54 results on '"Gionfriddo E"'
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2. Advances in Solid Phase Microextraction (SPME) for Metabolomics
- Author
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Boyaci, E., primary, Gionfriddo, E., additional, Roszkowska, A., additional, and Bojko, B., additional
- Published
- 2021
- Full Text
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3. Characterization of a mixed mode fluorocarbon/weak anion exchange sorbent for the separation of perfluoroalkyl substances.
- Author
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Olomukoro AA, Xie R, Paucar FXF, DeRosa C, Danielson ND, and Gionfriddo E
- Abstract
The ubiquitous presence and persistence of per- and polyfluoroalkyl substances (PFAS) in the environment have raised concerns in the scientific community. Current research efforts are prioritizing effective PFAS remediation through novel sorbents with orthogonal interaction mechanisms. Recognized sorption mechanisms between PFAS and sorbents include hydrophobic, electrostatic, and fluorine-fluorine interaction. The interplay of these mechanisms contributes significantly to improved sorption capacity and selectivity in PFAS separations. In this study, a primary/secondary amine-functionalized polystyrene-divinylbenzene (Sepra-WAX) polymer was modified to create a fluorinated WAX resin (Sepra-WAX-KelF-PEI). The synthesis intermediate (Sepra-WAX-KelF) was also tested to assess the improvement of the final product (Sepra-WAX-KelF-PEI). The adsorption capacity of Sepra-WAX, Sepra-WAX-KelF, and Sepra-WAX-KelF-PEI, and their interactions with PFAS were evaluated. The effect of pH, ionic strength, and organic solvents on PFAS sorption in aqueous solution was also investigated. The sorbents showed varied adsorption capacities for perfluorooctanoic acid, perfluoropentanoic acid, perfluoro-n-decanoic acid, and hexafluoropropylene oxide dimer acid, with the average extraction capacity of the four analytes being Sepra-WAX-KelF-PEI (523 mg/g) > Sepra-WAX (353 mg/g) > Sepra-WAX-KelF (220 mg/g). Sepra-WAX-KelF-PEI provided the highest adsorption capacity for all analytes tested, proving that the combination of electrostatic and hydrophobic/fluorophilic interactions is crucial for the effective preconcentration of PFAS and its future applications for PFAS remediation from aqueous solutions., (© 2024 Wiley‐VCH GmbH.)
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- 2024
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4. Enhancing Quantitative Analysis of Xenobiotics in Blood Plasma through Cross-Matrix Calibration and Bayesian Hierarchical Modeling.
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Godage NH, Qian SS, Cudjoe E, and Gionfriddo E
- Abstract
This study addresses the challenges of matrix effects and interspecies plasma protein binding (PPB) on measurement variability during method validation across diverse plasma types (human, rat, rabbit, and bovine). Accurate measurements of small molecules in plasma samples often require matrix-matched calibration approaches with the use of specific plasma types, which may have limited availability or affordability. To mitigate the costs associated with human plasma measurements, we explore in this work the potential of cross-matrix-matched calibration using Bayesian hierarchical modeling (BHM) to correct for matrix effects associated with PPB. We initially developed a targeted quantitative approach utilizing biocompatible solid-phase microextraction coupled with liquid chromatography-mass spectrometry for xenobiotic analysis in plasma. The method was evaluated for absolute matrix effects across human, bovine, rat, and rabbit plasma comparing pre- and postmatrix extraction standards. Absolute matrix effects from 96 to 108% for most analytes across plasma sources indicate that the biocompatibility of the extraction phase minimizes interference coextraction. However, the extent of PPB in different media can still affect the accuracy of the measurement when the extraction of small molecules is carried out via free concentration, as in the case of microextraction techniques. In fact, while matrix-matched calibration revealed high accuracy, cross-matrix calibration (e.g., using a calibration curve generated from bovine plasma) proved inadequate for precise measurements in human plasma. A BHM was used to calculate correction factors for each analyte within each plasma type, successfully mitigating the measurement bias resulting from diverse calibration curve types used to quantify human plasma samples. This work contributes to the development of cost-effective, efficient calibration strategies for biofluids. Leveraging easily accessible plasma sources, like bovine plasma, for method optimization and validation prior to analyzing costly plasma (e.g., human plasma) holds substantial advantages applicable to biomonitoring and pharmacokinetic studies., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)
- Published
- 2023
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5. Matrix effects demystified: Strategies for resolving challenges in analytical separations of complex samples.
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Williams ML, Olomukoro AA, Emmons RV, Godage NH, and Gionfriddo E
- Abstract
Matrix effects can significantly impede the accuracy, sensitivity, and reliability of separation techniques presenting a formidable challenge to the analytical process. It is crucial to address matrix effects to achieve accurate and precise measurements in complex matrices. The multifaceted nature of matrix effects which can be influenced by factors such as target analyte, sample preparation protocol, composition, and choice of instrument necessitates a pragmatic approach when analyzing complex matrices. This review aims to highlight common challenges associated with matrix effects throughout the entire analytical process with emphasis on gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, and sample preparation techniques. These techniques are susceptible to matrix effects that could lead to ion suppression/enhancement or impact the analyte signal at various stages of the analytical workflow. The assessment, quantification, and mitigation of matrix effects are necessary in developing any analytical method. Strategies can be implemented to reduce or eliminate the matrix effect by changing the type of ionization, improving extraction and clean-up methods, optimization of chromatography conditions, and corrective calibration methods. While development of an effective strategy to completely mitigate matrix effects remains elusive, an integrated approach that combines sample preparation, analytical extraction, and effective instrumental analysis remains the most promising avenue for identifying and resolving matrix effects., (© 2023 The Authors. Journal of Separation Science published by Wiley-VCH GmbH.)
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- 2023
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6. Rapid Screening and Quantification of PFAS Enabled by SPME-DART-MS.
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Emmons RV, Fatigante W, Olomukoro AA, Musselman B, and Gionfriddo E
- Abstract
Per- and polyfluoroalkyl substances (PFAS), an emerging class of toxic anthropogenic chemicals persistent in the environment, are currently regulated at the low part-per-trillion level worldwide in drinking water. Quantification and screening of these compounds currently rely primarily on liquid chromatography hyphenated to mass spectrometry (LC-MS). The growing need for quicker and more robust analysis in routine monitoring has been, in many ways, spearheaded by the advent of direct ambient mass spectrometry (AMS) technologies. Direct analysis in real time (DART), a plasma-based ambient ionization technique that permits rapid automated analysis, effectively ionizes a broad range of compounds, including PFAS. This work evaluates the performance of DART-MS for the screening and quantification of PFAS of different chemical classes, employing a central composite design (CCD) to better understand the interactions of DART parameters on their ionization. Furthermore, in-source fragmentation of the model PFAS was investigated based on the DART parameters evaluated. Preconcentration of PFAS from water samples was achieved by solid phase microextraction (SPME), and extracts were analyzed using the optimized DART-MS conditions, which allowed obtaining linear dynamic ranges (LDRs) within 10 and 5000 ng/L and LOQs of 10, 25, and 50 ng/L for all analytes. Instrumental analysis was achieved in less than 20 s per sample.
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- 2023
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7. Quantitative determination of pesticides in human plasma using bio-SPME-LC-MS/MS: a robust tool to assess occupational exposure to pesticides.
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Godage NH, Cudjoe E, Chau T, and Gionfriddo E
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- Humans, Chromatography, Liquid methods, Solid Phase Microextraction methods, Tandem Mass Spectrometry methods, Solid Phase Extraction methods, Pesticides analysis, Pesticide Residues analysis
- Abstract
Analysis of biofluids, such as plasma, can be used to investigate occupational pesticide exposure in the agricultural industry. Considering the chemical complexity and variability of plasma samples, any protocol for pesticide analysis should achieve efficient sample cleanup to minimize matrix effects and enhance method sensitivity through analyte pre-concentration. In this work, a high-throughput method was developed for analysis of 79 pesticides, commonly used in agricultural practices, in human plasma, using biocompatible solid-phase microextraction (SPME) coupled to liquid chromatography-tandem mass spectrometry. An SPME method was developed using a biocompatible hydrophilic-lipophilic balance/polyacrylonitrile (HLB/PAN) extraction phase and demonstrated negligible matrix effects. The performance of the developed SPME method was compared to a QuEChERS -Quick, Easy, Cheap, Effective, Rugged, and Safe- method, the most common sample preparation and cleanup approach for pesticide analysis in complex matrices. Comparable accuracy and precision were achieved for both methods, with accuracy values within 70-120% and relative standard deviation < 15%. Overall, the developed SPME and QuEChERS methods extracted 79 out of 82 monitored pesticides in human plasma. The SPME protocol demonstrated higher sensitivity than the QuEChERS method and a drastic reduction of matrix effects., (© 2023. Springer-Verlag GmbH Germany, part of Springer Nature.)
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- 2023
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8. Investigation of the adsorption/desorption mechanism of perfluoroalkyl substances on HLB-WAX extraction phases for microextraction.
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Olomukoro AA, DeRosa C, and Gionfriddo E
- Abstract
The C-F alkyl structural backbone of per- and polyfluoroalkyl substances makes this class of molecules resistant to heat and degradation, leading to their high persistence and mobility in the environment and bioaccumulation in the tissues of living organisms. In this study, 15 PFAS with an alkyl chain length from C
4 to C14 , currently monitored by the U.S. Environmental Protection Agency (EPA), were preconcentrated by solid-phase microextraction (SPME) and analyzed by liquid chromatography-tandem mass spectrometry. The adsorption and desorption mechanisms of PFAS onto ion-exchange extraction phases was evaluated to understand the extraction process of PFAS from various environmental matrices under different conditions. This was achieved using two SPME geometries, namely fibers and thin films. The use of thin films resulted in a twofold improvement in extraction efficiency compared to fibers, especially for the short-chain PFAS. Methanol:water (80:20, v/v) was chosen as the optimized desorption solution, with ammonium formate added to minimize carryover. Extraction time profiles for both SPME geometries showed faster equilibration with thin films (30 min) compared to fibers (90-120 min). The linear dynamic range obtained with this method using fibers and thin films ranged from 10 to 5000 ng L-1 and 2.5-5000 ng L-1 , respectively, with acceptable accuracy (70-130%) and precision (<15%). LOD ranged within 2.5-10 ng L-1 for fibers and 0.01-0.25 ng L-1 for thin films. Investigating the factors affecting PFAS recovery in complex samples enabled the quantitative assessment of PFAS contamination in various environmental water samples such as seawater, melted snow and biospecimens like human plasma. A 96-SPME holder was used for validation, which is compatible with sampling in 96-well plates and ensures high throughput in the analysis of real samples. The total concentration of PFAS detected in seawater and snow was 51.3 ng L-1 and 16.4 ng L-1 , respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)- Published
- 2023
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9. Design and Preclinical Evaluation of Nicotine-Stearic Acid Conjugate-Loaded Solid Lipid Nanoparticles for Transdermal Delivery: A Technical Note.
