SPME arrow-based extraction for enhanced targeted and untargeted urinary volatilomics

Author, as appears in the article.: Llambrich, Maria; Ramirez, Noelia; Cumeras, Raquel

Department: Enginyeria Electrònica, Elèctrica i Automàtica

URV's Author/s: Brezmes Llecha, Jesús Jorge / Cumeras Olmeda, Raquel / Llambrich Rodriguez, Maria / Ramírez González, Noelia

Keywords: Volatilomics; Volatile organic compounds; Urine; Untargeted analysis; Tobacco smoke exposure; Tobacco smoke exposur; Spme arrow; Solid-phase microextraction; Solid phase microextraction; Organic-compounds; Metabolomics; Humans; Gas chromatography-mass spectrometry; Devic; Combination; Biomarkers

Abstract: Background: Volatile organic compounds (VOCs) present in human urine are promising biomarkers for various health conditions and environmental exposures. However, their reliable detection is challenging due to the complexity of urinary matrices and the low concentrations of VOCs. Moreover, untargeted approaches present considerable challenges in terms of data interpretation, increasing the complexity of method development. Here we address these challenges by developing a new method that combines solid-phase microextraction (SPME) Arrow with gas chromatography-high resolution mass spectrometry (GC-HRMS), using a design of experiments (DOE) approach for targeted and untargeted compounds. This methodology, specifically tailored for SPME Arrow, represents a significant advancement in untargeted urinary analysis. Results: The method was developed based on targeted and untargeted outcomes, were ranking results focus on the highest response area of 11 spiked target VOCs representative of urinary volatilomics, and on identifying the maximum untargeted number of VOCs. The method was developed focusing on the highest response area of 11 spiked target VOCs representative of urinary volatilomics and identifying the maximum number of VOCs. A univariate method determined the optimal coating type, urine volume, and salt addition. Subsequently, a central composite design (CCD) DOE was used to determine ideal temperature, extraction, and incubation times. The best method obtained has an extraction time of 60 min at a temperature of 53 degrees C, with an SPME Arrow CAR/ PDMS using 2 mL of urine, with 0.25 % w/v of NaCl and a pH of 2. Compared to conventional SPME fibers, the SPME Arrow showed improved extraction efficiency, detecting more VOCs. Finally, the enhanced method was successfully applied to urine samples from children exposed and non-exposed to tobacco smoke, identifying specific VOCs, like p-cymene and p-isopropenyl toluene related to tobacco exposure. Significance: By integrating both targeted and untargeted approaches, the developed method comprehensively captures the complexity of urinary metabolomics. This dual strategy ensures the precise identification of known compounds and the discovery of novel biomarkers, thereby providing a more complete metabolic profile. Such an approach is crucial for advancing in non-invasive diagnostics and environmental health studies, as it offers deeper insights into the intricate relationships between metabolic processes and various health conditions.

Thematic Areas: Spectroscopy; Química; Odontología; Medicina ii; Medicina i; Materiais; Matemática / probabilidade e estatística; Interdisciplinar; Geociências; General medicine; Farmacia; Environmental chemistry; Engenharias iv; Engenharias iii; Engenharias ii; Enfermagem; Ciências biológicas iii; Ciências biológicas ii; Ciências biológicas i; Ciências agrárias i; Ciência de alimentos; Ciência da computação; Chemistry, analytical; Biotecnología; Biodiversidade; Biochemistry; Astronomia / física; Analytical chemistry

licence for use: https://creativecommons.org/licenses/by/3.0/es/

Author's mail: raquel.cumeras@urv.cat; noelia.ramirez@urv.cat; maria.llambrich@iispv.cat; jesus.brezmes@urv.cat

Record's date: 2025-02-18

Paper version: info:eu-repo/semantics/publishedVersion

Link to the original source: https://www.sciencedirect.com/science/article/pii/S0003267024010626?via%3Dihub

Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/

Paper original source: Analytica Chimica Acta. 1329 343261-

APA: Llambrich, Maria; Ramirez, Noelia; Cumeras, Raquel (2024). SPME arrow-based extraction for enhanced targeted and untargeted urinary volatilomics. Analytica Chimica Acta, 1329(), 343261-. DOI: 10.1016/j.aca.2024.343261

Article's DOI: 10.1016/j.aca.2024.343261

Entity: Universitat Rovira i Virgili

Journal publication year: 2024

Publication Type: Journal Publications