Solid-phase Extraction Cartridges Research Articles

Qualitative Analysis of Daphnane Diterpenoids in Various Parts of Daphne pontica L. by UHPLC-Q-Exactive-Orbitrap MS.

Daphne pontica L. is an evergreen shrub that is recorded as an anti-diarrheic plant in Turkish folk medicine. Previous studies on D. pontica have reported, albeit slightly, the isolation of daphnane diterpenoids, but no systematic phytochemical analysis of daphnane diterpenoids has been conducted. This study aimed to comprehensively investigate daphnane diterpenoids in the extracts from the different parts (stems, leaves, and fruits) of D. pontica. An ultra-high-performance liquid chromatography coupled with Q-Exactive hybrid quadrupole Orbitrap mass spectrometer (UHPLC-Q-Exactive-Orbitrap MS) was used for the qualitative analysis of D. pontica. The stems, leaves, and fruits of D. pontica were extracted with diethyl ether. Each extract was then pretreated by a solid phase extraction cartridge and subjected to LC-MS/MS analysis. Detected daphnane diterpenoids were tentatively identified by comparison with an in-house daphnane library, and their chemical structures were estimated in detail by MS/MS fragmentation evaluation. A total of 33 kinds of daphnanes were identified from the different parts of D. pontica, and were classified into three subtypes: daphnane orthoester, polyhydroxy daphnane, and macrocyclic daphnane orthoester. Among them, six daphnanes were postulated to be previously unreported compounds based on MS/MS fragmentation elucidation. Furthermore, the three plant parts showed similar daphnane diterpenoid profiles, with the stems containing the most abundant daphnane diterpenoids. This is the first study to perform qualitative analysis of daphnane diterpenoids systematically and comprehensively in different parts of D. pontica. The results revealed that D. pontica is a plant resource rich in a variety of daphnane diterpenoids.

Comparative Analysis of Pharmaceutical Persistence in Canadian Wastewater Treatment Plants Utilizing Molecularly Imprinted Polymers and Commercial Solid Phase Extraction Sorbents

In this study, the performances of a synthesized Molecularly Imprinted Polymer (MIP) and a commercial Solid Phase Extraction (SPE) cartridge were compared in terms of the removal efficiency and quantification of pharmaceutical compounds in wastewater samples. Concentration analysis of Emtricitabine, Tenofovir, Naproxen, Diclofenac, Ibuprofen, and Efavirenz was conducted in influent, primary effluent, secondary effluent, and post-chlorination water samples using liquid chromatography-UV detection. Regressions analysis revealed high linearity (R2 values from 0.9980 to 0.9999) for the compounds, alongside recoveries ranging from 90.9% to 100%. The method detection limits (MDLs) were also determined. Removal efficiencies were computed, with Naproxen and Ibuprofen demonstrating complete removal (100%), while other compounds displayed different of removal efficiency levels. The MIP was found to perform slightly better than traditional SPE cartridges in terms of selectivity, efficiency, and overall performance. This study provides valuable insights into the concentrations of target compounds at various treatment stages, emphasizing the importance of choosing extraction cartridges in wastewater treatment processes.

A guidance for the enrichment of micropollutants from wastewater by solid-phase extraction before bioanalytical assessment

BackgroundWastewater can contain a complex mixture of organic micropollutants, with both chemical analysis and effect-based methods needed to identify relevant micropollutants and detect mixture effects. Solid-phase extraction (SPE) is commonly used to enrich micropollutants prior to analysis. While the recovery and stability of individual micropollutants by SPE has been well studied, few studies have optimized SPE for effect-based methods. The aim of the current study was to develop and evaluate two standard operating procedures (SOPs) for the enrichment of micropollutants in preparation for chemical analysis and bioanalysis, one covering a broad range of chemicals and the other selective for estrogenic chemicals.ResultsPristine surface water spiked with > 600 micropollutants was used to develop a generic extraction method for micropollutants with a wide range of physiochemical properties, while water spiked with estrogenic chemicals was used to identify a selective extraction method. Three different SPE sorbents were tested, with recoveries of individual chemicals and effect in assays indicative of mutagenicity, estrogenic activity, and fish embryo toxicity assessed. The sorbent HRX at pH 7 was selected for the generic extraction method as it showed the best recovery of both individual chemicals and effect in the bioassays. The sorbent HLB at pH 3 showed optimal recovery of estrogenic chemicals and estrogenic activity. The two optimal SPE methods were applied to spiked and unspiked wastewater effluents, with the concentrations of detected chemicals and observed effects similar to those of previous studies. The long-term storage of both extracts and SPE cartridges for estrogens and estrogenic activity after extraction with the HRX and HLB methods were evaluated, with estrogenic effectiveness close to 100% after 112 days when HLB was used.ConclusionsHRX is recommended for generic extraction, while HLB is optimal for the selective extraction of estrogenic micropollutants. However, if a laboratory only wants to use a single SPE sorbent, HLB can be used for both generic and selective extraction as it yielded similar chemical and effect recovery as HRX for a wide range of micropollutants. This paper is supplemented by the final SOP that includes a variant for generic extraction and one for the extraction of estrogenic chemicals.

