•A low-sample-volume SPE-HPLC–MS/MS method was developed.•Antibiotics, metabolites and tracers were separated by RP and HILIC.•The method was established for long-term monitoring of an urban sewage ...treatment plant.•Recovery rates ranged between 51% and 111%.•The method is simple, fast and easily applicable to other sewage monitorings.
A rapid analytical method was developed for the application of a long-term monitoring (>one year) of the most prescribed and often in hospitals used antibiotics in diverse wastewaters of an urban sewage treatment plant (STP). Additionally to the selected multi-class antibiotics amoxicillin, penicillin V and piperacillin (penicillins), cefotaxime and cefuroxime (cephalosporins), azithromycin, clarithromycin and roxithromycin (macrolids), ciprofloxacin and levofloxacin–ofloxacin (fluoroquinolones), clindamycin (lincosamide), doxycycline (tetracycline), sulfamethoxazole (sulfonamide) and trimethoprim (dihydrofolate reductase inhibitor), the bioactive metabolite clindamycin-sulfoxide, the reserve antibiotic vancomycin (glycopeptide) and as tracer of the STP the anticonvulsant carbamazepine and the antifungal fluconazole were involved. The analytical method combines a low-sample-volume solid phase extraction (SPE), followed by a chromatographic separation using a reversed phase (RP) and hydrophilic interaction liquid chromatography (HILIC) technique, respectively, coupled to a triple quadrupole mass spectrometer. Detection was performed with multiple reaction monitoring (MRM) measured with positive electrospray ionization (ESI+). The extraction efficiency of different SPE cartridges and optimized pH-values of the preparation procedure were tested. Finally, the extraction of antibiotics was realized with the Oasis HLB cartridge and a pH adjustment at 3.5. An external calibration curve in diluted blank urine was used for quality control of the sample set of daily composite samples of the STP for the duration of one year monitoring. The squared coefficient of determination (r2) in the concentration range (20–20,000ng/L or 100–100,000ng/L) of the calibration curves for the method was higher than 0.99 for all determined substances. The limit of quantification (LoQ) ranged between 0.8ng/L (azithromycin) and 245.1ng/L (vancomycin). Furthermore, a standard addition was used for quantification in wastewater samples. The process efficiencies ranged from 20% (doxycycline) to 134% (cefuroxime) in influent samples and from 31% (doxycycline) to 171% (cefuroxime) in effluent samples of the STP. All selected substances have been found in wastewater samples. Cefuroxime, doxycycline, levofloxacin, piperacillin, sulfamethoxazole and carbamazepine showed highest concentrations up to 6.2μg/L.
•A new method was developed to separate and determine oxypeucedanin enantiomers.•Stereoselective differences were found in Angelica dahuricae Radix and rat plasma.•(+)-oxypeucedanin was present at a ...relative high level in Angelica dahuricae Radix.•(−)-oxypeucedanin showed higher plasma concentration in stereoselectivity.
In this study, a new enantioseparation method was established for the quantitative analysis of the oxypeucedanin enantiomers by using cellulose tris(3,5-dichlorophenyl carbamate) stationary phase column Chiralpak IC. For this method, enantiomeric separation of oxypeucedanin was achieved with the mobile phase consisting of acetonitrile-water (60:40, v/v) at a flow rate of 0.5 mL/min by changing the type and proportion of mobile phase. And the quantitative determination of racemic oxypeucedanin in Angelica Dahuricae Radix (in vitro) and rat plasma (in vivo) were performed on above-mentioned condition by High PerformanceLiquid Chromatography combined with diode arrangement detector (HPLC-DAD) and mass spectrometry (HPLC-MS/MS). The precision, repeatability, stability, recovery were within the acceptance criteria. And the method was validated in the concentration range of 1-400 μg/mL for the two enantiomers in vitro and 0.2–600 ng/mL in vivo. After validation, the established method was successfully applied to the stereoselective analysis of racemic oxypeucedanin in Angelica dahurica from different regions and the stereoselective pharmacokinetic investigation in rat. Results showed that the (+)-oxypeucedanin was at a relative high level in Angelica dahuricae Radix and (−)-oxypeucedanin performed a higher plasma concentration, which demonstrated the difference of oxypeucedanin enantiomers both in vitro and in vivo.