- Author
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Renukuntla J, Peterson-Sockwell S, Clark BA, Godage NH, Gionfriddo E, Bolla PK, and Boddu SHS
- Abstract
This study aimed to develop and evaluate nicotine--stearic acid conjugate-loaded solid lipid nanoparticles (NSA-SLNs) for transdermal delivery in nicotine replacement therapy (NRT). Nicotine conjugation to stearic acid prior to SLN formulation greatly increased drug loading. SLNs loaded with a nicotine-stearic acid conjugate were characterized for size, polydispersity index (PDI), zeta potential (ZP), entrapment efficiency, and morphology. Pilot in vivo testing was carried out in New Zealand Albino rabbits. The size, PDI, and ZP of nicotine-stearic acid conjugate-loaded SLNs were 113.5 ± 0.91 nm, 0.211 ± 0.01, and -48.1 ± 5.75 mV, respectively. The entrapment efficiency of nicotine-stearic acid conjugate in SLNs was 46.45 ± 1.53%. TEM images revealed that optimized nicotine-stearic acid conjugate-loaded SLNs were uniform and roughly spherical in shape. Nicotine-stearic acid conjugate-loaded SLNs showed enhanced and sustained drug levels for up to 96 h in rabbits when compared with the control nicotine formulation in 2% HPMC gel. To conclude, the reported NSA-SLNs could be further explored as an alternative for treating smoking cessation.
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- 2023
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10. Automated method using direct-immersion solid-phase microextraction and on-fiber derivatization coupled with comprehensive two-dimensional gas chromatography high-resolution mass spectrometry for profiling naphthenic acids in produced water.
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Crucello J, Sampaio NM, Junior IM, Carvalho RM, Gionfriddo E, Marriott PJ, and Hantao LW
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- Immersion, Gas Chromatography-Mass Spectrometry methods, Carboxylic Acids analysis, Solid Phase Microextraction, Water Pollutants, Chemical analysis
- Abstract
Naphthenic acids (NAs) are naturally occurring organic acids in petroleum and are found in waste waters generated during oil production (produced water, PW). Profiling this class of compounds is important due to flow assurance during oil exploration. Compositional analysis of PW is also relevant for waste treatment to reduce negative impacts on the environment. Here, comprehensive two-dimensional gas chromatography coupled with high-resolution mass spectrometry (GC×GC-HRMS) was applied as an ideal platform for qualitative analysis of NAs by combining the high peak capacity of the composite system with automated scripts for group-type identification based on accurate mass measurements and fragmentation patterns. To achieve high-throughput profiling of NAs in PW samples, direct-immersion solid phase microextraction (DI-SPME) was selected for extraction, derivatization and preconcentration. A fully automated DI-SPME method was developed to combine extraction, fiber rinsing and drying, and on-fiber derivatization with N-methyl-N‑tert-butyldimethylsilyltrifluoroacetamide (MTBSTFA). Data processing was based on filtering scripts using the Computer Language for Identifying Chemicals (CLIC). The method successfully identified up to 94 NAs comprising carbon numbers between 6 and 18 and hydrogen deficiency values ranging from 0 to -4. The proposed method demonstrated wider extraction coverage compared to traditional liquid-liquid extraction (LLE) - a critical factor for petroleomic investigations. The method developed also enabled quantitative analysis, exhibiting detection limits of 0.5 ng L
-1 and relative standard deviation (RSD) at a concentration of NAs of 30 µg L-1 ranging from 4.5 to 25.0%., Competing Interests: Declaration of Competing Interest The authors declare no competing financial interest. This article does not contain any studies with human participants or animals performed by any of the authors., (Copyright © 2023 Elsevier B.V. All rights reserved.)- Published
- 2023
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11. Leveraging multi-mode microextraction and liquid chromatography stationary phases for quantitative analysis of neurotoxin β-N-methylamino-L-alanine and other non-proteinogenic amino acids.
- Author
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Emmons RV, Karaj E, Cudjoe E, Bell DS, Tillekeratne LMV, and Gionfriddo E
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- Chromatography, Liquid, Amino Acids, Neurotoxins
- Abstract
Effective quantitative analysis of BMAA (β-N-methylamino-L-alanine) and its isomers without the need for derivatization has always been an analytical challenge due to their poor retention and separation on various liquid chromatography stationary phases. Previous studies that utilized conventional hydrophilic interaction chromatography (HILIC) demonstrate false negatives compared to reverse-phase workflows with derivatization. This work evaluates the chromatographic behavior of BMAA and its isomers, in their underivatized forms, on selected stationary phases, in particular fluorophenyl-based columns, to attain effective retention and separation. Detection and quantification were achieved with an ion-trap mass spectrometer. Extraction and preconcentration were achieved via solid phase microextraction (SPME) by assessing the effectiveness of multiple extraction phases, including hydrophilic-lipophilic balanced (HLB) and mixed-mode (MM). A MM extraction phase consisting of C
8 and benzene sulfonic acid moieties provided ideal extraction performance for BMAA and its isomers (2,4-diaminobutyric acid, DABA; N-(2-aminoethyl) glycine, AEG). Chromatographic separation was achieved within 8 min on a fluorophenyl stationary phase, ensuring high throughput without derivatization, and showing exceptional improvement from conventional HILIC methods. Limits of quantification in water for BMAA and AEG were 2.5 µg L-1 and DABA was 5 µg L-1 , with linear dynamic ranges from 2.5 µg L-1 - 200 µg L-1 for BMAA and AEG and 5 µg L-1 - 200 µg L-1 for DABA., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)- Published
- 2022
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12. Biocompatible SPME coupled to GC/MS for analysis of xenobiotics in blood plasma.
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Godage NH and Gionfriddo E
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- Animals, Cattle, Dimethylpolysiloxanes chemistry, Gas Chromatography-Mass Spectrometry methods, Plasma, Rabbits, Rats, Reproducibility of Results, Solid Phase Microextraction methods, Xenobiotics
- Abstract
This work proposes a new method for biomonitoring studies focused on the screening and quantification of xenobiotics in blood-derived samples. The performance of a polydimethylsiloxane/divinylbenzene/polydimethylsiloxane (PDMS/DVB/PDMS) biocompatible extraction phase was investigated for extraction of pesticides and pharmaceuticals from plasma samples via direct immersion solid-phase microextraction (SPME) prior to gas chromatography-mass spectrometry. Under the optimum extraction settings, which included an attentive optimization of the fiber rinsing conditions, the microextraction device was able to endure 100 consecutive extractions from undiluted and diluted plasma with an overall reproducibility up to 28% for all the analytes tested, except chlorpyrifos-methyl. Optimized conditions were used to validate a quantitative method using matrix-matched calibration with isotopically labeled internal standard correction. Accuracy and precision values obtained for analysis of bovine plasma were within 96-132% and 0.05-5.82% respectively. LLOQs for all the analytes were at 1 µg L
-1 and LDR ranged within 1-100 µg L-1 . The applicability of this method to plasma from different species (human, rat, rabbit) was also investigated. This work represents the first step toward broader use of the biocompatible PDMS/DVB/PDMS extraction phases for analysis of multiclass xenobiotics in plasma and other complex biofluids., (Copyright © 2022 Elsevier B.V. All rights reserved.)- Published
- 2022
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13. Unraveling the Complex Composition of Produced Water by Specialized Extraction Methodologies.
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Emmons RV, Shyam Sunder GS, Liden T, Schug KA, Asfaha TY, Lawrence JG, Kirchhoff JR, and Gionfriddo E
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- Solid Phase Microextraction, Wastewater chemistry, Water, Polycyclic Aromatic Hydrocarbons analysis, Water Pollutants, Chemical analysis
- Abstract
Produced water (PW), a waste byproduct of oil and gas extraction, is a complex mixture containing numerous organic solubles and elemental species; these constituents range from polycyclic aromatic hydrocarbons to naturally occurring radioactive materials. Identification of these compounds is critical in developing reuse and disposal protocols to minimize environmental contamination and health risks. In this study, versatile extraction methodologies were investigated for the untargeted analysis of PW. Thin-film solid-phase microextraction with hydrophilic-lipophilic balance particles was utilized for the extraction of organic solubles from eight PW samples from the Permian Basin and Eagle Ford formation in Texas. Gas chromatography-mass spectrometry analysis found a total of 266 different organic constituents including 1,4-dioxane, atrazine, pyridine, and PAHs. The elemental composition of PW was evaluated using dispersive solid-phase extraction followed by inductively coupled plasma-mass spectrometry, utilizing a new coordinating sorbent, poly(pyrrole-1-carboxylic acid). This confirmed the presence of 29 elements including rare earth elements, as well as hazardous metals such as Cr, Cd, Pb, and U. Utilizing chemometric analysis, both approaches facilitated the discrimination of each PW sample based on their geochemical origin with a prediction accuracy above 90% using partial least-squares-discriminant analysis, paving the way for PW origin tracing in the environment.
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- 2022
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14. Ion exchange solid phase microextraction coupled to liquid chromatography/laminar flow tandem mass spectrometry for the determination of perfluoroalkyl substances in water samples.
