•A method for the determination of 24 emerging pharmaceuticals has been developed.•The analysis of 21 samples revealed the occurrence of 20 selected pharmaceuticals.•The highest concentration was ...found for caffeine and acetaminophen.
A multi-class method for the determination of 24 emerging pharmaceutical residues has been developed and validated. The method is based on solid-phase extraction of wastewater samples using Strata-X cartridges followed by high performance liquid chromatography coupled to hybrid quadrupole − Orbitrap high resolution mass spectrometry (HPLC-Q-Orbitrap-HRMS). A single-laboratory validation procedure showed satisfactory analytical performance. The analysis of 21 samples collected at the wastewater treatment plant in Riga revealed the occurrence of 20 compounds of different therapeutic classes. The highest concentration was found for the central nervous system stimulator caffeine − up to 12μgL−1, the analgesic acetaminophen up to 4.2μgL−1, the antibiotic ciprofloxacin in the concentration range of 250–400ngL−1, and the non-steroidal anti-inflammatory drug (NSAID) ibuprofen at 100–325ngL−1.
Flame retardants (FRs) are additives used in consumer products to reduce flammability, even though they can easily contaminate the indoor environment. Since it is common for people in modern cities ...to spend up to 85% of time indoors, the quality of the indoor environment is critical for human health. In this study, polybrominated diphenyl ethers (PBDEs), organophosphorus flame retardants (OPFRs), emerging brominated flame retardants (EBFRs), and dechlorane-related compounds (DRCs) were measured in household dust samples (
n = 34
) from Latvia, followed by human exposure assessment. Among all studied compounds, OPFRs showed the highest concentrations (1380–133,000 ng g
−1
). Despite the phase-out of PBDEs, they were the second most significant flame retardants in the studied dust samples (468–25,500 ng g
−1
) and the predominant compound was BDE-209. The concentrations of EBFRs were in the range of 120–7295 ng g
−1
, with the most abundant contaminant being DBDPE, which is widely used as a substitute for the deca-BDE formulation. DRCs were the least common flame retardants in the Latvian indoor environments, with concentrations ranging 22.4–192 ng g
−1
. Although the concentrations of specific FRs are known to vary between different countries, the levels and patterns observed in dust samples from Latvia were similar to those reported from Central Europe. Human exposure was evaluated as the estimated daily intake (EDI). The calculated exposure to most of the FRs was several orders of magnitude lower than the available reference dose (RfD) values.
•Sensitive and accurate analysis for very low concentrations of PAHs was developed.•GC-MS/MS and GC-HRMS methods were compared.•Methods LODs varied between 0.002μgkg−1 and 0.006μgkg−1.•Methods ...demonstrated appropriate performance in PAHs analysis even at low contamination levels.
Due to the high consumption level, cereals represent one of the major sources of human exposure to PAHs. Taking into account the low maximum permitted level (ML) established in the European Union (EU) for the sum of four priority PAHs (PAH4) in processed cereal-based foods, sensitive and selective analysis for very low concentrations of these carcinogenic compounds was developed and compared by applying two different analytical techniques. Elaborated methods demonstrated appropriate performance in PAHs analysis even at low contamination levels. Limits of detection (LOD) for the PAH4 varied between 0.002μgkg−1 and 0.006μgkg−1, recoveries were in the range of 92–103% for GC-MS/MS and 108–117% for GC-HRMS. Elaborated methods were applied for the analysis of 35 Latvian cereals and bread samples. The concentrations of PAH4 were in a range of 0.22–1.62μgkg−1 with 14% of samples exceeding the current EU maximum permitted levels.
The food and feed sector in Europe is rapidly evolving to address contemporary challenges, striving for fairer, safer, greener and more sustainable food systems. This includes the exploration of new ...protein sources for human consumption and animal feed such as protein derived from insects, algae or novel plant‐derived proteins, and the re‐evaluation of existing sources like processed animal protein (PAP). To generate reliable data on the diverse array of emerging protein sources for future food and feed safety assessments, a growing demand for the development and implementation of advanced analytical techniques exists. New approach methodologies (NAMs) including, mass spectrometry (MS)‐based proteomics methods have been emerging as valuable techniques which potentially can be implemented in regulatory laboratory settings to complement conventional approaches in this realm. These MS‐driven strategies have already proven their utility in diverse applications, including the detection of prohibited substances in feed, identification of allergens, differentiation of fish species in complex mixtures for fraud detection and the verification of novel foods and alternative protein sources. This EU‐FORA programme was focused on three core objectives namely: (i) the training of the fellow in utilising MS‐based proteomics for food and feed safety analyses, (ii) the involvement of the fellow in the development of standardised operating procedures (SOP) for targeted and non‐targeted proteomic MS‐based workflows for species and tissues specific PAP identification in a national reference laboratory (NRL) and (iii) the transfer and implementation of MS‐based approaches and standardised protocols for PAP analysis at the fellow's home institution. Altogether, this programme facilitates the broadening and diversification of use of MS‐based proteomic methodologies for reinforcing their significance within the domains of food and feed safety research and regulatory science applications.