Display omitted
•A multi-analytical approach based on four different analytical methods was used for the first time.•The approach is very effective in characterizing organic materials used in the ...past.•The ointment bases of historical ointment remains from the 18th century were identified.•Contemporary pharmacists often modified the formulations to suit their needs.
A multi-analytical approach based on four different analytical methods was used for the first time to study six historical ointments from the 18th century belonging to the baroque pharmacy of Capuchin Monastery in Hradčany (Prague, Czech Republic) in order to gain information on the ointment formulation, the presence of active substances, and also possible chemical modification deriving from the procedures used for their preparation. All ointments were initially characterized by gas chromatography/mass spectrometry following saponification, extraction and derivatization to identify the main classes of ingredients. The volatile organic compounds emitted by the ointments were then characterized by gas chromatographic analysis following solid-phase microextraction, providing complementary information on the possible more volatile and active ingredients present in the ointments. Finally, the botanical/animal origin of triacylglycerols was investigated by liquid chromatography-high resolution mass spectrometry, while the presence of beeswax was proved by flow injection analysis. The results obtained were used to hypothesize the probable original medical purpose of the ointments by comparing the results with historical recipes and the period literature. The use of this comprehensive multi-analytical approach allowed us to contribute to the knowledge of ancient ointments and to obtain information on the alteration of the chemical compounds in the ointment formulations.
The glucosinolates (GSLs) is a well-defined group of plant metabolites characterized by having an S-β-d-glucopyrano unit anomerically connected to an O-sulfated (Z)-thiohydroximate function. After ...enzymatic hydrolysis, the sulfated aglucone can undergo rearrangement to an isothiocyanate, or form a nitrile or other products. The number of GSLs known from plants, satisfactorily characterized by modern spectroscopic methods (NMR and MS) by mid-2018, is 88. In addition, a group of partially characterized structures with highly variable evidence counts for approximately a further 49. This means that the total number of characterized GSLs from plants is somewhere between 88 and 137. The diversity of GSLs in plants is critically reviewed here, resulting in significant discrepancies with previous reviews. In general, the well-characterized GSLs show resemblance to C-skeletons of the amino acids Ala, Val, Leu, Trp, Ile, Phe/Tyr and Met, or to homologs of Ile, Phe/Tyr or Met. Insufficiently characterized, still hypothetic GSLs include straight-chain alkyl GSLs and chain-elongated GSLs derived from Leu. Additional reports (since 2011) of insufficiently characterized GSLs are reviewed. Usually the crucial missing information is correctly interpreted NMR, which is the most effective tool for GSL identification. Hence, modern use of NMR for GSL identification is also reviewed and exemplified. Apart from isolation, GSLs may be obtained by organic synthesis, allowing isotopically labeled GSLs and any kind of side chain. Enzymatic turnover of GSLs in plants depends on a considerable number of enzymes and other protein factors and furthermore depends on GSL structure. Identification of GSLs must be presented transparently and live up to standard requirements in natural product chemistry. Unfortunately, many recent reports fail in these respects, including reports based on chromatography hyphenated to MS. In particular, the possibility of isomers and isobaric structures is frequently ignored. Recent reports are re-evaluated and interpreted as evidence of the existence of “isoGSLs”, i.e. non-GSL isomers of GSLs in plants. For GSL analysis, also with MS-detection, we stress the importance of using authentic standards.
Display omitted
•List of glucosinolates characterized satisfactorily using NMR and MS data, in total 88.•Selected glucosinolate structures deduced indirectly, in total 47.•Review of glucosinolate nomenclature, chemistry, organic synthesis and plant biochemistry.•Review of glucosinolate identification and guidelines for scientific reporting.
•Fe3O4@SiO2@MOF core–shell magnetic microspheres were prepared as MSPE sorbent.•Fe3O4@SiO2@MOF core–shell magnetic microspheres were used for MSPE of polar analytes.•Fe3O4@SiO2@MOF core–shell ...magnetic microspheres achieved high extraction efficiency.
