAH elution order with the NIST (US National Institute of Standards and Technology) Standard Reference Material 1597 for complex mixture of PAHs from coal tar; (4) a positive match of the distribution patterns of PAH isomers in the SIM mode between the tire fire samples and the NIST Standard Reference Materials and well-characterized reference oils. Quantitation of target PAHs was done on the GC-MS in the selected ion monitoring (SIM) mode using the internal standard method. The relative response factors (RRF) for target PAHs were obtained from analyses of authentic PAH standard compounds. Alkylated PAH homologues were quantitated using straight baseline integration of each level of alkylation.     

The determination of the linear alkylbenzene sulfonate isomers in water samples by gas-chromatography/mass spectrometry

A number of 20 compounds of linear alkylbenzene sulfonates (LASs) family were identified by electron impact mass spectrometry (EI-MS) in water samples collected from wastewater treatment plants (WWTP). This paper presents the mass spectra of 20 compounds, the proposed mechanism of formation of the diagnostic ions obtained by EI-MS and the distribution of individual isomers in water samples collected from compartments of WWTP. The individual isomers from four homolog series C(10)-, C(11)-, C(12)- and C(13)-LAS were analyzed as methyl derivatives.     

Comprehensive identification and structural characterization of target components from Gelsemium elegans by high‐performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry based on accurate mass databases combined with MS/MS spectra

This study reports an applicable analytical strategy of comprehensive identification and structure characterization of target components from Gelsemium elegans by using high‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry (LC‐QqTOF MS) based on the use of accurate mass databases combined with MS/MS spectra. The databases created included accurate masses and elemental compositions of 204 components from Gelsemium and their structural data. The accurate MS and MS/MS spectra were acquired through data‐dependent auto MS/MS mode followed by an extraction of the potential compounds from the LC‐QqTOF MS raw data of the sample. The same was matched using the databases to search for targeted components in the sample. The structures for detected components were tentatively characterized by manually interpreting the accurate MS/MS spectra for the first time. A total of 57 components have been successfully detected and structurally characterized from the crude extracts of G. elegans , but has failed to differentiate some isomers. This analytical strategy is generic and efficient, avoids isolation and purification procedures, enables a comprehensive structure characterization of target components of Gelsemium and would be widely applicable for complicated mixtures that are derived from Gelsemium preparations. Copyright © 2017 John Wiley & Sons, Ltd.     

Positional isomer differentiation of synthetic cannabinoid JWH‐081 by GC‐MS/MS

Like many new designer drugs of abuse, synthetic cannabinoids (SC) have structural or positional isomers which may or may not all be regulated under law. Differences in acute toxicity may exist between isomers which impose further burden in the fields of forensic toxicology, medicine and legislation. Isomer differentiation therefore becomes crucial from these standpoints as new designer drugs continuously emerge with just minor positional modifications to their preexisting analogs. The aim of this study was to differentiate the positional isomers of JWH‐081. Purchased standard compounds of JWH‐081 and its positional isomers were analyzed by gas chromatography‐electron ionization‐mass spectrometry (GC‐EI‐MS) first in scan mode to investigate those isomers who could be differentiated by EI scan spectra. Isomers with identical or near‐identical EI spectra were further subjected to GC‐tandem mass spectrometry (MS/MS) analysis with appropriate precursor ions. EI scan was able to distinguish 3 of the 7 isomers: 2‐methoxy, 7‐methoxy and 8‐methoxy. The remaining isomers exhibited near‐identical spectra; hence, MS/MS was performed by selecting m/z 185 and 157 as precursor ions. 3‐Methoxy and 5‐methoxy isomers produced characteristic product ions that enabled the differentiation between them. Product ion spectrum of 6‐methoxy isomer resembled that of JWH‐081; however, the relative ion intensities were clearly different from one another. The combination of EI scan and MS/MS allowed for the regioisomeric differentiation of the targeted compounds in this study. Copyright © 2015 John Wiley & Sons, Ltd.     

