Negative Ionization Mass Spectrometry Research Articles

Identification of a Chimera Mass Spectrum of Isomeric Lipid A Species Using Negative Ion Tandem Mass Spectrometry.

The toxic nature of bacterial endotoxins is affected by the structural details of lipid A, including the variety and position of acyl chains and phosphate group(s) on its diglucosamine backbone. Negative-ion mode tandem mass spectrometry is a primary method for the structure elucidation of lipid A, used independently or in combination with separation techniques. However, it is challenging to accurately characterize constitutional isomers of lipid A extracts by direct mass spectrometry, as the elemental composition and molecular mass of these molecules are identical. Thus, their simultaneous fragmentation leads to a composite, so-called chimera mass spectrum. The present study focuses on the phosphopositional isomers of the classical monophosphorylated, hexaacylated Escherichia coli-type lipid A. Collision-induced dissociation (CID) was performed in an HPLC-ESI-QTOF system. Energy-resolved mass spectrometry (ERMS) was applied to uncover the distinct fragmentation profiles of the phosphorylation isomers. A fragmentation strategy applying multi-levels of collision energy has been proposed and applied to reveal sample complexity, whether it contains only a 4'-phosphorylated species or a mixture of 1- and 4'-phosphorylated variants. This comparative fragmentation study of isomeric lipid A species demonstrates the high potential of ERMS-derived information for the successful discrimination of co-ionized phosphorylation isomers of hexaacylated lipid A.

Persistent and Bioaccumulative Halogenated Natural Products in Various Tropical Reef Fish Species from the Seychelles, Western Indian Ocean.

Gas chromatography with electron capture negative ion mass spectrometry (GC/ECNI-MS) was used to quantify and compare halogenated natural products (HNPs) and selected anthropogenic persistent organic pollutants (POPs) in individual samples of 17 fish species from the Seychelles (Western Indian Ocean). The sum-HNP amounts (9.5-1100 ng/g lipid mass (lm)) were between 1 and 2 orders of magnitude higher than those of the sum of seven abundant polychlorinated biphenyl (PCB) congeners (0.2-15 ng/g lm) and dichlorodiphenyltrichloroethane-related compounds (DDTs) (<1.1-43 ng/g lm). Within the group of HNPs, the two tetrabrominated phenoxyanisoles (aka methoxylated diphenyl ethers, MeO-BDEs), 2'-MeO-BDE 68 ≫ 6-MeO-BDE 47, were predominant in most cases. Pearson correlation analysis showed that MeO-BDE levels were positively correlated with less abundant HNPs (2,2'-diMeO-BB 80, 2',6-diMeO-BDE 68, and Br6-DBP) (p < 0.01). Accordingly, HNPs, rather than PCBs and DDTs, were the predominant polyhalogenated contaminants in the current species.

Characterization and identification of chemical components from Euodiae Fructus based on UHPLC-Q-TOF-MS

A sensitive and efficient ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry(UHPLC-Q-TOF-MS) approach was established. Based on the self-developed information library, the chemical components from Euodiae Fructus were systematically characterized and identified. The chromatographic separation conditions(e. g., stationary phase,mobile phase, column temperature, and elution gradient) and MS detection conditions(nozzle voltage, capillary voltage, fragmentor,and collision energy) were optimized. Ultimately, an HSS T3 column(2. 1 mm×100 mm, 1. 8 μm) maintained at 35 ℃ was used,and 0. 1% formic acid water-acetonitrile at the flow rate of 0. 4 m L·min~(-1) was used as the mobile phase. Electrospray ionization was adopted to collect the positive and negative ion mass spectrometry data in Auto MS/MS mode. According to the reference compound comparison, fragment ion information interpretation, literature, and retrieval in the self-developed information library, 92 compounds were characterized or derived from the decoction of Euodiae Fructus, including 33 alkaloids, 23 flavonoids, 12 terpenoids, 12phenylpropanoids, and 12 others. Among them, 17 compounds were identified by comparison with the reference compounds, and 11compounds were unreported from Euodiae Fructus. This study realizes the rapid characterization and identification of multi-class chemical components in the decoction of Euodiae Fructus and provides a reference for the studies regarding its effective substances and quality control.

Multinozzle Emitter for Improved Negative Mode Analysis of Reduced Native N-Glycans by Microflow Porous Graphitized Carbon Liquid Chromatography Mass Spectrometry.