Fe3O4@SiO2@UiO-66 core–shell magnetic microspheres were synthesized and characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectrometry, vibrating sample magnetometry, nitrogen adsorption porosimetry and zeta potential analyzer. The synthesized Fe3O4@SiO2@UiO-66 microspheres were first used for magnetic solid-phase extraction (MSPE) of domoic acid (DA) in shellfish samples. Combined with high performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS), a fast, simple and sensitive method for the determination of DA was established successfully. Under the optimized conditions, the developed method showed short analysis time, good linearity (r2=0.9990), low limit of detection (1.45pgmL−1; S/N=3:1), low limit of quantification (4.82pgmL−1; S/N=10:1), and good extraction repeatability (RSD≤5.0%; n=5). Real shellfish samples were processed using the developed method, and trace level of DA was detected. The results demonstrate that Fe3O4@SiO2@UiO-66 core–shell magnetic microspheres are the promising sorbents for rapid and efficient extraction of polar analytes from complex biological samples.
Non‐small‐cell lung carcinomas (NSCLC) is the most common type of lung cancer and it has a poor prognosis, because overall survival after 5 years is 20–25% for all stages. Thus, it is extremely ...important to increase the survival rate in the early stages NSCLC by focusing on novel screening tests of cancer identifying specific biomarkers expression associated with a more accurate tumor staging and patient prognosis. In this study, we focused our attention on quantitative proteomics of three heavily glycosylated serum proteins: AMBP, α2 macroglobulin, and SERPINA1. In particular, we analyzed serum samples from 20 NSCLC lung adenocarcinoma cancer patients in early and advanced stages, and 10 healthy donors to obtain a relative quantification through the MRM analysis of these proteins that have shown to be markers of cancer development and progression. AMBP, α2 macroglobulin, and SERPINA1 were chosen because all of them possess endopeptidase inhibitor activity and play key roles in cancer. We observe a variation in the expression of these proteins linked to the stage of the disease. Therefore, we believe that proteins like α2 macroglobulin, αmicroglobulin/bikunin, and SERPINA1 could be useful biomarkers for early detection of lung cancer and in monitoring its evolution.
It is extremely important to increase the survival rate in the early stages non‐small‐cell lung carcinomas by focusing on novel screening tests of cancer identifying specific biomarkers expression associated with a more accurate tumor staging, and patient prognosis. We observe a variation in the expression of these proteins linked to the stage of the disease. Therefore, we believe that proteins like α2 macroglobulin, α microglobulin/bikunin, and SERPINA1 could be useful biomarkers for early detection of lung cancer and in monitoring its evolution.
Pressurized liquid extraction (PLE) has been used for the first time in this work to extract phenolic compounds from Goji berries according to a multilevel factorial design using response surface ...methodology. The global yield (% w/dw, weight/dry‐weight), total phenolic content (TPC), total flavonoid (TF) and antioxidant activity (determined via ABTS assay, expressed as TEAC value) were used as response variables to study the effects of temperature (50–180°C) and green solvent composition (mixtures of ethanol/water). Phenolic compounds characterization was performed by high performance liquid chromatography–diode array detector–tandem mass spectrometry (HPLC‐DAD‐MS/MS). The optimum PLE conditions predicted by the model were as follows: 180°C and 86% ethanol in water with a good desirability value of 0.815. The predicted conditions were confirmed experimentally and once the experimental design was validated for commercial fruit samples, the PLE extraction of phenolic compounds from three different varieties of fruit samples (Selvatico mongolo, Bigol, and Polonia) was performed. Nine phenolic compounds were tentatively identified in these extracts, including phenolic acids and their derivatives, and flavonols. The optimized PLE conditions were compared to a conventional solid‐liquid extraction, demonstrating that PLE is a useful alternative to extract phenolic compounds from Goji berry.