- Author
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Olomukoro AA, Emmons RV, Godage NH, Cudjoe E, and Gionfriddo E
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- Caprylates analysis, Fluorocarbons isolation & purification, Water Pollutants, Chemical isolation & purification, Chromatography, Liquid, Fluorocarbons analysis, Ion Exchange, Solid Phase Microextraction, Tandem Mass Spectrometry, Water Pollutants, Chemical analysis
- Abstract
Per- and polyfluoroalkyl substances (PFAS) are toxic and bioaccumulative compounds that are persistent in the environment due to their water and heat resistant properties. These compounds have been demonstrated to be ubiquitous in the environment, being found in water, soil, air and various biological matrices. The determination of PFAS at ultra-trace levels is thus critical to assess the extent of contamination in a particular matrix. In this work, solid phase microextraction (SPME) was evaluated as a pre-concentration technique to aid the quantitation of this class of pollutants below the EPA established advisory limits in drinking water at parts-per-trillion levels. Four model PFAS with varying physicochemical properties, namely hexafluoropropylene oxide dimer acid (GenX), perfluoro-1- butanesulfonate (PFBS), perfluoro-n-octanoic acid (PFOA) and perfluoro-1-octanesulfonate (PFOS) were studied as a proof of concept. Analysis was performed with the use of ultra-high pressure liquid chromatography-laminar flow tandem mass spectrometry (UHPLC-MS/MS). This study proposes the use of hydrophilic-lipophilic balance-weak anion-exchange/polyacrylonitrile (HLB-WAX/PAN) as a SPME coating, ideal for all model analytes. A sample volume of 1.5 mL was used for analysis, the optimized protocol including 20 min extraction, 20 min desorption and 6 min LC/MS analysis. This method achieved LOQs of 2.5 ng L
- 1 (PFOS) and 1 ng L- 1 (GenX, PFBS and PFOA) with satisfactory precision and accuracy values evaluated over a period of 5 days., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)- Published
- 2021
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15. Direct immersion thin film solid phase microextraction of polychlorinated n-alkanes in cod liver oil.
- Author
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Gruszecka D, Grandy J, Gionfriddo E, Singh V, and Pawliszyn J
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- Calibration, Dimethylpolysiloxanes chemistry, Immersion, Alkanes chemistry, Cod Liver Oil chemistry, Hydrocarbons, Chlorinated chemistry, Solid Phase Microextraction methods
- Abstract
A thin film-solid phase microextraction (TF-SPME) method was developed to test for 5 individual polychlorinated n-alkanes (PCAs) from commercial cod liver oil samples. This was accomplished by preparing a novel aluminum supported, hydrophilic-lipophilic balance/polydimethylsiloxane (HLB/PDMS) TF-SPME device that enabled direct immersion extraction from fish oil. Matrix-matched calibration gave a linear range from 0.075 µg/g to 0.75 µg/g with method limits of quantitation (MLOQ) ranging from 0.07 µg/g to 0.217 µg/g in oil. Standard addition calibration was performed using other fish oils demonstrating comparable slope to the external calibration. As a proof of concept, four fish oil brands were tested for contaminants; 1,1,1,3-tetrachlorodecane, 1,2,9,10-tetrachlorodecane, 1,2,13,14-tetrachlorotetradecane, and 1,1,1,3,14,15-hexachloropentadecane were detected above the MLOQ but below the range provided by the Stockholm Convention. This method provides an effective approach for cleanup and preconcentration of PCAs from oily matrices using inexpensive, and reusable microextraction devices that limit environmental impact of the sample preparation protocol., (Copyright © 2021 Elsevier Ltd. All rights reserved.)
- Published
- 2021
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16. Minimizing transient microenvironment-associated variability for analysis of environmental anthropogenic contaminants via ambient ionization.
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Emmons RV and Gionfriddo E
- Abstract
The rapid and quantitative analysis of anthropogenic contaminants in environmental matrices is crucial for regulatory testing and to elucidate the environmental fate of these pollutants. Direct ambient mass spectrometry (AMS) methodologies greatly increase sample throughput, can be adapted for onsite analysis and are often regarded as semi-quantitative by most developed protocols. One of the limitations of AMS, especially for on site analysis applications, is the irreproducibility of the measurements related to the occurrence of transient microenvironments (TME) and variable background interferences. In this work we report an effective strategy to minimize these effects by hyphenating, for the first time, solid phase microextraction (SPME) arrow to mass spectrometry via a thermal desorption unit (TDU) and direct analysis in real time (DART) source. The developed method was optimized for the extraction and analysis of pesticides and pharmaceuticals from surface water. It was demonstrated that the hyphenation of the SPME and TDU-DART resulted in reduced background contamination, indicating the suitability of the method for onsite analysis even in variable and non-ideal environments. Model analytes were quantitated in the low μg/L range with a total analysis time of less than 5 min, linear dynamic ranges (LDR) and interday reproducibility for most compounds being 2.5-500 μg/L and lower than 10%, respectively. The developed approach provides an excellent analytical tool that can be applied for the onsite high-throughput analysis of water samples as well as air and aereosols. Considering the tunability of our extraction process, time-resolved environmental monitoring can be achieved onsite within minutes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)
- Published
- 2021
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17. Analysis of food samples made easy by microextraction technologies directly coupled to mass spectrometry.
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Gionfriddo E and Gómez-Ríos GA
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- Food Analysis instrumentation, Limit of Detection, Mass Spectrometry instrumentation, Solid Phase Microextraction instrumentation, Spectrometry, Mass, Electrospray Ionization instrumentation, Spectrometry, Mass, Electrospray Ionization methods, Food Analysis methods, Mass Spectrometry methods, Solid Phase Microextraction methods
- Abstract
Because of the complexity and diversity of food matrices, their chemical analysis often entails several analytical challenges to attain accurate and reliable results, especially for multiresidue analysis and ultratrace quantification. Nonetheless, microextraction technology, such as solid-phase microextraction (SPME), has revolutionized the concept of sample preparation for complex matrices because of its nonexhaustive, yet quantitative extraction approach and its amenability to coupling to multiple analytical platforms. In recent years, microextraction devices directly interfaced with mass spectrometry (MS) have redefined the analytical workflow by providing faster screening and quantitative methods for complex matrices. This review will discuss the latest developments in the field of food analysis by means of microextraction approaches directly coupled to MS. One key feature that differentiates SPME-MS approaches from other ambient MS techniques is the use of matrix compatible extraction phases that prevent biofouling, which could drastically affect the ionization process and are still capable of selective extraction of the targeted analytes from the food matrix. Furthermore, the review examines the most significant applications of SPME-MS for various ionization techniques such as direct analysis in real time, dielectric barrier desorption ionization, and some unique SPME geometries, for example, transmission mode SPME and coated blade spray, that facilitate the interface to MS instrumentation., (© 2020 John Wiley & Sons, Ltd.)
- Published
- 2021
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18. Implementing Green Analytical Methodologies Using Solid-Phase Microextraction: A Review.
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Billiard KM, Dershem AR, and Gionfriddo E
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- Animals, Chickens, Food Analysis, Food Contamination, Fruit, Gas Chromatography-Mass Spectrometry, Microwaves, Red Meat, Triazoles chemistry, Green Chemistry Technology methods, Solid Phase Microextraction methods
- Abstract
Implementing green analytical methodologies has been one of the main objectives of the analytical chemistry community for the past two decades. Sample preparation and extraction procedures are two parts of analytical method development that can be best adapted to meet the principles of green analytical chemistry. The goal of transitioning to green analytical chemistry is to establish new methods that perform comparably-or superiorly-to traditional methods. The use of assessment tools to provide an objective and concise evaluation of the analytical methods' adherence to the principles of green analytical chemistry is critical to achieving this goal. In this review, we describe various sample preparation and extraction methods that can be used to increase the greenness of a given analytical method. We gave special emphasis to modern microextraction technologies and their important contributions to the development of new green analytical methods. Several manuscripts in which the greenness of a solid-phase microextraction (SPME) technique was compared to other sample preparation strategies using the Green Analytical Procedure Index (GAPI), a green assessment tool, were reviewed.
- Published
- 2020
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19. Biocompatible SPME fibers for direct monitoring of nicotine and its metabolites at ultra trace concentration in rabbit plasma following the application of smoking cessation formulations.
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Godage NH, Cudjoe E, Neupane R, Boddu SH, Bolla PK, Renukuntla J, and Gionfriddo E
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- Anabasine blood, Anabasine isolation & purification, Anabasine standards, Animals, Chromatography, High Pressure Liquid standards, Cotinine analogs & derivatives, Cotinine blood, Cotinine isolation & purification, Cotinine standards, Isotope Labeling, Limit of Detection, Nicotine analogs & derivatives, Nicotine isolation & purification, Nicotine metabolism, Nicotine standards, Rabbits, Reference Standards, Reproducibility of Results, Smoking Cessation, Solid Phase Microextraction, Tandem Mass Spectrometry standards, Time Factors, Nicotine blood
- Abstract
The ultra-trace determination of nicotine and its 4 major metabolites (cotinine, nornicotine, norcotinine and anabasine) from rabbit plasma was achieved by a newly developed solid phase microextraction-liquid chromatography-tandem mass spectrometry method. Extraction of the target analytes was performed with hydrophilic/lipophilic balance-polyacrylonitrile SPME fibers. Dual fiber extraction was necessary to guarantee improved recovery at parts-per-trillion levels. Liquid chromatographic analysis was achieved in a 6-min run using a C18 (1.9 µm C18, 50 mm x 2.1 mm) column with a mobile phase flow rate of 0.4 mL/min. Tandem mass spectrometry was used for detection and quantification in positive electrospray ionization (ESI+) mode for all the targeted analytes. Two stable isotope-labeled internal standards were used for signal correction and accurate quantification. The mass spectrometer with laminar flow ion flux transport, guaranteed improved signal stability, minimal contamination of the ion guide and reproducibility into the first quadrupole analyzer. The method was validated in line with the Food and Drug Administration (FDA) guidelines for bioanalytical method validation. The results met the acceptance criteria as proposed by the FDA: accuracy was tested at 0.35, 10 and 75 µg L
- 1 and ranged between 98.3-112.2% for nicotine, 94.1-101.9% for cotinine, 94.7-107.0% for nornicotine, 81.1-107.2% for norcotinine and 94.3-115.2% for anabasine, with precision up to 14.2%. Stability tests indicated that all the targeted analytes were stable in the desorption solution for at least 1 week. LOQs ranged from 0.05 to 1 µg L-1 . The method was successfully applied to analyze plasma samples obtained from rabbits following transdermal application of a smoking cessation formulation loaded with solid lipid nanoparticles containing a nicotine-stearic acid conjugate., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)- Published
- 2020
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20. Use of natural sorbents as alternative and green extractive materials: A critical review.