Microflow porous graphitized carbon liquid chromatography (PGC-LC) combined with negative mode ionization mass spectrometry (MS) provides high resolution separation and identification of reduced native N-glycan structural isomers. However, insufficient spray quality and low ionization efficiency of N-glycans present challenges for negative mode electrospray. Here, we evaluated the performance of a recently developed multinozzle electrospray source (MnESI) and accompanying M3 emitter for microflow PGC-LC-MS analysis of N-glycans in negative mode. In comparison to a standard electrospray ionization source, the MnESI with an M3 emitter improves signal intensity, identification, quantification, and resolution of structural isomers to accommodate low-input samples.

Fragmentation patterns of DNA-stabilized silver nanoclusters under mass spectrometry.

DNA-stabilized silver nanoclusters (AgN-DNAs) are emitters with tuneable structures and photophysical properties. While understanding of the sequence-structure-property relationships of AgN-DNAs has advanced significantly, their chemical transformations and degradation pathways are far less understood. To advance understanding of these pathways, we analysed the fragmentation products of 21 different red and NIR AgN-DNAs using negative ion mode electrospray ionization mass spectrometry (ESI-MS). AgN-DNAs were found to lose Ag+ under ESI-MS conditions, and sufficient loss of silver atoms can lead to a transition to a lesser number of effective valence electrons, N0. Of more than 400 mass spectral peaks analysed, only even values of N0 were identified, suggesting that solution-phase AgN-DNAs with odd values of N0 are unlikely to be stable. AgN-DNAs stabilized by three DNA strands were found to fragment significantly more than AgN-DNAs stabilized by two DNA strands. Moreover, the fragmentation behaviour depends strongly on the DNA template sequence, with diverse fragmentation patterns even for AgN-DNAs with similar molecular formulae. Molecular dynamics simulations, with forces calculated from density functional theory, of the fragmentation of (DNA)2(Ag16Cl2)8+ with a known crystal structure show that the 6-electron Ag16Cl2 core fragments into a 4-electron Ag10 and a 2-electron Ag6, preserving electron-pairing rules even at early stages of the fragmentation process, in agreement with experimental observation. These findings provide new insights into the mechanisms by which AgN-DNAs degrade and transform, with relevance for their applications in sensing and biomedical applications.

Analysis of O-acetylated sialic acids by 3-nitrophenylhydrazine derivatization combined with LC-MS/MS.

Sialic acids are a family of monosaccharides that share a nine-carbon backbone and a carboxyl group. A recent derivatization method based on 3-nitrophenylhydrazine (3-NPH) provides a mild chemical labeling technique for biomolecules containing carbonyl or carboxyl groups. In this study, we utilized 3-NPH to label sialic acids via a two-step derivatization process. The derivatized species can produce a common reporter ion corresponding to C1-C3 with two labels, and a fragment differentiating between Neu5Ac, Neu5Gc, and KDN. This method is compatible with O-acetylated sialic acids and provides high sensitivity to Neu5Gc and KDN, and since the utilization of dual labeling significantly enhances the hydrophobicity of derivatives, it can effectively mitigate matrix effects when combined with parallel reaction monitoring technology. Negative-ion tandem mass spectrometry (MS/MS) analysis reveals a distinctive fragmentation profile for the 4-O-acetylated species, while the other sialic acids yield similar MS/MS spectra with a high abundance of reporter ions. Using the reporter ion as a transition, this analytical strategy is effective for analyzing complex biological samples. For example, it was successfully employed to quantify sialic acids in the intestinal tissues of several carp species, demonstrating its potential in sialylation research.

A simple laboratory method for the generation of mixed brominated-chlorinated paraffin single chain mixtures

Brominated-chlorinated paraffins (Br-CPs) are a comparably new compound class that features both Cl and Br atoms on one or several alkane backbones. Due to legal restrictions in the use of conventional chlorinated paraffins (CPs), Br-CPs have the potential to become emerging contaminants. Currently, their determination is hampered by the lack of suitable reference standards. Here, we present a simple synthesis procedure with single chain alkanes that leads to Br-CPs with ∼4–8 chlorine and 1 to 4 bromine substituents according to gas chromatography with electron capture negative ion mass spectrometry (GC/ECNI-MS). The single-chain Br-CP mixtures were obtained by the shared chlorination and bromination of eight single-chain alkanes (C10 to C17) at two reaction times, respectively. The carbon content of the 16 single-chain Br-CP products, determined by elemental analysis (EA), ranged from 30.8 to 43.8 %. The typical hump peak known from CPs was detected with GC with flame ionization detection (GC/FID), electron capture detection (GC/ECD) and GC/ECNI-MS. The complexity indicated that low-resolution mass spectrometry is not sufficient for an adequate analysis of Br-CPs. A mathematical formula was developed which allows to calculate all possible combinations of Br and Cl that are in line with the carbon content. The proton magnetic resonance spectroscopy (1H NMR) spectra showed similarities to the ones of CPs with one chemical shift range for protons on nonhalogenated carbons and one for protons with one halogen on the same carbon.