Determination and evaluation of canthaxanthin and β-apo-8’-carotenoid ethyl ester in chicken eggs and meat in Tianjin

Canthaxanthin and β-apo-8’-carotenoid ethyl ester are widely used as feed additives in poultry feed for enhancing the color of poultry products. The excessive intake of the two colorants can cause health damage. According to the European Food Safety Authority (EFSA), the acceptable daily intake (ADI) of canthaxanthin and β-apo-8’-carotenoid ethyl ester are 0.03 mg/kg·bw and 0.015 mg/kg·bw, respectively. Ultra-high-performance liquid chromatography-diode array detector (UPLC-DAD) was used to determine two colorants in chicken eggs and meat. A PRiME HLB solid-phase extraction cartridge was used to extract and clean-up the sample. BEH C18 column was used as the separation column, with water containing 0.1% formic acid and acetonitrile as the mobile phase. The limit of detection (LOD) was 0.05 mg/kg, and the limit of quantification (LOQ) was 0.1 mg/kg. The recoveries were between 90% and 104%. The daily intake of two colorants in chicken eggs and meat was evaluated based on the detection data, food consumption data and weight data of the population. The mean estimated daily intake (EDI) values of canthaxanthin through chicken eggs and meat were 1.09 µg/(kg·bw·d) and 0.013 µg/(kg·bw·d), respectively. The mean EDI value of β-apo-8’-carotenoid ethyl ester through eggs was 0.44 µg/(kg·bw·d). The results showed that eggs were the main contributor to the daily intake of two colorants. The mean hazard quotients (HQ) values of two colorants through chicken eggs and meat was within a safe range.

Systematization of a toxicity screening method based on a combination of chemical analysis and the delayed fluorescence algal growth inhibition test for use in emergency environmental surveys.

In recent years, heavy rainfall disasters linked to climate change have become more frequent, raising concerns about the release of chemicals stored in factories. Assessing chemical contamination during such emergencies therefore necessitates the development of a quick and easy method for evaluating hazardous contaminants in combination with toxicity testing. This study proposes a "toxicity screening" method that combines biological response testing and chemical analysis to systematically evaluate hazardous contaminants in emergency situations. The toxicity screening method evaluates the water quality in three steps, including water quality measurements and a delayed fluorescence (DF) assay, metal content measurements and a DF assay, and targeted screening analysis and a DF assay. The efficacy of this method was tested using industrial wastewater from 14 locations. Seven of the samples were non-toxic, while the other seven samples were toxic, displaying no observed effect concentration (NOEC) values ranging from 0.625 to 20%. Two toxic samples in the first phase possessed high total chlorine concentrations (0.4mg L-1) and conductivities (2200 mS m-1), indicating that the main sources of toxicity were residual chlorine and a high salt concentration. In the second phase, metal content analysis identified metals as the toxicity cause in four samples. In the third phase, the organic contaminants were analyzed, and tri-n-octyl phosphate (TNOP) was detected at a concentration of 0.00027mg L-1. The results of solid-phase extraction experiments and exposure tests with TNOP alone indicated that the contribution of TNOP to the toxicity was negligible and that chemicals not adsorbed on the solid-phase extraction cartridges were the cause of toxicity. The proposed method can therefore be considered effective for disaster-related water quality assessment, delivering results within 12days.