Searching for anthropogenic contaminants in human breast adipose tissues using gas chromatography‐time‐of‐flight mass spectrometry

The potential of gas chromatography‐time‐of‐flight mass spectrometry (GC‐TOF MS) for screening anthropogenic organic contaminants in human breast adipose tissues has been investigated. Initially a target screening was performed for a list of 125 compounds which included persistent halogen pollutants [organochlorine (OC) pesticides, polychlorinated biphenylss (PCBs), polybrominated diphenyl ethers (PBDEs)], polyaromatic hydrocarbons (PAHs), alkylphenols, and a notable number of pesticides from the different fungicide, herbicide and insecticide families. Searching for target pollutants was done by evaluating the presence of up to five representative ions for every analyte, all measured at accurate mass (20‐mDa mass window). The experimental ion abundance ratios were then compared to those of reference standards for confirmation. Sample treatment consisted of an extraction with hexane and subsequent normal‐phase (NP) High performance liquid chromatography (HPLC) or SPE cleanup. The fat‐free LC fractions were then investigated by GC‐TOF MS. Full‐spectral acquisition and accurate mass data generated by GC‐TOF MS also allowed the investigation of nontarget compounds using appropriate processing software to manage MS data. Identification was initially based on library fit using commercial nominal mass libraries. This was followed by comparing the experimental accurate masses of the most relevant ions with the theoretical exact masses with calculations made using the elemental composition calculator included in the software. The application of both target and nontarget approaches to around 40 real samples allowed the detection and confirmation of several target pollutants including p,p′‐DDE, hexachlorobenzene (HCB), and some polychlorinated biphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). Several nontarget compounds that could be considered anthropogenic pollutants were also detected. These included 3,5‐di‐tert‐butyl‐4‐hydroxy‐toluene (BHT) and its metabolite 3,5‐di‐tert‐butyl‐4‐hydroxybenzaldehyde (BHT‐CHO), dibenzylamine, N‐butyl benzenesulfonamide (N‐BBSA), some naphthalene‐related compounds and several PCBs isomers not included in the target list. As some of the compounds detected are xenoestrogens, the methodology developed in this paper could be useful in human breast cancer research. Copyright © 2008 John Wiley & Sons, Ltd.     

New isomeric 2‐ortho‐(meta‐ and para‐) chloro‐(bromo and nitro‐)benzylthio‐6‐aminouracils

Ten new ortho, meta and para substituted derivatives of 2‐benzylthio‐6‐aminouracils have been prepared. Electron Impact (EI) induced mass spectral fragmentation of these compounds was investigated. Fragmentation pathways are proposed on the basis of accurate mass and metastable transition measurements. The correlation between the intensities of the M⁺‐ and the selected fragment ions of these compounds is discussed. The data obtained create the basis for dinstinguishing isomers. The ¹H and ¹³C NMR spectra of these compounds were assigned unambiguously using a combination of heteronuclear (HETCOR) spectra the chemical shifts. The data derived from these spectra can be used to differentiate the isomers.     

Determination of sixteen polycyclic aromatic hydrocarbons in aqueous and solid samples from an Italian wastewater treatment plant

