QuEChERS-Based Extraction Procedures for the Analysis of Bisphenols S and A in Breast Milk Samples by LC-QqQ-MS

2019 ◽  
Vol 102 (1) ◽  
pp. 23-32 ◽  
Author(s):  
Tomasz Tuzimski ◽  
Dominika Pieniążek ◽  
Grzegorz Buszewicz ◽  
Grzegorz Teresiński
Keyword(s):  
Breast Milk ◽  
Solid Phase ◽  
Multiple Reaction Monitoring ◽  
High Sensitivity ◽  
Bisphenol S ◽  
Milk Samples ◽  
Multiple Reaction Monitoring Mode ◽  
Sensitivity And Selectivity ◽  
Primary Secondary Amine ◽  
Array Detection

Abstract Different extraction and clean-up protocols, based on either the dispersive solid-phase extraction (d-SPE) and the quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach, were optimized and compared for the determination of selected bisphenols such as bisphenol A (BPA) and bisphenol S (BPS) in breast milk samples. QuEChERS-based sample preparation procedure was optimized by evaluation of different clean-up sorbents including zirconium-based sorbents (Z-Sep and Z-Sep Plus) and primary secondary amine. Negligible matrix interference was observed for most of the analytes due to application of 45 mg Z-Sep or 45 mg Z-Sep + 5 mg Z-Sep Plus sorbents in d-SPE clean-up step. Acceptable analytical performance for the BPA and BPS was observed with recoveries percentage in the range of 70–92% and RSD less than 15%. The pilot study was performed by applying HPLC with diode-array detection, and optimized procedures were transferred to the LC triple-quadrupole MS system. LC with electrospray ionization and tandem MS operating in the multiple reaction monitoring mode provide high sensitivity and selectivity for trace analysis. The LODs were 0.10 and 0.54 ng/mL, and the LOQs were 0.20 and 1.35 ng/mL for BPS and BPA, respectively. The developed procedures were evaluated in terms for material collection obtained from women (inhabitants of Lublin, Poland). In 20 samples, bisphenol residues were detected at concentrations from 0.09 to 11.56 ng/mL.

Comparison of SPE/d-SPE and QuEChERS-Based Extraction Procedures in Terms of Fungicide Residue Analysis in Wine Samples by HPLC–DAD and LC-QqQ-MS

2016 ◽  
Vol 99 (6) ◽  
pp. 1436-1443 ◽  
Author(s):  
Tomasz Tuzimski ◽  
Tomasz Rejczak ◽  
Dominika Pieniążek ◽  
Grzegorz Buszewicz ◽  
Grzegorz Teresiński
Keyword(s):  
Multiple Reaction Monitoring ◽  
Residue Analysis ◽  
High Sensitivity ◽  
Extraction Procedures ◽  
Multiple Reaction Monitoring Mode ◽  
Sensitivity And Selectivity ◽  
Dispersive Spe ◽  
Array Detection ◽  
Fungicide Residue

Abstract Two different extraction and clean-up protocols, based on either the SPE/dispersive SPE (d-SPE) or the quick, easy, cheap, effective, rugged, and safe approach, were optimized and compared for determination of six selected fungicides (benalaxyl, metalaxyl, triadimenol, tebuconazole, diniconazole, and epoxiconazole) in wine samples. The pilot study was performed by applying HPLC with diode-array detection, and optimized procedures were easily transferred to the LC triple-quadrupole MS system. Both extraction procedures presented good performance for all the analytes, with recoveries in the range of 70–132% and SDs ≤20%. The d-SPE clean-up step included in both procedures allows obtaining colorless extracts with the majority of coextracted matrix compounds removed. LC with electrospray ionization and tandem MS operating in the multiple reaction monitoring mode provide high sensitivity and selectivity for trace analysis. Both developed procedures were evaluated in terms of commercial wine sample analysis. In three wine samples, metalaxyl and tebuconazole residues were detected at concentrations from 0.14 to 30.7 ng/mL. Both approaches showed satisfactory feasibility for fungicide residue analysis in wine samples.