Assessment of Polycyclic Aromatic Hydrocarbons in Urban Water Bodies: A Study of Rivers and Lakes in Dhaka, Bangladesh

Polycyclic aromatic hydrocarbons (PAHs) pose significant environmental and health risks due to their toxic properties,making their assessment in urban water bodies crucial. This study aims to evaluate the presence of three notable PAHs—anthracene, fluoranthene, and benzo[a]pyrene—in the surface water of three rivers (Buriganga, Meghna, and Turag) andtwo lakes (Hatirjheel and Gulshan) in Dhaka, Bangladesh. High-performance liquid chromatography with fluorescencedetector (HPLC-FD) was employed and validated for PAH determination, using solid phase extraction (SPE) withpreconditioned C-18 SPE cartridge for sample extraction. Calibration showed excellent linearity with correlation coefficient (R²) ≥ 0.999. The limits of detection (LODs) were 200 ng/L for anthracene and 0.63 ng/L for both fluoranthene and benzo[a]pyrene, with corresponding limits of quantification (LOQs) of 660 ng/L and 2.08 ng/L, respectively. Percent recovery was 91.38% for anthracene, 85.49% for fluoranthene, and 95.72% for benzo[a]pyrene, with relative standard deviations (RSD) of 5.27, 17.55 and 2.84%, respectively. Most water samples had PAH levels below detection limits (bdl) such as anthracene (bdl-1789.57 ng/L), fluoranthene (bdl-1309.23 ng/L), and benzo[a]pyrene (bdl-25.17 ng/L), and the detected concentrations were significantly lower than WHO and USEPA guideline values. This indicates a relatively low level of PAHs contamination in the studied water bodies. Dhaka Univ. J. Sci. 72(2): 75-83, 2024 (July)

"One Method to Label Them All": A Single Fully Automated Protocol for GMP-Compliant 68Ga Radiolabeling of PSMA-11, Transposable to PSMA-I&T and PSMA-617.

Prostate-specific membrane antigen (PSMA) is an ideal target for molecular imaging and targeted radionuclide therapy in prostate cancer. Consequently, various PSMA ligands were developed. Some of these molecules are functionalized with a chelator that can host radiometals, such as 68Ga for PET imaging. The 68Ga radiolabeling step benefits from process automation, making it more robust and reducing radiation exposure. To design a single automated radiolabeling protocol for the GMP-compliant preparation of [68Ga]Ga-PSMA-11, transposable to the production of [68Ga]Ga-PSMA-617 and [68Ga]Ga-PSMA-I&T. A GAIA® synthesis module and a GALLIAD® generator were used. Radio-TLC and radio-HPLC methods were validated for radiochemical purity (RCP) determination. Three [68Ga]Ga-PSMA-11 validation batches were produced and thoroughly tested for appearance and pH, radionuclide identity and purity, RCP, stability, residual solvent and sterility. Minimal modifications were made to the reagents and disposables for optimal application to other PSMA ligands. [68Ga]Ga-PSMA-11 for clinical application was produced in 27 min. The 3 validation batches met the quality criteria expected by the European Pharmacopoeia to allow routine production. For optimal transposition to PSMA-617, the solid phase extraction cartridge was changed to improve purification of the radiolabeled product. For application to PSMA-I&T, the buffer solution initially used was replaced by HEPES 2.7 M to achieve good radiochemical yields. Residual HEPES content was checked in the final product and was below the Ph. Eur. threshold. A single automated radiolabeling method on the GAIA® module was developed and implemented for 68Ga radiolabeling of 3 PSMA ligands, with slight adjustments for each molecule.

Determination of fluoroquinolones residues in bean sprouts using covalent organic framework based solid-phase extraction coupled with UHPLC-MS/MS

A solid-phase extraction (SPE) method using three-dimensional covalent organic framework (COFs) coupled with ultra-high performance liquid chromatography-mass spectrometry was developed for the detection of 13 fluoroquinolones (FQs) in bean sprout samples. Critical extraction parameters influencing SPE efficiency were optimized and matrix-matched standard curves were used to eliminate matrix effects and validate the proposed method. The analytical method proved to have good linearity in the concentration range of 1.0–100 μg L–1 with correlation coefficients of r≥0.9995. The limits of detection were 0.10–0.45 μg kg–1, whereas the limits of quantification were 0.34–1.51 μg kg–1. The recoveries ranged from 92.7 % to 105 % with satisfactory precision (< 4.82 %). The COFs-packed SPE cartridge maintained recovery efficiency for the target FQs over five reuse cycles. The adsorption selectivity was mainly attributed to π–π interactions, hydrogen bonding, and electrostatic attraction between FQs and the adsorbent. Analysis of actual samples revealed the presence of enrofloxacin, ciprofloxacin, and norfloxacin in three batches of bean sprout samples. These results highlight the importance of monitoring antibiotics residues in bean sprouts.