A robust procedure for the determination of 16 US EPA PAHs in both aqueous (e.g. wastewaters, industrial discharges, treated effluents) and solid samples (e.g. suspended solids and sludge) from a wastewater treatment plant (WWTP) is presented. Recovery experiments using different percentages of organic modifier, sorbents and eluting solvent mixtures were carried out in Milli-Q water (1000 mL) spiked with a mixture of the PAH analytes (100 ng/L of each analyte). The solid phase extraction (SPE) procedures applied to spiked waste water samples (1000 mL; 100 ng/L spiking level) permitted simultaneous recovery of all the 16PAHs with yields >70% (6-13% RSD). SPE clean up procedures applied to sewage and stabilized sludge extracts, showed percent recoveries in the range 73-92% (7-13% RSD) and 71-89% (7-12% RSD), respectively. The methods were used for the determination of PAHs in aqueous and solid samples from the WWTP of Fusina (Venice, Italy). Mean concentrations, as the sum of the 16PAHs in aqueous and suspended solid samples, were found to be approx. in the 1.12-4.62 microg/L range. Sewage and stabilized sludge samples contained mean PAH concentrations, as sum of 16 compounds, in the concentration range of 1.44-1.26 mg/kg, respectively. Extraction and clean up procedures for sludge samples were validated using EPA certified reference material IRM-104 (CRM No. 912). Instrumental analyses were performed by coupling HPLC with UV-diode array detection (UV-DAD) and fluorescence detection (FLD).     

Quantum chemical electron impact mass spectrum prediction for de novo structure elucidation: Assessment against experimental reference data and comparison to competitive fragmentation modeling

We investigate the success of the quantum chemical electron impact mass spectrum (QCEIMS) method in predicting the electron impact mass spectra of a diverse test set of 61 small molecules selected to be representative of common fragmentations and reactions in electron impact mass spectra. Comparison with experimental spectra is performed using the standard matching algorithms, and the relative ranking position of the actual molecule matching the spectra within the NIST‐11 library is examined. We find that the correct spectrum is ranked in the top two matches from structural isomers in more than 50% of the cases. QCEIMS, thus, reproduces the distribution of peaks sufficiently well to identify the compounds, with the RMSD and mean absolute difference between appropriately normalized predicted and experimental spectra being at most 9% and 3% respectively, even though the most intense peaks are often qualitatively poorly reproduced. We also compare the QCEIMS method to competitive fragmentation modeling for electron ionization, a training‐based mass spectrum prediction method, and remarkably we find the QCEIMS performs equivalently or better. We conclude that QCEIMS will be very useful for those who wish to identify new compounds which are not well represented in the mass spectral databases.     

Investigation of the photochemical behaviour of pyrethroids lacking the cyclopropane ring by photo‐solid‐phase microextraction and gas chromatography/mass spectrometry

The characterization of by‐products arising from the UV photodegradation of two insecticide pyrethroids lacking the cyclopropane ring (flucythrinate and fenvalerate) has been investigated by gas chromatography coupled with mass spectrometry (GC/MS). Twenty photoproducts were tentatively identified mainly based on the interpretation of the experimental mass spectra or by using reference mass spectra. Some of these compounds had not previously been detected. Furthermore, the generation of some of the photoproducts might be a matter for concern due to their potential toxicity. The corresponding photodegradation routes, including postulation of the intermediate radicals, have also been proposed. These photodegradation studies were performed by photo‐solid‐phase microextraction (photo‐SPME) in which the SPME fibre was exposed to light after extraction of the target analytes from aqueous solutions. The degradation kinetics of the investigated pyrethroids and the photoformation‐photodegradation curves of the photoproducts generated in situ were also monitored through the ion chromatograms obtained for different irradiation times and the corresponding mass spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Differentiation of isomeric dinitrotoluenes and aminodinitrotoluenes using electrospray high resolution mass spectrometry