The heterogeneity in severity and outcome of COVID-19 cases points out the urgent need for early molecular characterization of patients followed by risk-stratified care. The main objective of this ...study was to evaluate the fluctuations of serum metabolomic profiles of COVID-19 patients with severe illness during the different disease stages in a longitudinal manner. We demonstrate a distinct metabolomic signature in serum samples of 32 hospitalized patients at the acute phase compared to the recovery period, suggesting the tryptophan (tryptophan, kynurenine, and 3-hydroxy-DL-kynurenine) and arginine (citrulline and ornithine) metabolism as contributing pathways in the immune response to SARS-CoV-2 with a potential link to the clinical severity of the disease. In addition, we suggest that glutamine deprivation may further result in inhibited M2 macrophage polarization as a complementary process, and highlight the contribution of phenylalanine and tyrosine in the molecular mechanisms underlying the severe course of the infection. In conclusion, our results provide several functional metabolic markers for disease progression and severe outcome with potential clinical application.
Although the host defense mechanisms against SARS-CoV-2 infection are still poorly described, they are of central importance in shaping the course of the disease and the possible outcome. Metabolomic profiling may complement the lacking knowledge of the molecular mechanisms underlying clinical manifestations and pathogenesis of COVID-19. Moreover, early identification of metabolomics-based biomarker signatures is proved to serve as an effective approach for the prediction of disease outcome. Here we provide the list of metabolites describing the severe, acute phase of the infection and bring the evidence of crucial metabolic pathways linked to aggressive immune responses. Finally, we suggest metabolomic phenotyping as a promising method for developing personalized care strategies in COVID-19 patients.
The composition of lipophilic and hydrophilic components in cultivated (
C
.
tinctorius
) and wild (
C
.
oxyacantha
) safflower seed oils was studied. By LC–HRMS/MS
2
, a total of seven highly ...abundant bioactive compounds with hydrophilic nature, a lignan glycoside (tracheloside), two flavonoids (acacetin–glucuronide pentoside and acacetin-7-
O
-D-glucuronide), and four alkaloids (N-coumaroylserotonin glucoside, N-feruloylserotonin glucoside, N-coumaroylserotonin, and N-feruloylserotonin), in seeds of both species, were identified. Only a minor part of the hydrophilic compounds (≤ 0.05%) present in the seeds was transferred into the seed oil during the extraction. The linoleic (~ 78%), oleic (~ 15%), palmitic (~ 5%), and stearic (~ 2%) acids—constituted 99% of all detected fatty acids in both species. α-Tocopherol was a main form of tocochromanols (over 94%) in both safflower seed oils. β-Sitosterol was the predominate form (over 36%) of phytosterols, while high levels were also recorded for gramisterol (17.1%) and avenasterol (19.6%) in
C
.
oxyacantha
and
C
.
tinctorius
seed oils, respectively. Zeaxanthin was a predominated form of carotenoids (over 37%), while high levels were recorded for lutein and β-carotene 15 and 25%, mainly in
C. oxyacantha.
The total amount of minor lipophilic compounds such as tocochromanols, carotenoids and sterols in
C
.
oxyacantha
vs.
C. tinctorius
seed oil was 57.9 vs. 58.2, 0.76 vs. 0.5, and 185.5 vs. 274 mg/100 g oil, respectively. The presence of squalene was detected only in
C. oxyacantha
(10.4 mg/100 g oil). Despite the similar composition and levels of fatty acids and tocochromanols, species differed by the phytosterols, carotenoids, and bioactive compounds with hydrophilic nature.