Distribution and seasonal variations of perfluoroalkyl substances (PFAS) in streams within the Changwon region

This study investigates the distribution and seasonal variations of Poly- and Perfluoroalkyl Substances (PFAS) concentrations in local streams within the Changwon area, aiming to quantify the total PFAS load entering Masan Bay. Using solid-phase extraction (SPE) cartridges for pretreatment, we analyzed 36 types of Perfluorinated carboxylic acids (PFCAs), Perfluorinated sulfonates (PFSAs), and precursor compounds via liquid chromatography-high resolution mass spectrometry (LC-HRMS). The study observed varying concentration levels across different streams, with notable detections of Perfluorohexanoic acid (PFHxA), Perfluorooctanoic acid (PFOA), Perfluorobutanesulfonic acid (PFBS), Perfluoropentanoic acid (PFPeA), and Perfluoroheptanoic acid (PFHpA) at quantifiable levels. Except for the Sogye Stream (SGC), PFCA-based compounds comprised over 50% of the total PFAS detected, predominantly featuring shorter-chain compounds with fewer than eight carbon atoms. Seasonal trends indicated that PFAS concentrations were lowest during the high rainfall period in summer and peaked in winter and spring. The Nam Stream (NC) contributed the highest PFAS inflow into Masan Bay, attributed to its elevated flow rates, while Sum B had high concentrations but lower emissions due to its limited flow. The total annual PFAS discharge was estimated at 1.9 kg. These findings highlight the urgent need for targeted management and comprehensive countermeasures to protect environmental health.

Validated UPLC-MS/MS method for quantification of melatonin receptor agonists and dual orexin receptor antagonists in human plasma and breast milk: Application to quantify suvorexant and lemborexant in clinical samples

Pharmaceutical care is important for mental health during the perinatal period, which is often characterized by insomnia. In recent years, prescriptions of melatonin receptor agonists (MRAs) and dual orexin receptor antagonists (DORAs) for insomnia have increased; however, their use during the perinatal period has scarcely been reported. In the present study, we developed a UPLC-MS/MS method for the quantification of ramelteon, its metabolite M-II, suvorexant, and lemborexant in human plasma and breast milk to accumulate information on the safety and transfer of MRAs and DORAs into breast milk. Samples of MRAs (ramelteon and M-II) in plasma and breast milk were prepared using liquid–liquid extraction (LLE) with ethyl acetate. For DORAs (suvorexant and lemborexant), LLE with ethyl acetate was applied to plasma samples. For breast milk samples, significant ion suppression was observed for LLE with ethyl acetate. Solid-phase extraction (SPE) cartridges capable of removing phospholipids improved the matrix effects. Finally, protein precipitation with methanol and an SPE cartridge, InertSep® Phospholipid Remover, were selected for breast milk sample preparation. An ACQUITY UPLC BEH C18 column was used for analyte separation. MRAs and DORAs were eluted using isocratic and gradient elution, respectively, and analyzed using electrospray ionization in the positive mode with multiple reaction monitoring. The range of calibration curve for MRAs and DORAs was 0.1–25 and 0.5–50 ng/ml, respectively. Both the plasma and breast milk samples exhibited good linearity over this range. The method was validated by evaluating its accuracy and precision, matrix effect, recovery, carry-over, stability, and dilution integrity. The validated method was successfully applied to clinical samples donated by breastfeeding women and the milk/plasma (M/P) ratio and relative infant dose (RID) of lemborexant (one case) and suvorexant (two cases) were estimated. The M/P ratio of lemborexant was <1, and the RID was 1.05 %. The M/P ratio of suvorexant was <0.1, and RID was 0.11–0.20 %. This method will be useful for future studies evaluating the safety of these drugs during breastfeeding.

