Direct Coupling of Bio-SPME to Liquid Electron Ionization-MS/MS via a Modified Microfluidic Open Interface

Rocío‐Bautista, Priscilla; Famiglini, Giorgio; Termopoli, Veronica; Nazdrajić, Emir; Pawliszyn, Janusz; Palma, Pierangela

doi:10.1021/jasms.0c00303

Cited by 16 publications

(6 citation statements)

References 43 publications

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“…These compounds can enhance or suppress the analyte's signal and cause misleading results. The LEI shows negligible ME, as already demonstrated [37,40]. Nevertheless, because EVOO is a complex matrix, a thorough evaluation of the ME is mandatory.…”

Section: Evaluation Of Matrix Effectsmentioning

confidence: 59%

Tyrosol and Hydroxytyrosol Determination in Extra Virgin Olive Oil with Direct Liquid Electron Ionization-Tandem Mass Spectrometry

et al. 2021

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Extra virgin olive oil (EVOO) is one of the main ingredients of the Mediterranean diet. It is claimed as a functional food for its unique content of health-promoting compounds. Tyrosol (Tyr), Hydroxytyrosol (Htyr), and their phenolic derivatives present in EVOO show beneficial properties, and their identification and quantification, both in their free form and after the hydrolysis of more complex precursors, are important to certify its quality. An alternative method for quantifying free and total Tyr and Htyr in EVOO is presented using an LC–MS interface based on electron ionization (EI), called liquid electron ionization (LEI). This method requires neither sample preparation nor chromatography; the sample is diluted and injected. The selectivity and sensitivity were assessed in multiple reaction monitoring mode (MRM), obtaining confirmation and quantification in actual samples ranging from 5 to 11 mg/Kg for the free forms and from 32 to 80 mg/Kg for their total amount after hydrolysis. Two MS/MS transitions were acquired for both compounds using the Q/q ratios as confirmatory parameters. Standard addition calibration curves demonstrated optimal linearity and negligible matrix effects, allowing a correct quantification even without expensive and difficult to find labeled internal standards. After several weeks of operation, the system’s repeatability was excellent, with an intraday RSD (%) spanning from five to nine and an interday RSD (%) spanning from 9 to 11.

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Section: Evaluation Of Matrix Effectsmentioning

confidence: 59%

Tyrosol and Hydroxytyrosol Determination in Extra Virgin Olive Oil with Direct Liquid Electron Ionization-Tandem Mass Spectrometry

et al. 2021

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“…As with the previous design, the improved design considers replacing the MS standard electrospray capillaries with home-cut capillaries with 150 μm ID. Repercussions of using long and narrow tubing on peak shape can be seen in other works; , however, the very important aspect of those works is coupling liquid to electron impact ionization and matrix effect free ionization process, which importance heavily outweighs wide peaks.…”

Section: Resultsmentioning

confidence: 99%

Coupling of Solid-Phase Microextraction Directly to Mass Spectrometry via an Improved Microfluidic Open Interface to Facilitate High-Throughput Determinations

Nazdrajić

Murtada

Rickert

et al. 2023

J. Am. Soc. Mass Spectrom.

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Mass spectrometry analysis can be performed by introducing samples directly to mass spectrometry, allowing the increase of the analysis throughput; however, some disadvantages of direct-to-mass spectrometry analysis include susceptibility to matrix effects and risk of instrument contamination from inadequate sample preparation. Solid-phase microextraction is one of the most suitable sample preparation methods for direct-to-mass spectrometry analysis, as it offers matrix-compatible coatings which ensure analyte enrichment with minimal or no interference from matrix. One of the ways solidphase microextraction can be coupled directly to mass spectrometry is via a microfluidic open interface. This manuscript reports improvements made to the initial microfluidic open interface design, where the system components have been simplified to mostly commercially available materials. In addition, the analysis of samples has been automated by implementing software that fully controls the analysis workflow, where the washing procedure is optimized to completely reduce the carryover. Herein, the extraction and desorption time profiles from thin and thick SPME devices was studied where the overall workflow consisted of high-throughput sample preparation of 1.3 min per 96 samples and <1 min per sample instrumental analysis.M ass spectrometry (MS) is a powerful technology for the qualitative and quantitative analysis of samples applied in food, environmental, forensic, proteomics, and biological analysis, among other fields. 1−4 Thus, chromatographic techniques (e.g., LC) coupled with MS became a gold standard for quantitative and qualitative analysis of various complex samples. The outstanding performance of LC-MS can be achieved with adequate sample preparation and a separation step. 5 Due to recent improvements in the mass spectrometer, it can analyze complex samples directly to MS without chromatography, even under ambient conditions. 1 The most significant advantage of direct MS over chromatography coupled to MS is the circumvention of the typically lengthy separation step that does not allow for high-throughput or rapid analysis. Recent direct MS applications include the analysis of in vivo, 6 biological, 7 pharmaceutical, 8 food samples, 9 and other fields. The disadvantage of directly introducing samples to MS for the analysis of complex samples is the introduction of an enormous amount of matrix components that can interfere with or suppress the analyte's signal. Hence, coupling an appropriate sample preparation method to the overall workflow is crucial for the sensitivity of the overall direct-to-MS analysis and the mass spectrometer stability and cleanliness.