Short- and medium-chain chlorinated paraffins in sediment from the Haihe River Basin: Sources, distributions, and ecological risk assessment

Chlorinated paraffins (CPs) can accumulate in sediment and pose risks to ecological systems and human health. The Haihe River Basin is one of the seven main river basins in China and is mainly in the Beijing–Tianjin–Hebei region, which is densely populated and very urbanized. There is therefore a high probability of CP pollution in the Haihe River Basin. However, CP pollution and the environmental risks posed by CPs in the Haihe River are not well understood. In this study, the concentrations of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) in sediment from six rivers in the Haihe River Basin system were determined using two-dimensional gas chromatography electron-capture negative ionization mass spectrometry. The total SCCP and MCCP concentrations in the sediment samples ranged from 131.83 to 1767.71 and from 89.72 to 1442.82 ng/g dry weight, respectively. The total organic carbon content did not significantly correlate with the CP concentrations. The dominant SCCP congener groups were C10Cl6–7 and the dominant MCCP congener groups were C14Cl7–8. Significant relationships (R = 0.700, p < 0.05) were found between the SCCP and MCCP concentrations, indicating that SCCPs and MCCPs may have similar sources. Hierarchical cluster analysis and principal component analysis indicated that sediment in the study area was contaminated with CPs through the use of the CP-42 and CP-52 commercial products in industrial processes and human activities. The ecological risks posed by CPs were assessed and SCCPs were found to pose high risks in the Yongding New River but moderate risks in the other rivers. MCCPs were found to pose minimal risks to the aquatic environment at most of the sampling points.

UV-Vis absorption spectrophotometry and LC-DAD-MS-ESI(+)-ESI(−) coupled to chemometrics analysis of the monitoring of sulfamethoxazole degradation by chlorination, photodegradation, and chlorination/photodegradation

Sulfamethoxazole (SMX) is one of the most widely used antibiotics worldwide and has been detected at high concentrations in wastewater treatment plant effluents and river waters. In this study, the SMX degradation process combining the simultaneous chlorine oxidation and UV photodegradation is assessed and compared with both photodegradation and chlorine oxidation processes individually. Photodegradation and Chlorine/UV tests were performed using Suntest CPS equipment. Different experimental techniques, including UV–Visible spectrophotometry and liquid chromatography coupled to a diode array detector and positive and negative ionization mass spectrometry (LC-DAD-MS-ESI(+)-ESI(−)), were used to evaluate the degradation reaction of SMX.All the analytical data generated have been processed with the Multivariate Curve Resolution–Alternating Least Squares (MCR-ALS) method to monitor, resolve, and identify the several transformation products generated during the studied degradation processes. A new data fusion analysis strategy is proposed to examine the three processes simultaneously (with only photodegradation, only chlorination, and simultaneous chlorination+photodegradation). Combined with the analysis of different analytical techniques individually (spectrophotometry, LC-DAD, and LC-MS), the fusion of all generated data improved the description of the degradation processes.Detection using DAD allowed a better correspondence among the species monitored spectrophotometrically (UV–Vis) with those analyzed chromatographically. On the other side, detection using MS in both positive and negative acquisition modes allowed resolving a larger number of chemical compounds (specially SMX degradation subproducts) that could not be detected by UV–Vis spectrometry. The results obtained permitted the comparison of the effects produced by the three different degradation processes.

Predicting Sialic Acid Content of N-Linked Glycans Using the Isotopic Pattern of Chlorine.

Sialic acids play several roles in both physiological and pathological processes; however, due to their labile nature, they are difficult to analyze using mass spectrometry. Previous work has shown that infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) is able to detect intact sialylated N-linked glycans without the use of chemical derivatization. In this work, we describe a new rule that can predict the number of sialic acids on a glycan. Formalin-fixed paraffin-embedded human kidney tissue was prepared using previously established methods and analyzed using IR-MALDESI in negative-ion mode mass spectrometry. Using the experimental isotopic distribution of a detected glycan, we can predict the number of sialic acids on the glycan; #sialic acids is equal to the charge state minus the number of chlorine adducts, or z - #Cl-. This new rule grants confident glycan annotations and compositions beyond accurate mass measurements, thereby further improving the capability of IR-MALDESI to study sialylated N-linked glycans within biological tissues.