Natural deep eutectic solvent for the simultaneous derivatization and microextraction of isoniazid from human plasma

BackgroundPersonalized medicine is a rapidly revolving field that offers new opportunities for tailoring disease treatment to individual patients. The main idea behind this approach is to carefully select safe and effective medications and treatment plant based on each patient's unique pharmacokinetic profile. Isoniazid is a first-line anti-tuberculosis drug that has interindividual variability in its metabolic processing, leading to significant differences in plasma concentrations among patients receiving equivalent doses. This variability necessitates the creation of individualized treatment regimens as part of personalized medicine to achieve more effective therapy. ResultsIn this work, a deep eutectic solvent-based liquid-liquid microextraction approach for the separation and determination of isoniazid in human plasma by high-performance liquid chromatography with UV–Vis detection was developed for the first time. A new natural deep eutectic solvent based on thymol as a hydrogen bond donor and 4-methoxybenzaldehyde as a hydrogen bond acceptor was proposed as the extraction solvent. The developed microextraction procedure assumed two simultaneous processes during the mixing of the sample and extraction solvent: the derivatization of the polar analyte in the presence of 4-methoxybenzaldehyde (component of the natural deep eutectic solvent) with the formation of a hydrophobic Schiff base (1); mass transfer of the Schiff base from the sample phase to the extraction solvent phase (2). Under optimal conditions, the limits of detection and quantification were 20 and 60 μg L−1, respectively. The RSD value was <10 %, the extraction recovery was 95 %. SignificanceIn this work, the possibility of isoniazid derivatization in the natural deep eutectic solvent phase with the formation of the Schiff base was presented for the first time. The approach provided the separation and preconcentration of polar isoniazid without the use of expensive derivatization agents and solid-phase extraction cartridges. The formation of the Schiff base was confirmed by mass spectrometry.

Air-surface exchange of halomethoxybenzenes in a Swedish subarctic catchment

Halomethoxybenzenes (HMBs) and related halomethoxyphenols are produced naturally in the marine and terrestrial environment and some also have anthropogenic origins. They are relatively volatile and water soluble and undergo atmospheric exchange with water bodies and soil. Here we report air-surface exchange of HMB compounds brominated anisoles and chlorinated dimethoxybenzenes in a Subarctic lake and catchment in Sweden during September 2022. HMBs were isolated from water on solid-phase extraction cartridges and from ground litter/soil by solvent extraction and determined by capillary gas chromatography - quadrupole mass spectrometry. Identified compounds in lake and stream water in the 10–100 pg L−1 range were 1,2,4,5-tetrachloro-3,6-dimethoxybenzene (DAME) > 2,4-dibromoanisole (DiBA) ≥ 2,4,6-tribromoanisole (TriBA) > 1,2,3,4-tetrachloro-5,6-dimethoxybenzene (tetrachloroveratrole, TeCV). DAME and the related compound 2,3,5,6-tetrachloro-4-methoxyphenol (DA) are reported in Subarctic litter/soil in the range 0.005–1.1 mg kg−1 dry weight (dw), whereas DiBA and TriBA were not detected in any litter/soil sample and TeCV in only one. Exchanges were assessed from concentrations in water and soil, air concentrations from a monitoring station at Pallas, Finland, and the physicochemical properties of the HMBs. Fluxes to and from the lake were estimated using the two-film gas exchange model. Net loadings (deposition minus volatilization) for the month of September were − 23, −15 and − 68 g for DiBA, TriBA and DAME, respectively, which amounted to about 4–7 % of the estimated lake inventory. An exchange assessment for DAME from litter/soil showed significant net volatilization at five sites, net deposition at one site and near-equilibrium at one site. The Torneträsk catchment appeared close to steady state with respect to HMB exchange during September 2022. The situation could be different during the warmer and colder seasons, and extending the study to cover these periods is a suggested next step.