Procyanidins are a polyphenolic group that can be found in a variety of foods such as chocolate, tea, cranberries and others. Type A procyanidins can be found in a handful of sources and one of the ...richest sources are American cranberries. These compounds possess antioxidative, anticancer and anti-inflammatory activities and are most widely used as prevention for urinary tract infections. Cranberries are utilized for jam and juice production, and the latter produces industrial food waste press residues. Press residues contain free and bound procyanidins which can be extracted for use as nutraceuticals. In this study, the extraction of cranberry press residues has been optimized using RSM and the resulting extracts have been purified and fractionated. The obtained procyanidin fractions have been investigated for their antioxidative potential and analyzed using LC-ESI-FTICR-HRMS to determine individual procyanidins. The optimization showed that the optimal extraction can be conducted using acetone in a concentration of 53% without the addition of an acidifying agent. Strong correlation was observed for procyanidin contents and their antioxidative activity using DPPH, ABTS and FRAP methods. The purified fractions contained 78 individual (65 Type A) procyanidins with the degree of polymerization of up to 9.
This study presents an HPLC-ESI-Q-TOF method for simultaneous quantification of short-chain chlorinated paraffins (SCCPs, C10-13) and an additional characterization of medium-chain chlorinated ...paraffins (MCCPs, C14-17) in oven-baked pastry products (n = 38) and unprocessed pastry dough material (n = 15). Almost 2 times higher SCCP levels were found in the dough material. ΣSCCP concentrations in products ranged from 0.3 ng g
to 23.0 ng g
(mean: 6.3 ng g
), while the results for dough ranged from 5.8 ng g
to 22.8 ng g
(mean: 12.9 ng g
). Regardless of the sample matrix, the most abundant CP homologue groups were hepta- and octa-chlorinated undecanes and dodecanes. The average chlorination degree found in dough samples fell within a range of 55-60% (w/w). Meanwhile, a slight decrease of CP chlorination degree was observed for oven-baked products, in particular for C10-C12 SCCPs, thus indicating that thermal decomposition of CPs occurs even under relatively mild conditions.
The risk assessment of chlorinated paraffins (CPs), chemicals of widespread industrial use, is struggling without standardized analytical methods to obtain reliable occurrence data. Indeed, ...scientists face analytical challenges that hinder the comparability of analytical methods, among them uncontrolled ionization efficiency and lack of quantification standards. In this study, our goal was to investigate potential issues faced when comparing data from different mass spectrometry platforms and quantification methods. First, the injection of the same set of single-chain length standards in three different instrumental mass spectrometry set-ups (liquid chromatography–electrospray-Orbitrap (LC/ESI-HRMS), liquid chromatography–electrospray-time-of-flight (LC/ESI-MS), and gas chromatography–electron capture negative ion-Orbitrap (GC/ECNI-HRMS)) revealed a shift of homologue response patterns even in-between LC/ESI-based set-ups, which was more pronounced for CPs of low chlorination degree. This finding emphasizes the need for a comprehensive description of instrument parameters when publishing occurrence data. Second, the quantification of a data set of samples with four quantification methods showed that quantification at the sum SCCP and MCCP levels presented good comparability, while quantification at the homologue level remained unsatisfactory. In light of those results, we suggest that (i) response pattern comparison should only be performed between similar instrumental set-ups, (ii) experimental chlorination degrees should be used when quantifying according to the %Cl (instead of those provided by the suppliers), and (iii) concentration results should be expressed as the sum of SCCPs and MCCPs primarily, with an indication on the match between samples and quantification standards (for example their chlorine content).
Plants produce anthocyanins to incite the pollination and seed dispersion performed by pigment-attracted animals. These natural blue-to-red-coloured pigments can be used as food colourants and ...antioxidants. For this purpose, microbial bioproduction of anthocyanins has become of industrial interest in recent years. 20 new alleles of anthocyanin production pathway genes were extracted and characterised for protein expression level and stability using a developed single-PCR product gene-entry system for tagged protein synthesis in yeast
S. cerevisiae.
Enzymatic activities of these proteins in the episomally complemented in vivo systems were compared by HPLC-MS analysis. Results show that the codon optimisation of the anthocyanin pathway genes is not essential for the effective heterologous expression in yeast. Elevating the cellular abundance of CHS and F3H enzymes can increase anthocyanidin production from supplemented precursors. New alleles
Vm
F3Hv1 and
Vu
CHS were shown to have the best performance in the analysed system. System complementation with flavonoid 3′,5′-hydroxylase substantially increases total anthocyanidin production. The described single-entry yeast episomal complementation system is a convenient and rapid tool for the complex evaluation of new alleles in vivo.
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