scholarly journals Comparison of DAD and FLD Detection for Identification of Selected Bisphenols in Human Breast Milk Samples and Their Quantitative Analysis by LC-MS/MS

2020 ◽  
Vol 103 (4) ◽  
pp. 1029-1042
Author(s):  
Tomasz Tuzimski ◽  
Szymon Szubartowski ◽  
Renata Gadzała-Kopciuch ◽  
Andrzej Miturski ◽  
Monika Wójtowicz-Marzec ◽  
...  
Keyword(s):  
Breast Milk ◽  
Solid Phase ◽  
Array Detector ◽  
Human Breast Milk ◽  
Human Breast ◽  
Bisphenol S ◽  
Fluorescence Detector ◽  
Detection Techniques ◽  
Milk Samples

Abstract Background Determination of bisphenols released from packaging material is undoubtedly a difficult and tricky task, requiring the chemical analyst to develop an individual approach to obtain reliable analytical information. Objective QuECHERS (Quick, Easy, Cheap, Effective, Rugged, and Safe)/dispersive solid-phase extraction (d-SPE) technique and high performance liquid chromatography (HPLC) coupled with modern detection techniques such as diode-array detector (DAD), fluorescence detector (FLD) or tandem mass spectrometry (MS/MS) for the determination of bisphenols such as bisphenol A (BPA), bisphenol S (BPS), bisphenol F (BPF), bisphenol B (BPB), 2-[[4-[2-[4-(Oxiran-2-ylmethoxy)phenyl]propan-2yl]phenoxy] methyl]oxirane (BADGE), 3-[4-[2-[4-(Oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]propane-1,2-diol (BADGE*H2O), 3-[4-[2-[4-(2,3-Dihydroxypropoxy)phenyl]propan-2-yl]phenoxy]propane-1,2-diol (BADGE*2H2O), 1-Chloro-3-[4-[2-[4-(3-chloro-2-hydroxypropoxy)phenyl] propan-2-yl]phenoxy]propan-2-ol (BADGE*2HCl) in human breast milk samples have been performed. Methods For the analysis of total analytes, prior to the extraction with acetonitrile, a deconjugation step was implemented in a tube by adding 1 mL of the enzymatic solution with the β-Glucuronidase to 5 mL of sample. The mix was homogenized and incubated for 17 h at 37°C. Ten milliliters of acetonitrile, and a QuEChERS salt packet with 4 g anhydrous MgSO4 and 1 g NaCl were added. During the d-SPE step the extract was transferred into tube with 30 mg Z-Sep and 50 mg PSA (and also 150 mg MgSO4 for LC-MS/MS analysis). MeOH–water (20:80, v/v) were added to the dry residue and the extract was reconstituted in 150 µL (25-fold analytes pre-concentration is achieved). Next bisphenols were identified by HPLC-DAD-FLD and quantified by LC-MS/MS equipment. Conclusions During the bisphenols HPLC-DAD-FLD analysis, from 6 min a reinforcement of 15 was used, which allowed analytes to be identified at 750 pg/mL. Application of LC-MS/MS allowed quantification of bisphenols in the range from 2.12 to 116.22 ng/mL in a total 27 human breast milk samples. Highlights First QuEChERS/d-SPE coupled with HPLC-DAD-FLD or LC-MS/MS method for the quantification of bisphenols and its analogues in breast milk Faster and cheaper alternative to traditional extraction methods The method was applied for the first biomonitoring of bisphenols and its analogues in breast milk.

scholarly journals Method Development for Selected Bisphenols Analysis in Sweetened Condensed Milk from a Can and Breast Milk Samples by HPLC–DAD and HPLC-QqQ-MS: Comparison of Sorbents (Z-SEP, Z-SEP Plus, PSA, C18, Chitin and EMR-Lipid) for Clean-Up of QuEChERS Extract

Molecules ◽  
2019 ◽  
Vol 24 (11) ◽  
pp. 2093 ◽  
Author(s):  
Tomasz Tuzimski ◽  
Szymon Szubartowski
Keyword(s):  
Breast Milk ◽  
Secondary Amine ◽  
Method Development ◽  
Solid Phase ◽  
Internal Standard ◽  
Matrix Composition ◽  
Milk Samples ◽  
Relative Standard ◽  
Primary Secondary Amine