Comprehensive methodology for semi-volatile organic compound determination in ambient air with emphasis on polycyclic aromatic hydrocarbons analysis by GC–MS/MS

Polycyclic aromatic hydrocarbons are air pollutants that affect the human health and the environment, and their accurate determination in outdoor and indoor environments is important. This study presents a methodology for sampling and analysis of semi-volatile compounds in ambient air with emphasis on the polycyclic aromatic hydrocarbons, collected with low-volume pumps (4.8 m3) in unconditioned solid phase extraction cartridges (Isolute ENV+). Sampling in SPE cartridges with low-volume pumps allows the collection of both gas and particulate phase compounds in indoor as well as outdoor environments, and reduces the number of extraction steps required as well as the solvent volume used for extraction. Analysis of the 16 US-EPA priority PAHs after extraction was conducted by GC–MS/MS with recoveries of the PAHs 40–118 %. No breakthrough was detected during sampling. Moreover, the methodology includes storage test to assess the conservation of PAHs in the SPE cartridges in heat-sealable Kapac bags; simulating transport from sampling sites to laboratory, and storage under room, cold and frozen conditions at different time-intervals, up to 3 months after sampling. The results showed that concentration levels remained constant across various storage time intervals and temperatures, with naphthalene and acenaphthylene being the only exceptions, showing high blank levels for the first and losses at room temperature for the later. The method quantification limits, including sampling, storage and GC–MS/MS analysis ranged from 2000 pg m-3 for naphthalene and 300 pg m-3 for phenanthrene to less than 20.0 pg m-3 for higher molecular and less volatile PAHs, such as benzo[a]pyrene (LOQ = 8.0 pg m-3). The feasibility of the method was tested by sampling indoors under urban background air conditions, showing individual PAH concentrations 4 to 10 times higher than their method quantification limits.

HPLC analysis of synthetic dyes in wastewater

The analysis of synthetic dyes in wastewater is an urgent task of modern analytical chemistry since an increased content of dyes in wastewater can have an adverse effect on the environment. Reverse phase high performance liquid chromatography (RP HPLC) is often used to control the content of dyes in various objects, which makes it possible to reliably determine the content of specified substances. The purpose of this work was to create and evaluate the metrological characteristics for the method of analysis of synthetic dyes in the industrial wastewater with a high content of inorganic salts. The chromatographic system used in this work was a Knauer high-pressure pump. The separation was performed on a Kromasil 100-5-C18 (w) reverse phase column (4.6 × 250 mm) in the gradient elution mode. Acetonitrile and ammonium acetate solution were used as the mobile phase. Synthetic dyes were detected on an Azura diode array detector. The paper presents the results of concentrating 10 synthetic dyes on commercially available solid phase extraction cartridges that were suitable for working with aqueous solutions with a high content of inorganic salts. For each substance, the degree of concentration from distilled and model wastewater was calculated, which varied from 2 to 98%. Among the analysed cartridges, the highest degree of concentration during operation in conditions close to real wastewater was shown by the Diapak P cartridge, at a pH of the concentrated solution equal to 4. The results of this study were used to develop and validate a method for a simultaneous detection of 10 synthetic food dyes (SFD) (E102, E104, E110, E122, E124, E129, E131, E133, E142, E151) in aqueous and organic solutions. The results of the study can be used to provide analytical control of the content of synthetic dyes in the industrial wastewater. The limit of intermediate precision of the method did not exceed 5%, and the expanded uncertainty of the measurements was less than 10%.

Determination of chloropropanol esters and glycidyl esters in nutritional foods by gas chromatography–tandem mass spectrometry based on acid hydrolysis and solid-phase extraction

This study presents a method based on acid transesterification and the purification by solid-phase extraction (SPE) coupled with gas chromatography–tandem mass spectrometry for quantifying 3- and 2-monochloropropanediol esters (3-MCPDE, 2-MCPDE) and glycidyl esters (GE) in nutritional foods. The fat was extracted by liquid–liquid extraction with petroleum ether and diethyl ether after the sample was hydrolysed with ammonia. Then the extract was purified by a SPE cartridge filled with the aminopropyl sorbents. It was demonstrated that the optimal elution volume for 3-MCPDE, 2-MCPDE and GE greatly depended on the sample matrix and varied from 6 to 12 mL for four different kinds of food matrices. All three analytes in the sample solution could be fully collected in the first 10–12 mL of eluate. By this way, monoacylglycerols commonly present in the samples were fully removed. Therefore, the overestimation of GE quantification was effectively eliminated. The modified analytical procedure was fully validated in a single laboratory and has been recommended as a Chinese Food Safety National Standard. In addition, two derivatisation agents, heptafluorobutyrylimidazole and phenylboronic acid, were proved to be equivalent in method accuracy and precision for the quantification of three analytes.