•A magnetic Fe3O4@LABSA-LDH@ZIF-8 nanocomposites were synthesized for the first time.•The Fe3O4@LABSA-LDH@ZIF-8 has a strong affinity for HAAs.•Fe3O4@LABSA-LDH@ZIF-8 has excellent adsorption property ...for HAAs in food substrates.•The current MSPE-HPLC-MS/MS was sensitive, accurate, and practical for detecting HAAs.
In this research, a novel magnetic nanocomposite (Fe3O4@Zn/Al-LABSA-LDH/ZIF-8) was synthesized using Fe3O4 as the magnetic core, layered double hydroxide (LDH) with linear alkylbenzene sulfonic acid (LABSA) intercalation and zeolitic imidazolate framework-8 (ZIF-8) as the shell. Benefiting from the intercalation of LABSA into LDH combined with ZIF-8, the multiple interactions, including π-π stacking, hydrogen bonding, and electrostatic interactions, conferred high selectivity and good extraction capability to the material towards heterocyclic aromatic amines (HAAs). Fe3O4@Zn/Al-LABSA-LDH@ZIF-8 was used as an adsorbent for magnetic solid-phase extraction (MSPE) to enrich HAAs in thermally processed meat samples, followed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) detection. The method exhibited a low detection limit (0.021–0.221 ng/g), good linearity (R2 ≥ 0.9999), high precision (RSD < 7.2 %), and satisfactory sample recovery (89.7 % -107.5 %). This research provides a promising approach for developing novel adsorbents in sample preparation and improving analytical performance.
Plants in natural environments are increasingly being subjected to a combination of abiotic stresses, such as drought and warming, in many regions. The effects of each stress and the combination of ...stresses on the functioning of shoots and roots have been studied extensively, but little is known about the simultaneous metabolome responses of the different organs of the plant to different stresses acting at once.
We studied the shift in metabolism and elemental composition of shoots and roots of two perennial grasses, Holcus lanatus and Alopecurus pratensis, in response to simultaneous drought and warming.
These species responded differently to individual and simultaneous stresses. These responses were even opposite in roots and shoots. In plants exposed to simultaneous drought and warming, terpenes, catechin and indole acetic acid accumulated in shoots, whereas amino acids, quinic acid, nitrogenous bases, the osmoprotectants choline and glycine betaine, and elements involved in growth (nitrogen, phosphorus and potassium) accumulated in roots. Under drought, warming further increased the allocation of primary metabolic activity to roots and changed the composition of secondary metabolites in shoots.
These results highlight the plasticity of plant metabolomes and stoichiometry, and the different complementary responses of shoots and roots to complex environmental conditions.
High molecular weight PAHs (HMW PAHs) are dangerous pollutants widely distributed in the environment. The use of microorganisms represents an important tool for HMW PAHs bioremediation, so, the ...understanding of their biochemical pathways facilitates the development of biodegradation strategies. For this reason, the potential role of species of microalgae, bacteria, and microalga-bacteria consortia in the degradation of HMW PAHs is discussed. The identification of their metabolites, mostly by GC–MS and LC-MS, allows a better approach to the enzymes involved in the key steps of the metabolic pathways of HMW PAHs biodegradation. So, this review intends to address the proteomic research on enzyme activities and their involvement in regulating essential biochemical functions that help bacteria and microalgae in the biodegradation processes of HMW PAHs. It is noteworthy that, given that to the best of our knowledge, this is the first review focused on the mass spectrometry identification of the HMW PAHs metabolites; whereby and due to the great concern of the presence of HMW PAHs in the environment, this material could help the urgency of developing new bioremediation methods. The elucidation of the metabolic pathways of persistent pollutant degrading microorganisms should lead to a better knowledge of the enzymes involved, which could contribute to a very ecological route to the control of environmental contamination in the future.
Display omitted
•Compilation of HMW PAHs degradative microalgae, bacteria, and consortia species•Metabolite identification by GC/LC-MS is helpful to elucidate degradation pathways.•Enzymes related to the key metabolites during HMW PAHs degradation processes•Degradative enzymes as potential promising tools in bioremediation strategies
PDF