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Godage NH and Gionfriddo E
- Subjects
- Adsorption, Molecularly Imprinted Polymers chemistry, Biopolymers chemistry, Green Chemistry Technology methods, Metals, Heavy isolation & purification, Organic Chemicals isolation & purification, Solid Phase Microextraction methods
- Abstract
The increasing concern about environmental degradation and resource depletion has inspired the analytical chemistry community to develop analytical methods that comply as much as possible with the principles of Green Analytical Chemistry. Significant progress has been made in greening sample preparation strategies by miniaturizing sampling devices and decreasing the amount of sorptive phase needed for efficient extraction of targeted molecules. In this context, the use of natural sorbents represents an additional and convenient option for green sample preparation. The advantages of using natural sorbents for extraction include their availability from renewable sources, low toxicity and biodegradability. In this review, we describe the use of various natural sorbents for metals and organic molecules extraction, focusing on the most innovative applications within the decade 2009-2019. Particular emphasis is given to the description of commonly used biopolymers - e.g. cellulose, chitin, and lignin - and their use in a variety of sample preparation strategies. We also refer to different functionalization approaches that enhance the extraction efficiency of natural sorbents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)
- Published
- 2020
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21. Corrigendum to "Blue light-triggered photochemistry and cytotoxicity of retinal cellular signalling" [Volume 69 (2020), 109,547].
- Author
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Ratnayake K, Payton JL, Meger ME, Godage NH, Rajanayake KK, Isailovic D, Gionfriddo E, and Karunarathne A
- Published
- 2020
- Full Text
- View/download PDF
22. Optimization of thin film solid phase microextraction and data deconvolution methods for accurate characterization of organic compounds in produced water.
- Author
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Emmons RV, Liden T, Schug KA, and Gionfriddo E
- Abstract
The continued rise in the extraction of unconventional oil and gas across the globe poses many questions about how to manage these relatively new waste-streams. Produced water, the primary waste by-product, contains a diverse number of anthropogenic additives together with the numerous hydrocarbons extracted from the well. Due to potential environmental hazards, it is critical to characterize the chemical composition of this type of waste before proper disposal or remediation/reuse. In this work, a thin film solid phase microextraction approach was developed and optimized to characterize produced water. The thin film device consisted of hydrophilic-lipophilic balance particles embedded in polydimethylsiloxane and immobilized on a carbon mesh surface. These devices were chosen to provide broad extraction coverage and high reusability. Various parameters were evaluated to ensure reproducible results while minimizing analyte loss. This optimized protocol, consisting of a 15 min extraction followed by a short (3 s) rinsing step, enabled the reproducible analysis of produced water without any sample pretreatment. Extraction efficiency was suitable for both produced water additives and hydrocarbons. The developed approach was able to tentatively identify a total of 201 compounds from produced water samples, by using one-dimensional gas chromatography hyphenated to mass spectrometry and data deconvolution., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2020
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23. Blue light-triggered photochemistry and cytotoxicity of retinal.
- Author
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Ratnayake K, Payton JL, Meger ME, Godage NH, Gionfriddo E, and Karunarathne A
- Subjects
- DNA Damage, HeLa Cells, Humans, Lipid Peroxidation, Oxidative Stress, Photochemical Processes, Reactive Oxygen Species metabolism, Light adverse effects, Retinaldehyde toxicity
- Abstract
The chemical- and photo- toxicity of chromophore retinal on cells have long been debated. Although we recently showed that retinal and blue light exposure interrupt cellular signaling, a comprehensive study examining molecular underpinnings of this perturbation and its consequences to cellular fate is lacking. Here, we report molecular evidence for blue light excited-retinal induced oxidative damage of polyunsaturated lipid anchors in membrane-interacting signaling molecules and DNA damage in cells using live-cell imaging and in vitro experimentation. The incurred molecular damage irreversibly disrupted subcellular localization of these molecules, a crucial criterion for their signaling. We further show retinal accumulation in lipid-bilayers of cell membranes could enhance the lifetime of retinal in cells. Comparative response-signatures suggest that retinal triggers reactions upon photoexcitation similar to photodynamic therapy agents and generate reactive oxygen species in cells. Additionally, data also shows that exposing retinal-containing cells to sunlight induces substantial cytotoxicity. Collectively, our results explain a likely in vivo mechanism and reaction conditions under which bio-available retinal in physiological light conditions damages cells., Competing Interests: Declaration of Competing Interest Authors declare no conflicts of interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)
- Published
- 2020
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24. Direct-immersion SPME in soy milk for pesticide analysis at trace levels by means of a matrix-compatible coating.
- Author
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Gionfriddo E, Gruszecka D, Li X, and Pawliszyn J
- Subjects
- Dimethylpolysiloxanes chemistry, Limit of Detection, Pesticide Residues analysis, Pesticide Residues isolation & purification, Polyvinyls chemistry, Soy Milk chemistry, Food Contamination analysis, Gas Chromatography-Mass Spectrometry methods, Pesticides analysis, Pesticides isolation & purification, Solid Phase Microextraction methods, Soy Milk metabolism
- Abstract
This study demonstrates a newly developed PDMS/DVB/PDMS fiber's suitability for the determination of pesticides in soy milk via direct-immersion solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry, eliminating the need for extensive sample pre-treatment procedures. Fouling accumulation on the coating surface was further minimized by implementing rapid and effective pre- and post-desorption cleaning steps. Under optimum conditions, the fiber was used to perform over 120 extractions while maintaining RSD values of less than 24.5% for 10 extracted pesticides. By comparison, the RSD values ranged from 8.4% to 42.8% over 80 extractions using a commercial PDMS/DVB fiber. The optimized conditions were used to fully validate a quantitative method for the targeted analytes by matrix-matched calibration and isotopically labeled internal standard correction. Significantly, the proposed method was able to achieve limits of quantitation (1-2.5 μg/kg) for the targeted analytes that were below the Maximum Residue Levels mandated for soy-based products. Accuracy, intra- and inter-day repeatability were also satisfactory. The proposed PDMS/DVB/PDMS fiber dramatically improved repeatability and suitability for direct-immersion SPME in soy milk, and represents a good alternative to other extraction methods for high-throughput quantitative analysis of pesticide residues in soy-based products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)
- Published
- 2020
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25. Application of in vivo solid phase microextraction (SPME) in capturing metabolome of apple (Malus ×domestica Borkh.) fruit.
- Author
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Risticevic S, Souza-Silva EA, Gionfriddo E, DeEll JR, Cochran J, Hopkins WS, and Pawliszyn J
- Subjects
- Discriminant Analysis, Gas Chromatography-Mass Spectrometry, Least-Squares Analysis, Malus growth & development, Fruit metabolism, Malus metabolism, Metabolome, Solid Phase Microextraction methods
- Abstract
An in vivo direct-immersion SPME sampling coupled to comprehensive two-dimensional gas chromatography - time-of-flight mass spectrometry (GCxGC-ToFMS) was employed to capture real-time changes in the metabolome of 'Honeycrisp' apples during ripening on the tree. This novel sampling approach was successful in acquiring a broad metabolic fingerprint, capturing unique metabolites and detecting changes in metabolic profiles associated with fruit maturation. Several metabolites and chemical classes, including volatile esters, phenylpropanoid metabolites, 1-octen-3-ol, hexanal, and (2E,4E)-2,4-hexadienal were found to be up-regulated in response to fruit maturation. For the first time, Amaryllidaceae alkaloids, metabolites with important biological activities, including anti-cancer, anti-viral, anti-parasitic, and acetylcholinesterase (AChE) inhibitory activity, were detected in apples. Considering the elimination of oxidative degradation mechanisms that adversely impact the representativeness of metabolome obtained ex vivo, and further evidence that lipoxygenase (LOX) pathway contributes to volatile production in intact fruit, in vivo DI-SPME represents an attractive approach for global plant metabolite studies.
- Published
- 2020
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26. Development and validation of a fully automated solid phase microextraction high throughput method for quantitative analysis of multiresidue veterinary drugs in chicken tissue.
- Author
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Khaled A, Gionfriddo E, Acquaro V Jr, Singh V, and Pawliszyn J
- Subjects
- Animals, Automation, Drug Residues chemistry, Hydrophobic and Hydrophilic Interactions, Solvents chemistry, Time Factors, Veterinary Drugs chemistry, Chickens, Drug Residues analysis, Drug Residues isolation & purification, Food Contamination analysis, Solid Phase Microextraction methods, Veterinary Drugs analysis, Veterinary Drugs isolation & purification
- Abstract
This paper presents the development and validation of a fully automated, high-throughput multiclass, multiresidue method for quantitative analysis of 77 veterinary drugs in chicken muscle via direct immersion solid phase microextraction (DI-SPME) and ultra-high pressure liquid chromatography-electrospray ionization - tandem mass spectrometry (UHPLC-ESI-MS/MS). The selected drugs represent more than 12 different classes of drugs characterized by varying physical and chemical properties. A Hydrophilic-lipophilic balance (HLB)/polyacrylonitrile (PAN) extraction phase, prepared using HLB particles synthesized in-house, yielded the best extraction/desorption performance among four different SPME extraction phases evaluated in the current work. The developed SPME method was optimized in terms of SPME coating and geometry, desorption solvent, extraction and rinsing conditions, and extraction and desorption times. Multivariate analysis was performed to determine the optimal desorption solvent for the proposed application. The developed method was validated according to the Food and Drug Administration (FDA) guidelines, taking into account Canadian maximum residue limits (MRLs) and US maximum tolerance levels for veterinary drugs in meat. Method accuracy ranged from 80 to 120% for at least 73 compounds, with relative standard deviation of 1-15%. Inter-day precision ranged from 4 to 15% for 70 compounds. Determination coefficients values were higher than 0.991 for all compounds under study with no significant lack of fit (p > 0.05) at the 5% level. In terms of limits of quantitation, the method was able to meet both Canadian and US regulatory levels for all compounds under study., (Copyright © 2018 Elsevier B.V. All rights reserved.)
- Published
- 2019
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27. Fast screening of illicit drugs in beverages and biological fluids by direct coupling of thin film microextraction to dielectric barrier discharge ionization-mass spectrometry.