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“…Herein, a green and fast method based on MOI-PFS-LEI coupled to QQQ (low-resolution analysis) or QTOF (high-resolution analysis) instruments in liquid-phase NCI mode for the simultaneous analysis of dicamba and tefluthrin in a CF is presented for the first time. The QQQ instrument is demonstrated to be a very sensitive and specific detector in MRM mode, even without chromatographic separation [6,27]. In this work, we also present the proofof-concept of the MOI-PFS-LEI system in NCI mode coupled with a Q-TOF instrument in MS mode for high-resolution experiments in full scan MS mode.…”

Section: Introductionmentioning

confidence: 98%

Sustainable and Rapid Determination of Two Halogenated Pesticides in a Commercial Formulation by Solid Phase Microextraction and Liquid Phase Chemical Ionization Mass Spectrometry

Marittimo,

Grasselli,

Arigò

et al. 2023

Separations

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This work presents a sustainable and rapid method for halogenated pesticide analysis without chromatographic separation. The system is composed of a microfluidic open interface (MOI) for solid-phase microextraction (SPME) liquid phase desorption, connected to a liquid electron ionization mass spectrometry interface (LEI-MS). Either a triple quadrupole mass spectrometer (QQQ-MS/MS, (low-resolution) or a quadrupole-time-of-flight tandem MS (QTOF-MS/MS, high-resolution) were employed, each operating in negative chemical ionization (NCI) conditions. The flow rate used (100 µL/min) to rapidly empty the MOI chamber (approximately 2.5 µL) is reduced to the working flow rate of the LEI interface (500 nL/min) by a passive flow splitter (PFS). NCI is an appropriate ionization technique for electrophilic compounds, increasing specificity and reducing background noise. Two halogenated pesticides, dicamba and tefluthrin, were extracted simultaneously from a commercial formulation matrix (CF) using a C18 fiber by direct immersion (3 min under vortex agitation). Analyte desorption occurred in static conditions inside MOI filled with acidified acetonitrile (ACN) (0.2% phosphoric acid, PA). Extraction and desorption steps were optimized to increase efficiency and accelerate the process. No chromatographic separation was involved; therefore, the system fully exploited MS/MS selectivity and HRMS accuracy demonstrating good linearity, repeatability and limits of detection (LODs) and limits of quantification (LOQs) in the pg/mL range (50 and 500 pg/mL, respectively). Low-resolution experiments showed that matrix effects (ME) did not affect the results. The fast workflow (5 min) makes the system suitable for high-throughput analysis observing the principles of green analytical chemistry (GAC).

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Direct Coupling of Bio-SPME to Liquid Electron Ionization-MS/MS via a Modified Microfluidic Open Interface

Cited by 16 publications

References 43 publications

Tyrosol and Hydroxytyrosol Determination in Extra Virgin Olive Oil with Direct Liquid Electron Ionization-Tandem Mass Spectrometry

Tyrosol and Hydroxytyrosol Determination in Extra Virgin Olive Oil with Direct Liquid Electron Ionization-Tandem Mass Spectrometry

Coupling of Solid-Phase Microextraction Directly to Mass Spectrometry via an Improved Microfluidic Open Interface to Facilitate High-Throughput Determinations

Sustainable and Rapid Determination of Two Halogenated Pesticides in a Commercial Formulation by Solid Phase Microextraction and Liquid Phase Chemical Ionization Mass Spectrometry

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