Explosive detection and identification play an important role in the environmental and forensic sciences. However, accurate identification of isomeric compounds remains a challenging task for current analytical methods. The combination of electrospray multistage mass spectrometry (ESI‐MSⁿ) and high resolution mass spectrometry (HRMS) is a powerful tool for the structure characterization of isomeric compounds. We show herein that resonant ion activation performed in a linear quadrupole ion trap allows the differentiation of dinitrotoluene isomers as well as aminodinitrotoluene isomers. The explosive‐related compounds: 2,4‐dinitrotoluene (2,4‐DNT), 2,6‐dinitrotoluene (2,6‐DNT), 2‐amino‐4,6‐dinitrotoluene (2A‐4,6‐DNT) and 4‐amino‐2,6‐dinitrotoluene (4A‐2,6‐DNT) were analyzed by ESI‐MS in the negative ion mode; they produced mainly deprotonated molecules [M ? H]^?. Subsequent low resolution MSⁿ experiments provided support for fragment ion assignments and determination of consecutive dissociation pathways. Resonant activation of deprotonated dinitrotoluene isomers gave different fragment ions according to the position of the nitro and amino groups on the toluene backbone. Fragment ion identification was bolstered by accurate mass measurements performed using Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR/MS). Notably, unexpected results were found from accurate mass measurements performed at high resolution for 2,6‐DNT where a 30‐Da loss was observed that corresponds to CH₂O departure instead of the expected isobaric NO^? loss. Moreover, 2,4‐DNT showed a diagnostic fragment ion at m/z 116, allowing the unambiguous distinction between 2,4‐ and 2,6‐DNT isomers. Here, CH₂O loss is hindered by the presence of an amino group in both 2A‐4,6‐DNT and 4A‐2,6‐DNT isomers, but nevertheless, these isomers showed significant differences in their fragmentation sequences, thus allowing their differentiation. DFT calculations were also performed to support experimental observations. Copyright © 2014 John Wiley & Sons, Ltd.     

Optimisation of the GC-MS conditions for the determination of the 15 EU foodstuff priority polycyclic aromatic hydrocarbons

European legislation has recently established a list of 15 priority polycyclic aromatic hydrocarbons (PAHs) to be monitored in foodstuff. Thus, the accurate determination of these compounds has become a highly relevant issue. The fact that some of these European Union (EU) PAHs differ from those typically analysed, requires the re-evaluation of the instrumental conditions for the proper determination of the new target compounds. In this study, the influence of the stationary phase and dimensions of the GC capillary column on the chromatographic resolution of the 15 EU PAHs has been investigated. Apolar (DB-5 type) and medium polar (DB-17 type) stationary phases with different lengths and film thickness have been evaluated for the separation of the target compounds, with special emphasis on those coelutions involving isomers such as the three benzofluoranthenes included in the EU PAHs. In addition, the influence of the injection technique and the column dimensions on the recovery of the high molecular mass PAHs has been studied. A programmable temperature vaporising (PTV) injector has been used in three different operational modes and the results were compared to those obtained using on-column injection. The experimental parameters involved in the injection step were optimised by using experimental design.     

Determination of volatile organic compounds in industrial wastewater plant air emissions by multi-sorbent adsorption and thermal desorption-gas chromatography-mass spectrometry

This paper describes the process of determining the presence of volatile organic compounds in air emissions from industrial wastewater treatment plants (WWTP). The analytical method, based on thermal desorption-gas chromatography-mass spectrometry, was developed to simultaneously determine of 99 volatile organic compounds (VOCs) in air samples. This method is rapid, environmentally-friendly (since no organic solvents are used to extract the analytes) and compatible with a large range of thermally stable polar and apolar compounds. The target VOCs were selected on the basis of their occurrence in real samples and their adverse effects on the environment and human health. To cover the wide range of target compounds, multisorbent tubes filled with Tenax TA and Carbograph 1TD were used. Method validation showed good repeatabilities, low detection limits, a high linear range and good recoveries. At a fixed sample volume of 600?mL no significant losses for any of the target compounds were found in the samples. Stability during storage indicated that samples must be keep refrigerated at 4°C and analysed within three days of collection. Real samples were taken from air emissions of an industrial wastewater treatment plant located in the Southern Industrial Area of Tarragona (Spain) with the aim of studying its contribution as a source of atmospheric VOCs. This WWTP collects wastewater from several chemical factories which produce isocyanates, polyurethanes, chlorinated organics and functional chemicals among other products. Samples from the collecting tank after the primary sedimentation showed higher VOC concentrations than samples from the secondary treatment tank. The most abundant VOCs found in these emissions are included in the USEPA List of Hazardous Air Pollutants. The highest values correspond to acrylonitrile (up to 1843?µg?m^?3) and styrene (up to 573.70?µg?m^?3). The levels of chloroform, 1,4-dioxane, ethylbenzene, 1,2,3-trimethylbenzene and 1,4-diethylbenzene were also high.     