- Author
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Mirabelli MF, Gionfriddo E, Pawliszyn J, and Zenobi R
- Subjects
- Humans, Limit of Detection, Male, Ultrasonic Waves, Beverages analysis, Food Contamination analysis, Illicit Drugs blood, Illicit Drugs urine, Mass Spectrometry methods, Solid Phase Microextraction methods
- Abstract
A direct and fast method for screening and quantification of illicit drugs in beverages and biological fluids was developed by using dielectric barrier discharge (DBD) as ionization technique, in combination with high-resolution mass spectrometry. Extraction of the targeted analytes was carried out with thin film microextraction (TFME) using ultrasound as agitation method. The targeted analytes were then thermally desorbed and introduced into the source without the need for any cryofocusing apparatus. The performance of this new analytical set up were compared to conventional TFME-TDU-GC/MS, showing enhanced linear dynamic range and lower limits of quantitation (low pg ml-1) achievable at the same extraction conditions (5 min extraction time). The performance of the method was tested in different beverages and body fluids, confirming its applicability for quantitative analysis of the targeted drugs in complex samples.
- Published
- 2019
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28. Development and validation of eco-friendly strategies based on thin film microextraction for water analysis.
- Author
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Piri-Moghadam H, Gionfriddo E, Grandy JJ, Alam MN, and Pawliszyn J
- Subjects
- Gas Chromatography-Mass Spectrometry, Solid Phase Microextraction, Environmental Monitoring methods, Green Chemistry Technology, Water chemistry, Water Pollutants, Chemical analysis
- Abstract
The aim of the current study is the establishment of Green Analytical Chemistry strategies for water analysis by elimination/reduction of hazardous chemicals, energy consumption, and waste generation throughout the entire analytical workflow. The first approach introduced in this manuscript consists of addition of water to a sampling vessel that contains a thin film microextraction (TFME) device, followed by removal of the device after equilibration, and subsequent quantification of the extracted components by thermal desorption GC/MS. In this approach, namely the in-bottle TFME approach, analyte-loss associated errors that stem from analyte adherence to glass surfaces and/or degradation are avoided as extraction occurs in situ, while analytes are isolated from a complex matrix that contains degradation agents (bacteria, oxidizing or reducing species, etc.). This procedure also circumvents the splitting of original samples into sub-samples. The second approach involves the use of portable TFME devices that facilitate on-site extraction of compounds, therefore eliminating the use of collection vessels, a factor known to potentially introduce errors into analysis. The herein described procedure involves attachment of the TFME device to drill accessories, analyte extraction via direct immersion into sampled site, and subsequent on-site instrumental analysis, which is carried out with the use of a portable GC/MS containing an appropriate thermal desorption interface, or alternatively, by transferring the membrane to the laboratory for bench-top GC/MS analysis. To facilitate a better understanding of the processes governing the developed approaches, modeling by COMSOL Multiphysics® software was performed. The findings of this study were applied for further method optimization, and the optimized developed methods were then applied for on-site surface water analyses. Finally, the greenness of the developed methods was evaluated with use of the eco-scale assessment, with obtained scores compared to that of the US EPA 8270 method., (Copyright © 2018 Elsevier B.V. All rights reserved.)
- Published
- 2018
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29. Direct immersion solid-phase microextraction analysis of multi-class contaminants in edible seaweeds by gas chromatography-mass spectrometry.
- Author
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Zhang L, Gionfriddo E, Acquaro V Jr, and Pawliszyn J
- Subjects
- Food Contamination analysis, Hydrophobic and Hydrophilic Interactions, Limit of Detection, Pesticide Residues isolation & purification, Polychlorinated Biphenyls isolation & purification, Polycyclic Aromatic Hydrocarbons isolation & purification, Solid Phase Microextraction, Temperature, Gas Chromatography-Mass Spectrometry, Pesticide Residues analysis, Polychlorinated Biphenyls analysis, Polycyclic Aromatic Hydrocarbons analysis, Seaweed chemistry
- Abstract
The present work aimed at the development of a simple and accurate direct immersion-solidphase microextraction-gas-chromatography-mass spectrometry (DI-SPME-GC-MS) method for simultaneous determination of PAHs, PCBs, and pesticide residues in edible seaweeds. As the target contaminants possess a wide range of physical-chemical properties, multivariate experimental design was used for method optimization. In particular, two different methods were optimized and validated: one that allows for simultaneous determination of all targets, and an ad hoc method for determination of hydrophobic analytes, a class that often poses a challenge for extraction from food matrices. Optimum conditions suitable for simultaneous quantitation of all targeted compounds, namely buffer at pH = 7.0, 20% acetone (v/v), 10% NaCl (w/w), 0.02% NaN
3 , 60 min DI extraction at 55 °C, and 20 min desorption at 270 °C, afforded limits of quantitation (LOQs) in the range of 1-30 μg kg-1 , a wide linear range of 5-2000 μg kg-1 , the attainment of satisfactory determination coefficients (R2 ˃0.99) with no significant lack of fit (p > 0.05) at the 5% level, and satisfactory accuracy and precision values. By modifying the extraction conditions to favor extraction of the most hydrophobic analytes (e.g. higher amount of organic modifier and pH, and lower salt content) lower LOQs were obtained for these compounds ranging from 0.2 to 13.3 μg kg-1 . The established methods were then used for screening of commercial, edible dry seaweeds, with PCBs (≤16.0 ng g-1 ) and PAHs (≤15.5 ng g-1 ) detected in some samples. This method overcomes most challenges commonly encountered in dry sample analysis applications, and represents the first report of a DI-SPME method employing the matrix-compatible fiber for simultaneous multiclass and multiresidue analysis of seaweeds., (Copyright © 2018 Elsevier B.V. All rights reserved.)- Published
- 2018
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30. Exploiting the tunable selectivity features of polymeric ionic liquid-based SPME sorbents in food analysis.
- Author
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Gionfriddo E, Souza-Silva ÉA, Ho TD, Anderson JL, and Pawliszyn J
- Abstract
In this work, the performances of polymeric ionic liquid (PIL) based solid-phase microextraction (SPME) coatings were assessed for applications concerning food safety and quality. Two different polymeric ionic liquid coatings, namely poly(1-4-vinylbenzyl-3-hexadecylimidazolium) bis[(trifluoromethyl)sulfonyl] imide (poly([VBHDIM][NTf2]), PIL 1, and N,N-didecyl-N-methyl-d-glucaminium poly(2-methyl-acrylic acid 2-[1-(3-{2-[2-(3-trifluoromethanesulfonylamino-propoxy)-ethoxy]-ethoxy}-propylamino)-vinylamino]-ethyl ester) (poly([DDMGlu][MTFSI]), PIL 2, were evaluated. The PIL-based coatings were compared to commercially available SPME coatings in terms of their performance toward extraction of pesticides and fruit metabolites. The partition coefficients (K
fs ) of the tested coatings were calculated, with PIL 1 demonstrating similar or better performance compared to the commercial coatings. Design of experiment (DoE) was applied to optimize the parameters that most influenced SPME extraction, and a quantitative method for determination of 5 organophosphorus pesticides was developed by using PIL-based coatings and commercial SPME fibers. Despite the thin layer of the sorbent coating, PIL 1 achieved limits of quantitation at the low part-per-billion level. Moreover, in a comparative investigation of analyte coverage carried out via HS-SPME-GCxGC-ToF/MS with grape homogenate as model matrix, excellent performances were observed for the PIL-based coatings toward the determination of fruit metabolites, demonstrating their capability towards broad extractive coverage of analytes characterized by various physicochemical properties., (Copyright © 2018 Elsevier B.V. All rights reserved.)- Published
- 2018
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31. A quantitative approach for pesticide analysis in grape juice by direct interfacing of a matrix compatible SPME phase to dielectric barrier discharge ionization-mass spectrometry.
- Author
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Mirabelli MF, Gionfriddo E, Pawliszyn J, and Zenobi R
- Abstract
We evaluated the performance of a dielectric barrier discharge ionization (DBDI) source for pesticide analysis in grape juice, a fairly complex matrix due to the high content of sugars (≈20% w/w) and pigments. A fast sample preparation method based on direct immersion solid-phase microextraction (SPME) was developed, and novel matrix compatible SPME fibers were used to reduce in-source matrix suppression effects. A high resolution LTQ Orbitrap mass spectrometer allowed for rapid quantification in full scan mode. This direct SPME-DBDI-MS approach was proven to be effective for the rapid and direct analysis of complex sample matrices, with limits of detection in the parts-per-trillion (ppt) range and inter- and intra-day precision below 30% relative standard deviation (RSD) for samples spiked at 1, 10 and 10 ng ml
-1 , with overall performance comparable or even superior to existing chromatographic approaches.- Published
- 2018
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32. Investigating the robustness and extraction performance of a matrix-compatible solid-phase microextraction coating in human urine and its application to assess 2-6-ring polycyclic aromatic hydrocarbons using GC-MS/MS.
- Author
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Naccarato A, Gionfriddo E, Elliani R, Pawliszyn J, Sindona G, and Tagarelli A
- Subjects
- Adult, Gas Chromatography-Mass Spectrometry, Healthy Volunteers, Humans, Young Adult, Polycyclic Aromatic Hydrocarbons urine, Solid Phase Microextraction
- Abstract
In this work, a polydimethylsiloxane/divinylbenzene fiber overcoated with a layer of polydimethylsiloxane was evaluated as analytical sampling tool for the first time in human urine. Urinary polycyclic aromatic hydrocarbons with 2-6 aromatic rings were considered as target compounds. The analyte uptake in kinetic and thermodynamic regime was evaluated and compared to the performances of polydimethylsiloxane/divinylbenzene and polydimethylsiloxane fibers. The assessment of the robustness and endurance of the overcoated fiber was carried out by direct immersion solid-phase microextraction in undiluted urine performing up to 120 consecutive extractions. The overcoated fiber was then used to develop a fast and easy direct immersion solid-phase microextraction with gas chromatography and triple quadrupole mass spectrometry protocol for the quantification of the target polycyclic aromatic hydrocarbons. The attained values of accuracy and precision were 75-114% and 2-19%, respectively, while the limits of quantification ranged between 0.05 and 1 ng/L. The proposed protocol was applied to the screening of urine samples collected from smoking and nonsmoking volunteers. The successful results obtained by using the overcoated fiber create not only new alternatives for polycyclic aromatic hydrocarbon exposure assessment but also new perspectives for the application of direct immersion solid-phase microextraction to the analysis of bioclinical matrixes., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2018
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33. Advances in Solid Phase Microextraction and Perspective on Future Directions.
