title: Headspace-programmed temperature vaporization-mass spectrometry for the rapid determination of possible volatile biomarkers of lung cancer in urine.
abstract: We propose a new method for the rapid determination of five volatile compounds described in the literature as possible biomarkers of lung cancer in urine samples. The method is based on the coupling of a headspace sampler, a programmed temperature vaporizer in solvent-vent injection mode, and a mass spectrometer (HS-PTV-MS). This configuration is known as an electronic nose based on mass spectrometry. Once the method was developed, it was used for the analysis of urine samples from lung cancer patients and healthy individuals. Multivariate calibration models were employed to quantify the biomarker concentrations in the samples. The detection limits ranged between 0.16 and 21 μg/L. For the assignment of the samples to the patient group or the healthy individuals, the Wilcoxon signed-rank test was used, comparing the concentrations obtained with the median of a reference set of healthy individuals. To date, this is the first time that multivariate calibration and non-parametric methods have been combined to classify biological samples from profile signals obtained with an electronic nose. When significant differences in the concentration of one or more biomarkers were found with respect to the reference set, the sample is considered as a positive one and a new analysis was performed using a chromatographic method (HS-PTV-GC/MS) to confirm the result. The main advantage of the proposed HS-PTV-MS methodology is that no prior chromatographic separation and no sample manipulation are required, which allows an increase of the number of samples analyzed per hour and restricts the use of time-consuming techniques to only when necessary. Graphical abstract Schematic diagram of the developed methodology.
authors.affiliation: Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008, Salamanca, Spain.
authors.forename: Ana
authors.initials: A
authors.lastname: Pérez Antón
authors.affiliation: Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008, Salamanca, Spain.
authors.forename: Álvaro García
authors.initials: ÁG
authors.lastname: Ramos
authors.affiliation: Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008, Salamanca, Spain. mns@usal.es.
authors.forename: Miguel
authors.initials: M
authors.lastname: Del Nogal Sánchez
authors.affiliation: Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008, Salamanca, Spain.
authors.forename: José Luis Pérez
authors.initials: JL
authors.lastname: Pavón
authors.affiliation: Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008, Salamanca, Spain.
authors.forename: Bernardo Moreno
authors.initials: BM
authors.lastname: Cordero
authors.affiliation: Servicio de Medicina Interna, Hospital Virgen de la Vega, Complejo Asistencial Universitario de Salamanca, 37007, Salamanca, Spain.
authors.forename: Ángel Pedro Crisolino
authors.initials: ÁP
authors.lastname: Pozas
mesh_terms: D014408:Biomarkers, Tumor / Q000652:urine*; D062609:Electronic Nose; D006801:Humans; D008175:Lung Neoplasms / Q000737:chemistry / Q000175:diagnosis* / Q000652:urine*; D013058:Mass Spectrometry / Q000379:methods*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D055549:Volatile Organic Compounds / Q000652:urine*
chemical_list: D014408:Biomarkers, Tumor; D055549:Volatile Organic Compounds
keywords: HS-PTV-MS; Lung cancer and urine; Multivariate calibration; Volatile biomarkers; Wilcoxon signed-rank test