Collision spectroscopy in isomer characterization: The case of (E)- and (Z)-p-nitrophenyldiazo tert-butyl sulphides

The structural characterization of the E and Z isomers of p-nitrophenyl-diazo tert-butyl sulphide has been achieved by means of different ionization methods (electron impact, fast atom bombardment, positive-ion chemical ionization) and collision experiments performed under different kinetic energy regimes (high- and low-energy collisions, angle-resolved mass spectrometry and energy-resolved mass spectrometry). The two compounds give rise to identical fragmentation patterns. Collision experiments, both at low energy and in the keV range at a scattering angle of 0°, in M^+· species obtained by electron impact on the two isomers, do not show any significant differences; the same experiments performed with 8 keV ions at a scattering angle of 2° indicate a clear difference in the absolute abundances of the two main daughter ions. High-energy collisions of MH⁺ ions obtained by fast atom bombardment lead to different spectra at both 0° and 2° scattering angles, proving that the energy deposition in the preselected species is an important parameter. Low-energy collisions with argon of MH⁺ ions generated by positive-ion chemical ionization (NH₄⁺) give rise to almost identical energy-resolved mass spectra, whereas the same experiments using helium as target gas lead to a clear distinction between the two isomers.     

Synthesis and physicochemical characterization of fluorescent (E)‐2‐stilbenyloxyalkylthiouracils and isomer differentiation using EIMS

Twelve new fluorescent (E)‐2‐stilbenyloxyalkylthiouracils and 6‐methyluracils 5a‐51 were prepared. EI induced mass spectral fragmentation of these compounds was investigated. Fragmentation pathways are proposed on the basis of accurate mass and metastable transition measurements. Correlation between the intensities of the M⁺ and the selected fragment ions of these compounds is discussed. The data obtained permit a distinction of the metamers. The ¹H and ¹³C NMR spectra of these compounds were assigned unambiguously using a combination of heteronuclear (HETCOR) spectra and the chemical shifts. The data derived from these spectra can be used to differentiate the isomers.     

Profiling the constituents of Dachuanxiong decoction by liquid chromatography with high‐resolution tandem mass spectrometry using target and nontarget data mining

Comprehensive characterization of the large number of compounds existing in traditional Chinese medicines is still a great challenge. In this study, a strategy of precursor ion selected acquisition coupled with target and nontarget data mining was established to systematically characterize the chemical constituents of traditional Chinese medicines. This strategy consisted of four steps: (1) precursor ion selected acquisition was developed to trigger additional tandem mass spectrometry fragmentation reactions, especially for trace constituents; (2) in‐house database of compounds was established and diagnostic characteristics were summarized; (3) compounds were identified by target and nontarget data mining; and (4) compound structures were elucidated based on accurate mass matching and comparison of fragment ions, and isomers were discriminated by the intensity of fragment ions, fragmentation pattern analysis, and calculated log P values. This strategy was successfully applied to comprehensively identify the constituents in Dachuanxiong decoction. Finally, a total of 218 compounds assigned to six categories were characterized, and 107 compounds were characterized by nontarget analysis for the first time. In addition, three new diagnostic characteristics of esters of citric acids were elucidated. This research enriched the material basis of Dachuanxiong decoction and provided a new strategy for identifying the chemical constituents of other traditional Chinese medicines.     