- Author
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Reyes-Garcés N, Gionfriddo E, Gómez-Ríos GA, Alam MN, Boyacı E, Bojko B, Singh V, Grandy J, and Pawliszyn J
- Published
- 2018
- Full Text
- View/download PDF
34. Towards on-site analysis of complex matrices by solid-phase microextraction-transmission mode coupled to a portable mass spectrometer via direct analysis in real time.
- Author
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Gómez-Ríos GA, Vasiljevic T, Gionfriddo E, Yu M, and Pawliszyn J
- Abstract
On-site screening for target analytes in complex matrices, such as biofluids and food specimens, not only requires reliable and portable analytical instrumentation, but also solvent-free and easy-to-use sampling/sample preparation approaches that allow analytes of interest to be isolated from such matrices. The integration of sampling devices with field deployable instruments should be as efficient as possible, and should aim to provide rapid, precise, and accurate results that enable quick on-site decision. In this study, we evaluated solid-phase microextraction-transmission (SPME-TM) coupled to a portable single quadrupole MS system, via direct analysis in real time (DART), as an effective tool for the rapid screening of target analytes in biological and food matrices. Limits of quantitation (LOQ) in the low parts-per-billion levels (≤50 ng mL
-1 ) were attained for most of the investigated analytes with total analysis times under 2 min per sample. Furthermore, we explored the suitability of this technology for on-site rapid molecular profiling of complex matrices. As a proof-of-concept, we demonstrate the rapid identification of milk samples from assorted animal and vegetal sources.- Published
- 2017
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- View/download PDF
35. Ultrafast Screening and Quantitation of Pesticides in Food and Environmental Matrices by Solid-Phase Microextraction-Transmission Mode (SPME-TM) and Direct Analysis in Real Time (DART).
- Author
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Gómez-Ríos GA, Gionfriddo E, Poole J, and Pawliszyn J
- Subjects
- Animals, Beverages analysis, Citrus sinensis chemistry, Limit of Detection, Rivers chemistry, Vitis chemistry, Food Contamination analysis, Pesticides analysis, Solid Phase Microextraction methods, Tandem Mass Spectrometry methods, Water Pollution, Chemical analysis
- Abstract
The direct interface of microextraction technologies to mass spectrometry (MS) has unquestionably revolutionized the speed and efficacy at which complex matrices are analyzed. Solid Phase Micro Extraction-Transmission Mode (SPME-TM) is a technology conceived as an effective synergy between sample preparation and ambient ionization. Succinctly, the device consists of a mesh coated with polymeric particles that extracts analytes of interest present in a given sample matrix. This coated mesh acts as a transmission-mode substrate for Direct Analysis in Real Time (DART), allowing for rapid and efficient thermal desorption/ionization of analytes previously concentrated on the coating, and dramatically lowering the limits of detection attained by sole DART analysis. In this study, we present SPME-TM as a novel tool for the ultrafast enrichment of pesticides present in food and environmental matrices and their quantitative determination by MS via DART ionization. Limits of quantitation in the subnanogram per milliliter range can be attained, while total analysis time does not exceed 2 min per sample. In addition to target information obtained via tandem MS, retrospective studies of the same sample via high-resolution mass spectrometry (HRMS) were accomplished by thermally desorbing a different segment of the microextraction device.
- Published
- 2017
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36. A new and efficient Solid Phase Microextraction approach for analysis of high fat content food samples using a matrix-compatible coating.
- Author
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De Grazia S, Gionfriddo E, and Pawliszyn J
- Subjects
- Dimethylpolysiloxanes, Gas Chromatography-Mass Spectrometry, Limit of Detection, Food Analysis methods, Food Contamination analysis, Persea chemistry, Solid Phase Microextraction methods
- Abstract
The current work presents the optimization of a protocol enabling direct extraction of avocado samples by a new Solid Phase Microextraction matrix compatible coating. In order to further extend the coating life time, pre-desorption and post-desorption washing steps were optimized for solvent type, time, and degree of agitation employed. Using optimized conditions, lifetime profiles of the coating related to extraction of a group of analytes bearing different physical-chemical properties were obtained. Over 80 successive extractions were carried out to establish coating efficiency using PDMS/DVB 65µm commercial coating in comparison with the PDMS/DVB/PDMS. The PDMS/DVB coating was more prone to irreversible matrix attachment on its surface, with consequent reduction of its extractive performance after 80 consecutive extractions. Conversely, the PDMS/DVB/PDMS coating showed enhanced inertness towards matrix fouling due to its outer smooth PDMS layer. This work represents the first step towards the development of robust SPME methods for quantification of contaminants in avocado as well as other fatty-based matrices, with minimal sample pre-treatment prior to extraction. In addition, an evaluation of matrix components attachment on the coating surface and related artifacts created by desorption of the coating at high temperatures in the GC-injector port, has been performed by GCxGC-ToF/MS., (Copyright © 2017 Elsevier B.V. All rights reserved.)
- Published
- 2017
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37. Inter-laboratory validation of a thin film microextraction technique for determination of pesticides in surface water samples.
- Author
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Piri-Moghadam H, Gionfriddo E, Rodriguez-Lafuente A, Grandy JJ, Lord HL, Obal T, and Pawliszyn J
- Abstract
The primary goal of the present study is the inter-laboratory evaluation of a thin film microextraction (TFME) technique to be used as an alternative approach to liquid-liquid extraction (LLE). Polydimethylsiloxane/divinylbenzene (PDMS/DVB) and PDMS/DVB-carbon mesh supported membranes were used for the extraction of 23 targeted pesticides, while a thermal desorption unit (TDU) was employed to transfer these analytes to a GC/MS instrument for separation and detection. After optimization of the most critical parameters, both membranes were capable of achieving limits of detection (LOD) in the low ng L
-1 range while demonstrating excellent robustness, withstanding up to 100 extractions/desorption cycles. Furthermore, limits of quantification (LOQ) between 0.025 and 0.50 μg L-1 were achieved for the 23 compounds selected from several classes of pesticides with a wide range of polarities. A wide linear range of 0.025-10.0 μg L-1 with strong correlation to response (R2 > 0.99) was attained for most of the studied analytes. Both membranes showed good accuracy and repeatability at three levels of concentration. Moreover, the method was also validated through blind split analyses of 18 surface water samples, collected within 3 months, using TFME at the University of Waterloo and LLE at Maxxam Analytics (Mississauga, ON) which is an accredited commercial analytical laboratory. Good agreement between the two methods was achieved with accuracy values ranging from 70 to 130%, for the majority of analytes in the samples collected. At the concentration levels investigated, 90% of the analytes were quantifiable by TFME, whereas only 53% of the compounds were reportable using the LLE method particularly at concentrations lower than 1 μg L-1 . The comparison of TFME and LLE from several analytical aspects demonstrated that the novel TFME method gave similar accuracy to LLE, while providing additional advantages including higher sensitivity, lower sample volume, thus reduced waste production, and faster analytical throughput. Given the sensitivity, simplicity, low cost, accuracy, greenness and relatively fast procedure of TFME, it shows great potential for adoption in analytical laboratories as an alternative to LLE., (Copyright © 2017 Elsevier B.V. All rights reserved.)- Published
- 2017
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38. New Generation of Solid-Phase Microextraction Coatings for Complementary Separation Approaches: A Step toward Comprehensive Metabolomics and Multiresidue Analyses in Complex Matrices.
- Author
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Gionfriddo E, Boyacı E, and Pawliszyn J
- Abstract
In this work, a new generation of solid-phase microextraction (SPME) coatings based on polytetrafluoroethylene amorphous fluoroplastics (PTFE AF 2400) as a particle binder is presented. The developed coating was tested for thermal and solvent-assisted desorption, demonstrating its compatibility with both gas- and liquid-chromatographic platforms. The incorporation of hydrophilic-lipophilic balance (HLB) adsorptive particles provided optimal extraction coverage for analytes bearing a broad range of hydrophobicities and molecular weights and of varied chemical diversity. The performance of the newly developed coating was compared to already established coatings based on different polymers such as divinylbenzene/carboxen/polydimethylsiloxane (DVB/Car/PDMS) and octadecyl/benzenesulfonic acid/polyacrylonitrile (C18/SCX/PAN) in order to assess the new prototype versus the existing technology. As this is the first documented instance of PTFE AF being used as a particle immobilizer for SPME, an assessment of the analyte uptake rate and extraction capability of the developed coating was carried out in comparison to other conventionally used polymers. Moreover, the new SPME probes were used to validate an analytical method for determination of banned doping substances, achieving limits of quantitation below the minimum required performance limits (MRPLs) set by the World Anti-Doping Agency (WADA) for most compounds. Considering the broad coverage of the coating in terms of analytes extracted and its suitability for both thermal- and solvent-assisted desorption, these new SPME probes will properly suit various metabolomics applications that involve the use of both gas- and liquid-chromatography.
- Published
- 2017
- Full Text
- View/download PDF
39. Insights into the Effect of the PDMS-Layer on the Kinetics and Thermodynamics of Analyte Sorption onto the Matrix-Compatible Solid Phase Microextraction Coating.
- Author
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Souza-Silva ÉA, Gionfriddo E, Alam MN, and Pawliszyn J
- Abstract
The currently presented research investigated the performance of matrix compatible PDMS-overcoated fibers (PDMS-DVB/PDMS) as compared to unmodified PDMS/DVB coatings using aqueous samples and employing a wide range of analyte polarities, molecular weights, and functionalities. In the first part of the work, a kinetic approach was taken to investigate the effect of the PDMS outer layer on the uptake rate of analytes during the mass transfer process. In short, the results can be simplified into two models: (1) the rate-limiting step is the diffusion through the coating and (2) the rate-limiting step is the diffusion through the aqueous diffusional boundary layer. For polar compounds, according to the theoretical discussion, the rate-limiting step is the diffusion through the coating; therefore, the outer PDMS layer influences the uptake rate into the matrix compatible coatings. On the other hand, for nonpolar compounds, the rate-limiting step of the uptake process is diffusion through the aqueous diffusional boundary layer; as such, the overcoated PDMS does not affect uptake rate into the matrix-compatible coatings as compared to DVB/PDMS fibers. From a thermodynamic point of view, the calculated fiber constants further corroborate the hypothesis that the additional PDMS layer does not impair the extraction phase capacity.
