Emanuela Gionfriddo

Review: multistage mass spectrometry in quality, safety and origin of foods.

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.

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

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.

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

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.

Headspace versus Direct Immersion Solid Phase Microextraction in Complex Matrixes: Investigation of Analyte Behavior in Multicomponent Mixtures

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.

Development of Needle Trap Technology for On-Site Determinations: Active and Passive Sampling

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.

Advances in Solid Phase Microextraction and Perspective on Future Directions

Solid phase microextraction (SPME) is a versatile, non-exhaustive sample preparation tool that has been demonstrated to be well-suited for facile and effective analysis of a broad range of compounds in a plethora of studies. A growing number of reports describing diverse SPME workflows for novel investigations in a variety of fields, such as flavor and fragrance investigations, environmental studies, and diverse bioanalytical applications, among others, corroborate the applicability of this microextraction tool in the analytical sciences

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)

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.

A new and efficient Solid Phase Microextraction approach for analysis of high fat content food samples using a matrix-compatible coating

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.

Solid Phase Microextraction On-Fiber Derivatization Using a Stable, Portable, and Reusable Pentafluorophenyl Hydrazine Standard Gas Generating Vial

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.

Insights into the Effect of the PDMS-Layer on the Kinetics and Thermodynamics of Analyte Sorption onto the Matrix-Compatible Solid Phase Microextraction Coating

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.