UiO-66-NH2: a recyclable and efficient sorbent for dispersive solid-phase extraction of fluorinated aromatic carboxylic acids from aqueous matrices.

The present study describes the trace analysis of 23 fluorinated aromatic carboxylic acids based on the dispersive solid-phase extraction (dSPE) technique using UiO-66-NH2 MOF as efficient, recyclable sorbent, and GC-MS negative ionization mass spectrometry (NICI MS) as determination technique. All 23 fluorobenzoic acids (FBAs) were enriched, separated, and eluted in a shorter retention time; the derivatization was done by pentafluorobenzyl bromide (1% in acetone), in which the use of inorganic base K2CO3 was improved by triethylamine to increase the lifespan of the GC column. The performance of UiO-66-NH2 was evaluated by dSPE in Milli-Q water, artificial seawater, and tap water samples, and the impact of various parameters on the extraction efficiency was investigated by GC-NICI MS. The method was found to beprecise, reproducible, and applicable to the seawater samples. In the linearity range, the regression value was foundto be >0.98; LOD and LOQ were foundto be in the range of0.33-1.17ng/mL and 1.23-3.33ng/mL, respectively; and the value of theextraction efficiency was found to range between 98.45 and 104.39% for Milli-Q water samples, 69.13-105.48% for salt-rich seawater samples, and 92.56-103.50% for tap water samples with amaximum RSD value of6.87% that confirms the applicability of the method to different water matrices.

Оценка сродства к электрону по данным о временах жизни отрицательных молекулярных ионов p-кумаровой и кумарин-3-карбоновых кислот

The molecules of p-coumaric and coumarin-3-carboxylic acids were studied by the method of mass spectrometry of negative ions of resonant electron attachment. The average lifetime of negative molecular ions relative to spontaneous electron emission has been experimentally measured. With Arrhenius approximation, the value of the adiabatic electron affinity (EAa) was estimated. It is established that the theoretical values of EAa calculated by the B3LYP/6-31+G(d) method with minimal addition of diffuse functions as the difference of the total energies of the neutral molecule and the radical anion correlate well with the values of EAa obtained from the experiment.

Resonance Electron Capture by 5-Methyluridine and 3'-Deoxythymidine Molecules

Negative ion mass spectrometry is used to study processes of resonant electron attachment by 5‑methyluridine and 3'-deoxythymidine nucleoside molecules in the electron 0–14 eV range of energies. It is established that they are similar to those in nucleosides studied earlier (uridine, deoxyuridine, thymidine). The main channels of the fragmentation of molecular ions are revealed, and the absolute cross sections for the formation of fragment ions are determined. It is found that the intensity of the breaking the glycosidic bond in 3'-deoxythymidine in the region of low energies is two and a half orders of magnitude below the one in stavudine, testifying to the prospect of replacing the antiretroviral drug stavudine with 3'-deoxythymidine if radiation therapy is required for oncological diseases contracted as complications of HIV.

Aging of α-Pinene Secondary Organic Aerosol by Hydroxyl Radicals in the Aqueous Phase: Kinetics and Products.

The reaction of hydroxyl radicals (OH) with a water-soluble fraction of the α-pinene secondary organic aerosol (SOA) was investigated using liquid chromatography coupled with negative electrospray ionization mass spectrometry. The SOA was generated by the dark ozonolysis of α-pinene, extracted into the water, and subjected to chemical aging by the OH. Bimolecular reaction rate coefficients (kOH) for the oxidation of terpenoic acids by the OH were measured using the relative rate method. The unaged SOA was dominated by the cyclobutyl-ring-retaining compounds, primarily cis-pinonic, cis-pinic, and hydroxy-pinonic acids. Aqueous oxidation by the OH resulted in the removal of early-stage products and dimers, including well-known oligomers with MW = 358 and 368 Da. Furthermore, a 2- to 5-fold increase in the concentration of cyclobutyl-ring-opening products was observed, including terpenylic and diaterpenylic acids and diaterpenylic acid acetate as well as some of the newly identified OH aging markers. At the same time, results obtained from the kinetic box model showed a high degree of SOA fragmentation following the reaction with the OH, which indicates that non-radical reactions occurring during the evaporation of water likely contribute to the high yields of terpenoic aqSOAs reported previously. The estimated atmospheric lifetimes showed that in clouds, terpenoic acids react with the OH exclusively in the aqueous phase. Aqueous OH aging of the α-pinene SOA results in a 10% increase of the average O/C ratio and a 3-fold decrease in the average kOH value, which is likely to affect the cloud condensation nuclei activity of the aqSOA formed after the evaporation of water.