Background: Identification and quantitative determination of analytes released from the packaging material is undoubtedly a difficult and tricky task, requiring the chemical analyst to develop an individual approach to obtain reliable analytical information. Unfortunately, it is still challenging for scientists to determine bisphenols at trace or even ultra-trace levels in samples characterized by a very complex, and often variable, matrix composition. Objective: Optimization and application of QuEChERS/d-SPE coupled with HPLC-DAD (and LC-QqQ-MS) method for the simultaneous determination of bisphenols (A, S, F, B, BADGE and derivatives) in milk samples from a can and breast milk samples have been performed. Methods: Concerning the analysis of unconjugated analytes, after the thawing and shaking the sample (5 mL breast milk or 10 mL milk samples from a can), it was transferred into a 50 mL polypropylene centrifuge tube. For the analysis of the total amount of analytes, prior to the extraction with acetonitrile, a deconjugation step was implemented in a tube by adding to sample, the an Isotopically Labelled Internal Standard (IS) solution (50 ng/mL) and 1 mL of the enzymatic solution with the β-Glucuronidase (3500 U/mL). The mix was homogenized and incubated for 16–18 h at 37 °C. Next, 10 mL of acetonitrile, and a QuEChERS salt packet (4 g anhydrous MgSO4, 1 g NaCl) were added. After shaking and centrifugation, the total acetonitrile layer was isolated in a polypropylene tube evaporate to dryness, and reconstitute in 1.2 mL acetonitrile. During d-SPE step the extract was transferred into a 15 mL polypropylene tube with Z-Sep and primary secondary amine (PSA). Next, shake the tube, store in fridge, and centrifuge for 15 min. The acetonitrile supernatant was obtained with a pipette and evaporated to dryness. Mixture MeOH: water (20:80, v/v) were added to the dry residue and the extract was reconstitute in 200 μL and analyzed by HPLC-DAD and HPLC–QqQ-MS equipment. Conclusion: Six different salts during d-SPE step were evaluated such as: zirconium dioxide-based sorbent (Z-Sep, Z-Sep Plus), primary secondary amine (PSA), octadecyl (C18), EMR-Lipid, Chitin and also their mixtures. Negligible matrix interference was observed for most of the analytes due to application of Z-Sep and PSA in dispersive-solid phase extraction clean-up step. Extraction of target analytes was performed using QuEChERS/d-SPE cleanup, and presents good performance for selected analytes with recoveries in the range of 15–103% and relative standard deviations (RSD) less than 10% in breast milk samples.

scholarly journals A Rapid and Selective LC-MS/MS Method for Quantification of Quetiapine in Human Plasma and its Application to Pharmacokinetic Study on Indian Schizophrenia Patients

2011 ◽  
Vol 8 (4) ◽  
pp. 1802-1814 ◽  
Author(s):  
S. Ravinder ◽  
A. T. Bapuji ◽  
K. Mukkanti ◽  
M. Nagesh ◽  
H. L. V. Ravikiran
Keyword(s):  
Mass Spectrometry ◽  
Human Plasma ◽  
Pharmacokinetic Study ◽  
Dynamic Range ◽  
Solid Phase ◽  
Multiple Reaction Monitoring ◽  
Internal Standard ◽  
Plasma Samples ◽  
Standard Curve ◽  
Multiple Reaction Monitoring Mode

A rapid, robust and selective high pressure liquid chromatography–positive electrospray ionization tandem mass spectrometry method has been developed and validated for the quantification of quetiapine (QUE) in human plasma with K2EDTA using oxcarbazepine (IS) as an internal standard. Analyte and internal standard were extracted from human plasma by solid-phase extraction using acetonitrile. The eluted samples were chromatographed on a C18 column by using a 10:75:15v/v mixture of ammonium formate buffer (5 mM, pH 4.50) and acetonitrile and methanol as an isocratic mobile phase at a flow rate of 0.4 mL/min and analyzed by mass spectrometry in the multiple reaction monitoring mode using the respective [M+H]+ions,m/z384.3/253.2 for Quetiapine andm/z253.1/208.1 for the internal standard. The assay exhibited a linear dynamic range of 5.01 - 2501.04 ng/mL for quetiapine in human plasma. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. A run time of 2.5 min for each sample made it possible to analyze 300 patient plasma samples per day. The validated method has been successfully used for the estimation of quetiapine in real time schizophrenia patient’s plasma samples for pharmacokinetic study.