- Published
- 2017
- Full Text
- View/download PDF
40. A facile and fully automated on-fiber derivatization protocol for direct analysis of short-chain aliphatic amines using a matrix compatible solid-phase microextraction coating.
- Author
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Gionfriddo E, Passarini A, and Pawliszyn J
- Subjects
- Benzaldehydes chemistry, Indicators and Reagents, Lakes chemistry, Rivers chemistry, Solid Phase Microextraction methods, Temperature, Amines analysis, Dimethylpolysiloxanes chemistry, Polyvinyls chemistry, Water Pollutants, Chemical analysis
- Abstract
Solid-phase microextraction (SPME) analysis of short-chain aliphatic amines (C3-C6) in aqueous solutions was investigated using pentafluorobenzaldehyde (PFBAY) as on-fiber derivatization reagent. A standard gas generating vial agent was used for on-fiber loading of the derivatization agent so as to avoid the need for its regeneration at each derivatization cycle. Several parameters such as loading time, reaction temperature, and reaction/extraction time were optimized for headspace and direct sampling in aqueous solutions. Three different coating chemistries were tested and their performances compared in order to achieve the best compromise between sensitivity and analysis throughput. The newly developed PDMS/DVB/PDMS coating showed superior performance in terms of extraction efficiency while the capability to prevent on-fiber degradation of the derivatizing products. The optimized method was used for quantitation of short-chain aliphatic amines in aqueous samples and provided detection limits in the low ppb range for all the amines tested with accuracy values between 79 and 120%. The method was applied towards the analysis of environmental water samples and the accuracy of the results was evaluated by different calibration approaches., (Copyright © 2016 Elsevier B.V. All rights reserved.)
- Published
- 2016
- Full Text
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41. Solid Phase Microextraction On-Fiber Derivatization Using a Stable, Portable, and Reusable Pentafluorophenyl Hydrazine Standard Gas Generating Vial.
- Author
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Poole JJ, Grandy JJ, Gómez-Ríos GA, Gionfriddo E, and Pawliszyn J
- Abstract
Solid phase microextraction (SPME) on-fiber derivatization methods have facilitated the achievement of lower detection limits and targeted analysis of various substances that exhibit poor chromatographic behavior, thermal instability, or high reactivity while limiting the use of organic solvents. However, previously developed on-fiber derivatization methods have been hindered by poor loading reproducibility and standard lifetime due to derivatization reagent reactivity. In addition, this reactivity often results in these reagents demonstrating toxic effects, complicating handling and standard formulation. To address this, a reusable standard gas generating vial containing pentafluorophenyl hydrazine (PFPH) has been developed. With this development, SPME fibers can now be reproducibly loaded with derivatization reagent, from an easy to use and safe platform. Validation of the vial using C4-C9 linear aldehyde standards as target analytes demonstrated intrabatch vial reproducibility (2% relative standard deviation (RSD), n = 4), along with PFPH headspace stability over a period of 11 weeks, facilitating reduced reagent consumption due to standard longevity. In addition, reproducibility of the derivatization reaction was observed over 1 week (RSD < 9%), and the linear concentration range was evaluated using headspace extractions from aqueous aldehyde solutions (R(2) > 0.996, 10-200 ppb v/v). Finally, the PFPH-generating vial was applied to the monitoring of volatile aldehydes generated during meat spoilage, as well as an on-site application where the free and total concentration of formaldehyde was determined in car exhaust using a portable GC/MS. To the best of our knowledge, the standard gas generating vial proposed in this work is the first documented device for the long-term storage of reusable headspace standards for a reactive, toxic, and otherwise unstable derivatization reagent standard.
- Published
- 2016
- Full Text
- View/download PDF
42. Methodical evaluation and improvement of matrix compatible PDMS-overcoated coating for direct immersion solid phase microextraction gas chromatography (DI-SPME-GC)-based applications.
- Author
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Souza-Silva ÉA, Gionfriddo E, Shirey R, Sidisky L, and Pawliszyn J
- Subjects
- Limit of Detection, Pesticides isolation & purification, Chromatography, Gas methods, Dimethylpolysiloxanes chemistry, Food Analysis methods, Fruit and Vegetable Juices analysis, Pesticides analysis, Solid Phase Microextraction methods
- Abstract
The main quest for the implementation of direct SPME to complex matrices has been the development of matrix compatible coatings that provide sufficient sensitivity towards the target analytes. In this context, we present here a thorough evaluation of PDMS-overcoated fibers suitable for simultaneous extraction of different polarities analytes, while maintaining adequate matrix compatibility. For this, eleven analytes were selected, from various application classes (pesticides, industrial chemicals and pharmaceuticals) and with a wide range of log P values (ranging from 1.43 to 6). The model matrix chosen was commercial Concord grape juice, which is rich in pigments such as anthocyanins, and contains approximately 20% of sugar (w/w). Two types of PDMS, as well as other intrinsic factors associated with the PDMS-overcoated fiber fabrication are studied. The evaluation showed that the PDMS-overcoated fibers considerably slowed down the coating fouling process during direct immersion in complex matrices of high sugar content. Longevity differences could be seen between the two types of PDMS tested, with a proprietary Sylgard(®) giving superior performance because of lesser amount of reactive groups and enhanced hydrophobicity. Conversely, the thickness of the outer layer did not seem to have a significant effect on the fiber lifetime. We also demonstrate that the uniformity of the overcoated PDMS layer is paramount to the achievement of reliable data and extended fiber lifetime. Employing the optimum overcoated fiber, limits of detection (LOD) in the range of 0.2-1.3 ng/g could be achieved. Additional improvement is attainable by introducing washing of the coatings after desorption, so that any carbon build-up (fouling) left on the coating surface after thermal desorption can be removed., (Copyright © 2016 Elsevier B.V. All rights reserved.)
- Published
- 2016
- Full Text
- View/download PDF
43. Headspace versus direct immersion solid phase microextraction in complex matrixes: investigation of analyte behavior in multicomponent mixtures.
- Author
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Gionfriddo E, Souza-Silva ÉA, and Pawliszyn J
- Subjects
- Dimethylpolysiloxanes analysis, Gas Chromatography-Mass Spectrometry, Gels chemistry, Hydrophobic and Hydrophilic Interactions, Porosity, Dimethylpolysiloxanes isolation & purification, Solid Phase Microextraction
- Abstract
This work aims to investigate the behavior of analytes in complex mixtures and matrixes with the use of solid-phase microextraction (SPME). Various factors that influence analyte uptake such as coating chemistry, extraction mode, the physicochemical properties of analytes, and matrix complexity were considered. At first, an aqueous system containing analytes bearing different hydrophobicities, molecular weights, and chemical functionalities was investigated by using commercially available liquid and solid porous coatings. The differences in the mass transfer mechanisms resulted in a more pronounced occurrence of coating saturation in headspace mode. Contrariwise, direct immersion extraction minimizes the occurrence of artifacts related to coating saturation and provides enhanced extraction of polar compounds. In addition, matrix-compatible PDMS-modified solid coatings, characterized by a new morphology that avoids coating fouling, were compared to their nonmodified analogues. The obtained results indicate that PDMS-modified coatings reduce artifacts associated with coating saturation, even in headspace mode. This factor, coupled to their matrix compatibility, make the use of direct SPME very practical as a quantification approach and the best choice for metabolomics studies where wide coverage is intended. To further understand the influence on analyte uptake on a system where additional interactions occur due to matrix components, ex vivo and in vivo sampling conditions were simulated using a starch matrix model, with the aim of mimicking plant-derived materials. Our results corroborate the fact that matrix handling can affect analyte/matrix equilibria, with consequent release of high concentrations of previously bound hydrophobic compounds, potentially leading to coating saturation. Direct immersion SPME limited the occurrence of the artifacts, which confirms the suitability of SPME for in vivo applications. These findings shed light into the implementation of in vivo SPME strategies in quantitative metabolomics studies of complex plant-based systems.
- Published
- 2015
- Full Text
- View/download PDF
44. A fast and simple solid phase microextraction coupled with gas chromatography-triple quadrupole mass spectrometry method for the assay of urinary markers of glutaric acidemias.
- Author
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Naccarato A, Gionfriddo E, Elliani R, Sindona G, and Tagarelli A
- Abstract
The analysis of characteristic urinary acidic markers such as glutaric, 3-hydroxyglutaric, 2-hydroxyglutaric, adipic, suberic, sebacic, ethylmalonic, 3-hydroxyisovaleric and isobutyric acid constitutes the recommended follow-up testing procedure for glutaric acidemia type 1 (GA-1) and type 2 (GA-2). The goal of the work herein presented is the development of a fast and simple method for the quantification of these biomarkers in human urine. The proposed analytical approach is based on the use of solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) afterward a rapid derivatization of acidic moieties by propyl chloroformate, propanol and pyridine. Trueness and precision of the proposed protocol, tested at 5, 30 and 80mgl
-1 , provided satisfactory values: recoveries were in the range between 72% and 116% and the relative standard deviations (RSD%) were between 0.9% and 18% (except for isobutyric acid at 5mgl-1 ). The LOD values achieved by the proposed method ranged between 1.0 and 473μgl-1 ., (Copyright © 2014 Elsevier B.V. All rights reserved.)- Published
- 2014
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45. Determination of hydrazine in drinking water: Development and multivariate optimization of a rapid and simple solid phase microextraction-gas chromatography-triple quadrupole mass spectrometry protocol.
- Author
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Gionfriddo E, Naccarato A, Sindona G, and Tagarelli A
- Subjects
- Multivariate Analysis, Drinking Water analysis, Gas Chromatography-Mass Spectrometry methods, Hydrazines analysis, Solid Phase Microextraction methods, Water Pollutants, Chemical analysis
- Abstract
In this work, the capabilities of solid phase microextraction were exploited in a fully optimized SPME-GC-QqQ-MS analytical approach for hydrazine assay. A rapid and easy method was obtained by a simple derivatization reaction with propyl chloroformate and pyridine carried out directly in water samples, followed by automated SPME analysis in the same vial without further sample handling. The affinity of the different derivatized compounds obtained towards five commercially available SPME coatings was evaluated, in order to achieve the best extraction efficiency. GC analyses were carried out using a GC-QqQ-MS instrument in selected reaction monitoring (SRM) acquisition mode which has allowed the achievement of high specificity by selecting appropriate precursor-product ion couples improving the capability in analyte identification. The multivariate approach of experimental design was crucial in order to optimize derivatization reaction, SPME process and tandem mass spectrometry parameters. Accuracy of the proposed protocol, tested at 60, 200 and 800 ng L(-1), provided satisfactory values (114.2%, 83.6% and 98.6%, respectively), whereas precision (RSD%) at the same concentration levels were of 10.9%, 7.9% and 7.7% respectively. Limit of detection and quantification of 4.4 and 8.3 ng L(-1) were obtained. The reliable application of the proposed protocol to real drinking water samples confirmed its capability to be used as analytical tool for routine analyses., (Copyright © 2014 Elsevier B.V. All rights reserved.)