Screening for pharmaco‐toxicologically relevant compounds in biosamples using high‐resolution mass spectrometry: a ‘metabolomic’ approach to the discrimination between isomers

High‐resolution mass spectrometry (HRMS) enables the identification of a chemical formula of small molecules through the accurate measurement of mass and isotopic pattern. However, the identification of an unknown compound starting from the chemical formula requires additional tools: (1) a database associating chemical formulas to compound names and (2) a way to discriminate between isomers. The aim of this present study is to evaluate the ability of a novel ‘metabolomic’ approach to reduce the list of candidates with identical chemical formula. Urine/blood/hair samples collected from real positive cases were submitted to a screening procedure using ESI‐MS‐TOF (positive‐ion mode) combined with either capillary electrophoresis or reversed phase liquid chromatography (LC). Detected peaks were searched against a Pharmaco/Toxicologically Relevant Compounds database (ca 50 500 compounds and phase I and phase II metabolites) consisting of a subset of PubChem compounds and a list of candidates was retrieved. Then, starting from the mass of unknown, mass shifts corresponding to pre‐defined biotransformations (e.g. demethylation, glucuronidation, etc.) were calculated and corresponding mass chromatograms were extracted from the total ion current (TIC) in order to search for metabolite peaks. For each candidate, the number of different functional groups in the molecule was automatically calculated using E‐Dragon software (Talete srl, Milan, Italy). Then, the presence of metabolites in the TIC was matched with functional groups data in order to exclude candidates with structures not compatible with observed biotransformations (e.g. loss of methyl from a structure not bearing methyls). The procedure was tested on 108 pharmaco‐toxicologically relevant compounds (PTRC) and their phase I metabolites were detected in real positive samples. The mean list length (MLL) of candidates retrieved from the database was 7.01 ± 4.77 (median, 7; range, 1–28) before the application of the ‘metabolomic’ approach, and after the application it was reduced to 4.08 ± 3.11 (median 3, range 1–17). HRMS allows a much broader screening for PTRC than other screening approaches (e.g. library search on mass spectra databases). The ‘metabolomic’ approach enables the reduction of the list of candidate isomers. Copyright © 2009 John Wiley & Sons, Ltd.     

Development of a multi-residue method for the determination of organic micropollutants in water, sediment and mussels using gas chromatography-tandem mass spectrometry

This study describes the development of a multiresidue method based on gas chromatography-electron ionization-tandem mass spectrometry (GC-EI-MS/MS) for the detection of sixteen polycyclic aromatic hydrocarbons (PAHs), five phthalate esters (PEs), seven polychlorinated biphenyls (PCBs), six polybrominated diphenyl ethers (PBDEs), six alkylphenols (APs), three organochlorined pesticides and their isomers or degradation products (OCPs) and bisphenol A in seawater, river water, wastewater treatment plant (WWTP) effluents, sediments and mussels. Solid phase extraction (SPE) was used for the extraction of target analytes in aqueous samples, and ultrasound assisted extraction for solid samples. GC-EI-MS/MS acquisition conditions in selected reaction monitoring (SRM) using two transitions per compound were optimized. In this way, quantification and unequivocal identification of organic micropollutants were performed in compliance with the Decision 2002/657/EC. Good linearity responses with coefficients of determination higher than 0.99 were obtained. Methodological detection limits (MDLs) in seawater ranged from 0.1 to 6 ng L(-1); in river water from 0.1 to 4.8 ng L(-1); in WWTP effluents from 1 to 75 ng L(-1); in sediments from 1 to 150 ng g(-1) and in mussels from 1 to 125 ng g(-1). MDLs and recovery yields were compared with other published methods and similarities or even improvements were achieved. The optimized method was applied to analyze five samples from each matrix collected in coastal areas, showing its potential use for marine pollution monitoring.     