Chlorinated paraffins in nut-nougat and chocolate spreads from the German market

Chlorinated paraffins (CPs) are amongst the most discussed polyhalogenated pollutants in recent years. Their ubiquitous occurrence in the environment and especially foodstuff has given rise to concerns about CP uptake levels. Especially animal products and oils, i.e. foodstuff with high fat contents showed comparably high CP contaminations. In this study, nut-nougat and chocolate spread samples (n = 30) from the German market were analyzed on the occurrence of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) via gas chromatography coupled with electron capture negative ion mass spectrometry (GC/ECNI-MS). Fifteen (= 50%) of the samples contained CPs, with MCCPs being much higher abundant (17–270 ng/g fresh weight (fw)) in most samples than SCCPs (7.5–50 ng/g fw). No statistical correlation could be established between SCCP or MCCP occurrence on one hand and manufacturer or ingredients, such as palm oil on the other hand. A preliminary risk assessment of the detected levels gave margins of exposure (MOE) to CPs from consumption of chocolate and nut-nougat spreads ranging from approx. 16,000 to 48,000. Since health concerns are expected at an MOE of <1,000, this indicated no risk from CP intake for the consumer by consumption of these products, based on current knowledge. • CPs were analyzed in 30 nut-nougat and chocolate spreads from the German market. • Short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) were separately quantified. • Fifteen samples (50%) contained CPs between 7.5 and 270 ng/g fat. • MCCPs were higher abundant than SCCPs in most samples. • A preliminary risk assessment indicated no risk from CP intake for consumers.

Occurrence of legacy organochlorine pesticides in small mammals from two mountainous National Parks in southeastern Brazil

In southeastern Brazil, particular altitudinal grassland ecosystems, known as campos de altitude, occur at mountainous summits that host an outstanding level of biodiversity and endemism. However, despite being environmentally protected areas, several studies have shown their susceptibility to the impacts of climate change and airborne pollution. Previous studies highlighted that organochlorine pesticides (OCPs), present higher atmospheric concentrations along altitudinal gradients and can be locally deposited. On top of that, formerly used OCPs are still detected in the atmosphere on those mountaintops, long after their phase-out. Nevertheless, the potential bioaccumulation of OCPs by endemic species has not yet been assessed. Thus, we aimed to investigate the occurrence of OCPs in terrestrial subalpine wildlife and to establish a baseline for further in-depth studies on OCPs, or similar hazardous chemicals, in these endangered environments. In summary, 28 OCP congeners were investigated in 49 liver samples of ten small mammal species collected in 2013 and in 2016. Chemical analyses were based on gas chromatography coupled with electron capture negative ionization mass spectrometry (GC/ECNI-MS). Additional stable isotope analyses (δ 15 N and δ 13C) were performed to elucidate the role of trophic position on OCP bioaccumulation. Mirex, heptachlor, hexachlorobenzene, chlordane, and hexachlorocyclohexane congeners were the most frequently detected OCPs (59–97% of all samples). Regarding OCP contents in liver tissues, Mirex was also dominant. The atmospheric transport from secondary sources was assumed to be the origin of OCPs in the studied environment and their occurrence and difference between the two sampling sites are in good agreement with previous atmospheric monitoring. Further studies are needed to evaluate the exposure of campos de altitude endemic organisms to other airborne hazardous chemicals and to assess the potential toxicity posed by contaminant mixtures.

Short and medium-chain chlorinated paraffins in indoor dust from a multistory residential building in Beijing, China: Vertical distribution and potential health risks

In this study, we conducted a preliminary investigation of the vertical distribution and potential health risks of short and medium-chain chlorinated paraffins (SCCPs and MCCPs) in indoor dust from a multistory residential building in Beijing, China. Forty-eight SCCP and MCCP congener groups in dust from different floors of the multistory residential building were determined by two-dimensional gas chromatography coupled with electron capture negative ionization mass spectrometry. The concentration ranges for SCCPs and MCCPs in the dust samples were 0.0239–207 μg/g and 0.135–2903 μg/g, respectively. MCCPs were the dominant group, on average accounting for 76.8 % of ∑CPs. Generally, the concentrations of both SCCPs and MCCPs greatly decreased as the floor level increased, which indicated that the CP contamination was attributed to exogenous atmospheric transport and deposition. C13Cl7–8 and C14Cl7–8 were the dominant SCCP and MCCP congener groups, possibly indicating the use of industrial CP-52 products was the main source of CPs. In the worst-case scenario using the maximum concentrations of CPs, the daily intake of SCCPs for toddlers was of the same order of magnitude as the reference dose. It should be noted that CPs exposure may be more serious when indoor decorations, furniture, and various plastic products are taken into consideration. Overall, more attention should be paid to CPs exposure and control measures in high-rise buildings.