- Published
- 2014
- Full Text
- View/download PDF
46. Development of needle trap technology for on-site determinations: active and passive sampling.
- Author
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Asl-Hariri S, Gómez-Ríos GA, Gionfriddo E, Dawes P, and Pawliszyn J
- Abstract
This study presents a thorough evaluation of new prototypes of extended tip needle trap devices (NT), as well as their application to in situ sampling of biological emissions and active/passive on-site sampling of indoor air. A new NT prototype was constructed with a side hole above the sorbent and an extended tip that fits inside the restriction of the narrow neck liner to increase desorption efficiency. New prototype needles were initially packed with divinylbenzene particles at SGE Analytical Science for the purpose of studying biogenic emissions of pine trees. Prior to their final application, they were evaluated in terms of robustness after multiple use (n > 10), as well as amount extracted of volatile organic compounds (VOCs). An ANOVA test for all the probes showed that at a 95% level of confidence, there were not statistical differences observed among the 9 NTs tested. In addition, the needles were also packed in laboratory with synthesized highly cross-linked PDMS as a frit to immobilize carboxen (Car) particles for spot sampling. For passive sampling, the needles were packed with Car particles embedded in PDMS to simplify calculations in passive mode. The use of NTs as spot samplers, as well as a passive sampler under controlled conditions in the laboratoryyielded a relative standard deviation of less than 15%. Finally, a new, reusable and readily deployable penlike diffusive sampler for needle traps (PDS-NT) was built and tested. Application of the PDS-NT in combination with NT-spot sampling toward the analysis of indoor air in a polymer synthesis laboratory showed good agreement between both techniques for the analyte studied, yielding averages of 0.03 and 0.025 ng/mL of toluene, respectively.
- Published
- 2014
- Full Text
- View/download PDF
47. Simultaneous determination of benzothiazoles, benzotriazoles and benzosulfonamides by solid phase microextraction-gas chromatography-triple quadrupole mass spectrometry in environmental aqueous matrices and human urine.
- Author
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Naccarato A, Gionfriddo E, Sindona G, and Tagarelli A
- Subjects
- Calibration, Gas Chromatography-Mass Spectrometry instrumentation, Humans, Solid Phase Microextraction instrumentation, Benzothiazoles urine, Gas Chromatography-Mass Spectrometry methods, Solid Phase Microextraction methods, Sulfonamides urine, Triazoles urine, Water chemistry, Water Pollutants, Chemical analysis
- Abstract
This work proposes a new approach for the simultaneous determination of benzothiazoles, benzotriazoles and benzosulfonamides in different environmental matrices and human urine, using solid-phase microextraction coupled with gas-chromatography-triple quadrupole mass spectrometry (SPME-GC-QqQMS). The analytes object of this investigation have been classified as toxic to aquatic organisms and their presence in human urine was reported to occur as result of human exposure to contaminated environment. In this work many of the challenges related to the chemical diversity and polarity of the analytes selected were overcame conducting a multivariate optimization of the working conditions by using the approach of "Experimental design". Tests performed to assess the performances of five SPME coatings in direct immersion mode revealed the polyacrylate coating to be the most suitable for the extraction of the probe analytes. A central composite design (CCD) was employed to determine the optimal conditions for four factors affecting the solid-phase microextraction process: extraction time, extraction temperature, pH and percentage of sodium chloride. The optimal working condition determined by using Derringer's desirability function were 40min as extraction time, pH 7.1 and 6.0% of NaCl. Since the extraction temperature do not significantly affects the responses for all the analytes considered, analyses were performed at room temperature. A careful evaluation of the matrix effect for all the matrices tested was carried out. The results obtained showed that the proposed method did not significantly influenced by matrix effects in most of the cases tested, and thus allows the use of simplified calibration procedure. Satisfactory values of accuracy and precision were also obtained for all the matrices considered., (Copyright © 2014 Elsevier B.V. All rights reserved.)
- Published
- 2014
- Full Text
- View/download PDF
48. Development of a simple and rapid solid phase microextraction-gas chromatography-triple quadrupole mass spectrometry method for the analysis of dopamine, serotonin and norepinephrine in human urine.
- Author
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Naccarato A, Gionfriddo E, Sindona G, and Tagarelli A
- Subjects
- Adult, Chromatography, Gas instrumentation, Dopamine chemistry, Female, Healthy Volunteers, Humans, Male, Mass Spectrometry instrumentation, Molecular Structure, Norepinephrine chemistry, Serotonin chemistry, Solid Phase Microextraction instrumentation, Young Adult, Chromatography, Gas methods, Dopamine urine, Mass Spectrometry methods, Norepinephrine urine, Serotonin urine, Solid Phase Microextraction methods
- Abstract
The work aims at developing a simple and rapid method for the quantification of dopamine (DA), serotonin (5-HT) and norepinephrine (NE) in human urine. The urinary levels of these biogenic amines can be correlated with several pathological conditions concerning heart disease, stress, neurological disorders and cancerous tumors. The proposed analytical approach is based on the use of solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) after a fast derivatization of both aliphatic amino and phenolic moieties by propyl chloroformate. The variables influencing the derivatization reaction were reliably optimized by the multivariate approach of "Experimental design". The optimal conditions were obtained by performing derivatization with 100μL of propyl chloroformate and 100μL of pyridine. The extraction ability of five commercially available SPME fibers was evaluated in univariate mode and the best results were obtained using the polyacrylate fiber. The variables affecting the efficiency of SPME analysis were again optimized by the multivariate approach of "Experimental design" and, in particular, a central composite design (CCD) was applied. The optimal values were extraction in 45min at room temperature, desorption temperature at 300°C, no addition of NaCl. Assay of derivatized analytes was performed by using a gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) system in selected reaction monitoring (SRM) acquisition. An evaluation of all analytical parameters demonstrates that the developed method provides satisfactory results. Indeed, very good linearities were achieved in the tested calibration range with correlation coefficient values of 0.9995, 0.9999 and 0.9997 for DA, 5-HT and NE, respectively. Accuracies and RSDs calculated for between-run and tested at concentrations of 30, 200, and 800μg L(-1) were in the range from 92.8% to 103.0%, and from 0.67 to 4.5%, respectively. Finally, the LOD values obtained can be considered very good (0.587, 0.381 and 1.23μg L(-1) for DA, 5-HT and NE, respectively)., (Copyright © 2013 Elsevier B.V. All rights reserved.)
- Published
- 2014
- Full Text
- View/download PDF
49. A reliable solid phase microextraction-gas chromatography-triple quadrupole mass spectrometry method for the assay of selenomethionine and selenomethylselenocysteine in aqueous extracts: difference between selenized and not-enriched selenium potatoes.
- Author
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Gionfriddo E, Naccarato A, Sindona G, and Tagarelli A
- Subjects
- Humans, Limit of Detection, Plant Extracts chemistry, Reproducibility of Results, Research Design, Selenium metabolism, Selenocysteine analysis, Solanum tuberosum, Gas Chromatography-Mass Spectrometry methods, Selenocysteine analogs & derivatives, Selenomethionine analysis, Solid Phase Microextraction methods, Tandem Mass Spectrometry methods, Water chemistry
- Abstract
A new analytical approach is exploited in the assay of selenium speciation in selenized and not selenium enriched potatoes based on the widely available solid-phase microextraction (SPME) coupled to-GC-triple quadrupole mass spectrometry (SPME-GC-QqQ MS) method. The assay of selenomethionine (SeMet) and selenomethylselenocysteine (SeMeSeCys) in potatoes here reported provides clues to the effectiveness of SPME technique combined with gas chromatography-tandem mass spectrometry, which could be of general use. For the exploitation of the GC method, the selected analytes were converted into their N(O,S)-alkoxycarbonyl alkyl esters derivatives by direct treatment with alkyl chloroformate in aqueous extracts. The performance of five SPME fibers and three chloroformates were tested in univariate mode and the best results were obtained using the divinylbenzene/carboxen/polydimethylsiloxane fiber and propylchloroformate. The variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of design of experiment (DoE) and, in particular, a central composite design (CCD) was applied. Tandem mass spectrometry in selected reaction monitoring (SRM) has allowed the elimination of matrix interferences, providing reconstructed chromatograms with well-resolved peaks and the achievement of very satisfactory detection and quantification limits. Both precision and recovery of the proposed protocol tested at concentration of 8 and 40 μg kg(-1) (dry matter), offered values ranging from 82.3 to 116.3% and from 8.5 to 13.1% for recovery and precision, respectively. The application of the method to commercial samples of selenized and not selenium enriched potatoes proved that the Se fertilization increases significantly the concentration of these bioavailable selenoamino acids., (Copyright © 2012 Elsevier B.V. All rights reserved.)
- Published
- 2012
- Full Text
- View/download PDF
50. Review: multistage mass spectrometry in quality, safety and origin of foods.
- Author
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Aiello D, De Luca D, Gionfriddo E, Naccarato A, Napoli A, Romano E, Russo A, Sindona G, and Tagarelli A
- Abstract
Quality and safety control and the validation of origin are hot issues in the production of food and its distribution, and are of primary concern to food and agriculture organization. Modern mass spectrometry (MS) provides unique, reliable and affordable methodologies to approach with a high degree of scientificity any problem which may be posed in this field. In this review the contribution of mass spectrometry to food analysis is presented aiming at providing clues on the fundamental role of the basic principles of gas-phase ion chemistry in applied research fields. Applications in proteomics, allergonomics, glycomics, metabolomics, lipidomics, food safety and traceability have been surveyed. The high level of specificity and sensitivity of the MS approach allows the characterization of food components and contaminants present at ultra-trace levels, providing a distinctive and safe validation of the products.
- Published
- 2011
- Full Text
- View/download PDF
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