A reliable analytical approach based on gas chromatography coupled to triple quadrupole and time‐of‐flight mass analyzers for the determination and confirmation of polycyclic aromatic hydrocarbons in complex matrices from aquaculture activities

The potential of gas chromatography coupled to tandem mass spectrometry (GC/MS/MS) with a triple quadrupole analyzer (QqQ) has been investigated for the quantification and reliable identification of sixteen polycyclic aromatic hydrocarbons (PAHs) from the EPA priority list in animal and vegetable samples from aquaculture activities, whose fat content ranged from 5 to 100%. Matrices analyzed included fish fillet, fish feed, fish oil and linseed oil. Combining optimized saponification and solid‐phase extraction led to high efficiency in the elimination of interfering compounds, mainly fat, from the extracts. The developed procedure minimized the presence of these interfering compounds in the extracts and provided satisfactory recoveries of PAHs. The excellent sensitivity and selectivity of GC/(QqQ)MS/MS in selected reaction monitoring (SRM) allowed to reach limits of detection at pg/g levels. Two SRM transitions were acquired for each analyte to ensure reliable identification of compounds detected in samples. Confirmation of positive findings was performed by GC coupled to high‐resolution time‐of‐flight mass spectrometry (GC/TOFMS). The accurate mass information provided by GC/TOFMS in full acquisition mode together with its high mass resolution makes it a powerful analytical tool for the unequivocal confirmation of PAHs in the matrices tested. The method developed was applied to the analysis of real‐world samples of each matrix studied with the result of detecting and confirming the majority of analytes at the µg/kg level by both QqQ and TOF mass spectrometers. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of phenolic choline esters from seeds of Arabidopsis thaliana and Brassica napus by capillary liquid chromatography/electrospray‐ tandem mass spectrometry

Total phenolic choline ester fractions prepared from seeds of Arabidopsis thaliana and Brassica napus were analyzed by capillary LC/ESI‐QTOF‐MS and direct infusion ESI‐FTICR‐MS. In addition to the dominating sinapoylcholine, 30 phenolic choline esters could be identified based on accurate mass measurements, interpretation of collision‐induced dissociation (CID) mass spectra, and synthesis of selected representatives. The compounds identified so far include substituted hydroxycinnamoyl‐ and hydroxybenzoylcholines, respective monohexosides as well as oxidative coupling products of phenolic choline esters and monolignols. Phenolic choline esters are well separable by reversed‐phase liquid chromatography and sensitively detectable using electrospray ionization mass spectrometry in positive ion mode. CID mass spectra obtained from molecular ions facilitate the characterization of both the type and substitution pattern of such compounds. Therefore, LC/ESI‐MS/MS represents a valuable tool for comprehensive qualitative and quantitative analysis of this compound class. Copyright © 2008 John Wiley & Sons, Ltd.     

Systematic screening and characterization of novel bufadienolides from toad skin using ultra‐performance liquid chromatography/electrospray ionization quadrupole time‐of‐flight mass spectrometry

During the discovery process of novel compounds, it is of significant importance to differentiate novel from known compounds in crude extracts before starting the time‐consuming process of purification. Bufadienolides are the main active components of the skin of the toad Bufo bufo gargarizans Cantor (toad skin), an important traditional Chinese medicine. The fragmentation behavior and mass spectra profiles of bufadienolides standards were investigated using ultra‐performance liquid chromatography/electrospray ionization quadrupole time‐of‐flight mass spectrometry (UPLC/ESI‐Q‐TOFMS). Several fragmentation rules were summarized and applied to characterize novel and known bufadienolides in toad skin. Characteristic substituent groups could be identified by both diagnostic ions and their relative abundance. Bufadienolide stereoisomers could be differentiated from positional isomers by comparing fragment abundance profiles. This was used to characterize new stereoisomers for known bufadienolides. A total of 39 bufadienolides were screened out using a systematic method developed in our laboratory. In addition to 19 known bufadienolides, 20 putative novel compounds, including 8 stereoisomers, were characterized. UPLC/Q‐TOFMS was demonstrated to be a powerful tool for the characterization of low‐abundance bufadienolides in complex samples. This study provides guidelines for the targeted isolation of novel bufadienolides from natural products. Copyright © 2010 John Wiley & Sons, Ltd.