scholarly journals Determination of Ergot Alkaloids: Purity and Stability Assessment of Standards and Optimization of Extraction Conditions for Cereal Samples

2008 ◽  
Vol 91 (6) ◽  
pp. 1363-1371 ◽  
Author(s):  
Rudolf Krska ◽  
Franz Berthiller ◽  
Rainer Schuhmacher ◽  
Kristian F Nielsen ◽  
Colin Crews
Keyword(s):  
Solid Phase ◽  
Ergot Alkaloids ◽  
Food Samples ◽  
Ambient Temperatures ◽  
Carbonate Buffer ◽  
Extraction Solvent ◽  
Flight Mass Spectrometry ◽  
Primary Secondary Amine ◽  
Array Detection ◽  
The Stability

Abstract Results obtained from a purity study on standards of the 6 major ergot alkaloids ergometrine, ergotamine, ergosine, ergocristine, ergocryptine, and ergocornine and their corresponding epimers are discussed. The 6 ergot alkaloids studied have been defined by the European Food Safety Authority as those that are the most common and physiologically active. The purity of the standards was investigated by means of liquid chromatography with diode array detection, electrospray ionization, and time-of-flight mass spectrometry (LC-DAD-ESI-TOF-MS). All of the standards assessed showed purity levels considerably above 98 apart from ergocristinine (94), ergosine (96), and ergosinine (95). Also discussed is the optimization of extraction conditions presented in a recently published method for the quantitation of ergot alkaloids in food samples using solid-phase extraction with primary secondary amine (PSA) before LC/MS/MS. Based on the results obtained from these optimization studies, a mixture of acetonitrile with ammonium carbonate buffer was used as extraction solvent, as recoveries for all analyzed ergot alkaloids were significantly higher than those with the other solvents. Different samplesolvent ratios and extraction times showed just minor influences in extraction efficacy. Finally, the stability of the ergot alkaloids in both raw cereals and cereal-based processed food extracts was studied. According to these studies, extracts should be prepared and analyzed the same day or stored below ambient temperatures. Barley and rye extracts, which were stored at 4 and 15C after PSA cleanup, proved to be stable overnight. However, storage over a period of 14 days at 4C resulted in significant epimerization, which was most pronounced in rye and particularly for ergocornine, ergocryptine, and ergocristine.

Determination of Residues of Seven Carbamate Pesticides in Milk Using Ultra-Performance Liquid Chromatography/Tandem Mass Spectrometry and QuEChERS Methods

2013 ◽  
Vol 96 (3) ◽  
pp. 657-662 ◽  
Author(s):  
Shao-Ying Liu ◽  
Quan Jin ◽  
Xi-Hui Huang ◽  
Guo-Nian Zhu
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Analytical Method ◽  
Multiple Reaction Monitoring ◽  
High Sensitivity ◽  
Ultra Performance Liquid Chromatography ◽  
Tandem Mass ◽  
Modified Quechers ◽  
Liquid Chromatography Tandem Mass ◽  
Multiple Reaction Monitoring Mode

Abstract An improved analytical method was developed for simultaneous quantification of seven carbamates in milk by ultra-performance LC combined with electrospray ionization triple quadrupole tandem mass spectrometry in the multiple reaction monitoring mode. Samples were extracted and purified using a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method. The LOQs ranged from 0.033 to 0.23 μg/kg; reasonable recoveries (85.4 to 110.9%) of the seven carbamates in milk were demonstrated at different spike levels. The developed analytical method would be appropriate for the routine, high throughput, high sensitivity quantification of the seven carbamates using modified QuEChERS pretreatment.

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