A LC-MS/MS method for the simultaneous determination of 6-cyanodopamine, 6-nitrodopamine, 6-nitrodopa, 6-nitroadrenaline and 6-bromodopamine in human plasma and its clinical application in patients with chronic kidney disease.

The aim of this study was to develop a high-performance liquid chromatography-tandem mass spectrometry method for the determination of 6-cyanodopamine, 6-nitrodopamine, 6-nitrodopa, 6-nitroadrenaline and 6-bromodopamine in human plasma samples. Strata-X 33 μm solid-phase extraction cartridges were used for the extraction of the catecholamines from human plasma samples. The catecholamines were separated in a 150 × 3 mm Shim-pack GIST C18-AQ column with 3μm particle size, placed in an oven at 40°C and perfused with 82% mobile phase A (acetonitrile-H2O; 90:10, v/v) + 0.4% acetic acid and 18% mobile phase B (deionized H2O) + 0.2% formic acid at a flow rate of 340 μl/min in isocratic mode. The injected volume was 4 μl and the run lasted 4 min. The method was linear from 0.1 to 20 ng/ml and the lower limit of quantification was 0.1 ng/ml for all analytes. The method was applied to evaluate the plasma levels of catecholamines in plasma of patients with chronic kidney disease and allowed the detection for the first time of circulating levels of the novel catecholamines 6-bromodopamine and 6-cyanodopamine.

Sensitivity and quantitativeness of large-volume injection combined with liquid chromatography/high-resolution mass spectrometry for target screening analysis of emerging contaminants

Solid phase extraction (SPE) has been widely used for pretreatment in target screening (TS) analysis. However, some compounds are difficult to recover by SPE or their recovery is unstable for environmental samples. In this study, we tested large-volume injection (LVI) without SPE for TS analysis of 103 compounds listed by the Ministry of the Environment (Japan)—so-called ‘items to be surveyed’—using liquid chromatography high-resolution mass spectrometry. We evaluated the limit of quantification (LOQ) by LVI and compared this LOQ with the LOQ by SPE pretreatment using a hydrophilic-lipophilic balance (HLB) combined with activated carbon, which was found previously to afford the best SPE cartridges for target compounds recovery. The LOQ generally decreased as the injection volume increased, and the LOQ was at least 250 times lower for a 500-μL injection than for a 2-μL injection for half of the compounds. LVI provided LOQs lower than the predicted no effect concentration for more compounds than the SPE method. The average matrix effect (ME) by LVI was in the range 70%–130% for 69 out of 97 compounds. The ME was higher or lower for some of the remaining compounds, but the ME was in the range 10%–1000% for all 18 water samples for 84 of the 97 compounds. Comparing the ME by LVI and the recovery ratio by the SPE method showed that LVI achieved more accurate quantitation than the SPE method for a larger number of compounds. Therefore, LVI provides better sensitivity and quantitativeness than the SPE method using HLB and activated carbon for TS analysis of as many ‘items to be surveyed’ as possible.

Hydroxylated hierarchical flower-like COF for solid-phase extraction of adrenergic receptor agonists in milk.

A new detection platform based on a hydroxylated covalent organic framework (COF) integrated with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was constructed and used for detecting adrenergic receptor agonists (ARAs) residues in milk. The hydroxylated COF was prepared by polymerization of tris(4-aminophenyl)amine and 1,3,5-tris(4-formyl-3-hydroxyphenyl)benzene and applied to solid-phase extraction (SPE) of ARAs. This hydroxylated COF was featured with hierarchical flower-like morphology, easy preparation, and copious active adsorption sites. The adsorption model fittings and molecular simulation were applied to explore the potential adsorption mechanism. This detection platform was suitable for detecting four α2- and five β2-ARAs residues in milk. The linear ranges of the ARAs were from 0.25 to 50 µg·kg-1; the intra-day and the inter-day repeatability were in the range 2.9-7.9% and 2.0-10.1%, respectively. This work demonstrates this hydroxylated COF has great potential as SPE cartridge packing, and provides a new way to determine ARAs residues in milk.