Legacy and novel brominated flame retardants in air of Ny-Ålesund, Arctic from 2011 to 2019

Concentrations of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in the atmosphere of Ny-Ålesund, Svalbard, were investigated. Passive air samples were collected for eight consecutive one-year periods from August 2011 to August 2019 at seven Arctic sampling sites. High-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC-HRMS) and gas chromatography coupled with election capture negative ionization mass spectrometry (GC-NCI-MS) were employed for PBDE and NBFR analysis, respectively. The median concentrations of Ʃ11PBDEs and Ʃ6NBFRs were 0.6 pg/m3 and 4.0 pg/m3, respectively. Hexabromobenzene and BDE-47 were the most abundant NBFR and PBDE congeners in the atmosphere, accounting for 31% and 24% of ƩNBFR and ƩPBDE concentrations, respectively. ƩNBFR concentration was approximately six times higher than that of ƩPBDEs in the same samples. Among NBFRs, the concentrations of 1,2,3,4,5-pentabromobenzene, 2,3,4,5,6-pentabromobenzene, and 2,3-dibromopropyl-2,4,6-tribromophenyl ether showed increasing temporal variations, with estimated doubling times of 3.0, 3.3, and 2.8 years, respectively. The concentrations of almost all PBDE congeners showed a decreasing variation, with halving times ranging from 2.1 to 9.5 years.

A fast gas chromatography coupled with electron capture negative ion mass spectrometry in selected ion monitoring mode screening method for short-chain and medium-chain chlorinated paraffins.

Chlorinated paraffins (CPs) are a group of anthropogenic pollutants that consist of complex mixtures of polychlorinated n-alkanes of different chain lengths (~C10 to C30 ). Persistence, bioaccumulation, toxicity, and long-range transport of short-chain chlorinated paraffins (SCCPs, C10 - to C13 -CPs) have prompted their classification as persistent organic pollutants (POPs) by the Stockholm Convention in 2017. Due to the varying chain lengths and chlorination degrees, quantification of SCCPs and medium-chain chlorinated paraffins (MCCPs, C14 - to C17 ) using gas chromatography coupled with electron capture negative ion mass spectrometry in selected ion monitoring mode (GC/ECNI-MS-SIM) is not only challenging but also very time consuming. In particular, up to eight GC runs per sample are required for the comprehensive GC/ECNI-MS-SIM quantification of SCCPs and MCCPs. These efforts are high especially if the samples do not contain CPs above the limit of detection (LOD), subsequently. We developed a semi-quantitative and sensitive method for the examination of SCCPs and MCCPs in one GC run. This GC/ECNI-MS-SIM screening method was based on the recording of Cl- (m/z 35 and 37), Cl2 - (m/z 70 and 72), and HCl2 - (m/z 71 and 73) isotope ions and evaluation of the ratios between them. Correctness of the results of the screening method was verified by analysis of edible oils with and without CPs, CP standards, as well as a technical CP mixture. Polychlorinated biphenyls (PCBs) and other polyhalogenated aromatic compounds, as well as brominated flame retardants, do not form all of the fragment ions analyzed by the screening method. After the screening, only CP-positive samples may need to be measured in detail. Measurement time will already be gained in the case of ~10% samples without CPs.

Определение примесных мод в спектрах диссоциативного захвата электронов молекулами бензофуран-3(2Н)-она и бензофуран-2(3Н)-она

The method of negative ion mass spectrometry of resonant attachment of low energy electrons (0-15 eV) was used to identify and determine the type of impurities in the studied samples of benzofuran-3(2H)-one and benzofuran-2(3H)-one. An analysis of the decay channels of molecular negative ions (NIs) into stable fragments using the results of quantum-chemical calculations in the approximation of the density functional theory made it possible to determine the most probable structures of impurity molecules, as well as fragment ions ([M - H]-, [M - 2H]-, [M - СО]-).