For the occurrence of PPCPs from source to tap: A novel approach modified in terms of sample preservation and SPE cartridge to monitor PPCPs in our water supply

BackgroundThe ongoing infusion of pharmaceutical and personal care products (PPCPs) into ecosystems sustains a perpetual life cycle and leads to multi-generational exposures. Limited understanding of their environmental impact and their intrinsic ability to induce physiological effect in humans, even at low doses, pose great risks to human health. Few scholarly works have conducted systematic research into the occurrence of PPCPs within potable water systems. Concurrently, the associated monitoring techniques have not been comprehensively examined with regards to the specific nature of drinking water, namely whether the significant presence of disinfectants may influence the detection of PPCPs. ResultsA modified approach in terms of detailed investigation of sample preservation and optimization of an in-lab fabricated solid phase extraction (SPE) cartridge filled with DVB-VP and PS-DVB sorbent was proposed. Favorable methodological parameters were achieved, with correlation coefficients spanning from 0.9866 to 0.9998. The LODs of the PPCPs fluctuated from 0.001 to 2 μg L−1, while the LOQs varied from 0.002 to 5 μg L−1. The analysis of spiked samples disclosed a methodological precision of 2.31–9.86 % and a recovery of 52.4–119 %. We utilized the established method for analyzing 14 water samples of three categories (source water, finished water and tap water) from five centralized water supply plants. A total of 24 categories encompassing 72 PPCPs were detected, with the concentrations of PPCPs manifested a marked decrease from source water to finished water and finally to tap water. SignificanceOur research meticulously examined the enhancement and purification effects of widely used commercial SPE cartridges and suggested the use of in-lab fabricated SPE cartridges packed with DVB-VP and PS-DVB adsorbents. We also conducted a systematic evaluation of the need to incorporate ascorbic acid and sodium thiosulfate as preservatives for PPCP measurement, in consideration of the unique characteristics of drinking water matrices, specifically, the significant concentration levels of disinfectants. Furthermore, the proposed method was effectively employed to study the presence of PPCPs in source water, finished water, and tap water collected from centralized water supply plants.

Optimization of volatile organic compounds sampling from dairy cow exhaled breath using polymer-based solid-phase extraction cartridges for gas chromatographic analysis

We explored appropriate technical setups for the detection of volatile organic compounds (VOCs) from exhaled cow breath by comparing six different polymer-based solid-phase extraction (SPE) cartridges currently on the market for gas chromatography/mass spectrometry (GC-MS) screening. Exhaled breath was sampled at a single timepoint from five lactating dairy cows using six different SPE cartridges (Bond Elut ENV (ENV); Chromabond HRX (HRX); Chromabond HRP (HRP); Chromabond HLB (HLB); Chromabond HR-XCW (XCW) and Chromabond HR-XAW (XAW)). The trapped VOCs were analyzed by dynamic headspace vacuum in-tube extraction GC-MS (DHS-V-ITEX-GC-MS). Depending on the SPE cartridge, we detected 1174–1312 VOCs per cartridge. Most VOCs were alkenes, alkanes, esters, ketones, alcohols, aldehydes, amines, nitriles, ethers, amides, carboxylic acids, alkynes, azoles, terpenes, pyridines, or sulfur-containing compounds. The six SPE cartridges differed in their specificity for the chemical compounds, with the XAW cartridge showing the best specificity for ketones. The greatest differences between the tested SPE cartridges appeared in the detection of specific VOCs. In total, 176 different VOCs were detected with a match factor >80%. The greatest number of specific VOCs was captured by XAW (149), followed by ENV (118), HLB (117), HRP (115), HRX (114), and XCW (114). We conclude that the tested SPE cartridges are suitable for VOC sampling from exhaled cow breath, but the SPE cartridge choice enormously affects the detected chemical groups and the number of detected VOCs. Therefore, an appropriate SPE adsorbent cartridge should be selected according to our proposed inclusion criteria. For targeted metabolomics approaches, the SPE cartridge choice depends on the VOCs or chemical compound groups of interest based on our provided VOC list. For untargeted approaches without information on the animals’ metabolic condition, we suggest using multi-sorbent SPE cartridges or multiple cartridges per animal.