Determinació i presència de compostos orgànics d'alt volum de producció, els seus productes de transformació i metabòlits en ambients aquàtics

Els compostos orgànics d’alt volum de producció són substàncies orgàniques que, a causa de les enormes quantitats amb què s’empren a la indústria i de la seva toxicitat, poden comportar riscos ecotoxicològics per al medi ambient i per la salut pública. Els medis aquàtics són particularment sensibles als efectes negatius d’aquestes substàncies que trenquen el delicat equilibri que mantenen els ecosistemes marins i d’aigua dolça. Aquesta Tesi Doctoral se centra en el desenvolupament de nous mètodes analítics per estudiar la presència de productes químics d’alt volum de producció com els derivats de la benzotriazola, la benzotiazola i la benzosulfonamida, els dièsters i monoèsters de l’àcid ftàlic i els dièsters de l’àcid fosfòric en mostres d’ambients aquàtics. Els mètodes que s’han desenvolupat es basen en la cromatografia de líquids acoblada a l’espectrometria de masses d’alta resolució i s’han aplicat diferents tècniques d’extracció i neteja com l’extracció en fase sòlida, l’extracció amb líquids pressuritzats i els QuEChERS. Per altra banda, un d’aquests mètodes s’ha aplicat pel monitoratge al llarg d’un any de la presència de dièsters de l’àcid fosfòric en espècies de peix i marisc de consum habitual per la població de Catalunya.Los compuestos orgánicos de alto volumen de producción son sustancias orgánicas que, debido a las enormes cantidades que se emplean en la industria y a su toxicidad, pueden comportar riesgos ecotoxicológicos para el medio ambiente. Los medios acuáticos son particularmente sensibles a los efectos negativos de estas sustancias que rompen el delicado equilibrio que mantienen los ecosistemas marinos y de agua dulce. Esta Tesis Doctoral se centra en el desarrollo de nuevos métodos analíticos para estudia la presencia de productos químicos de alto volumen de producción como los derivados de la benzotriazola, la benzotiazola y benzosulfonamida, los diésteres y monoésteres del ácido ftálico y los diésteres del ácido fosfórico en muestras de ambientes acuáticos. Los métodos que se han desarrollado se basan en la cromatografía de líquidos acoplada a la espectrometría de masas de alta resolución y se han aplicado diferentes técnicas de extracción y limpieza como la extracción en fase sólida, la extracción con líquidos presurizados y los QuEChERS. A su vez, uno de estos métodos se ha aplicado a la monitorización a lo largo de un año de la presencia de diésteres del ácido fosfórico en especies de pescado y marisco de consumo habitual en Catalunya.High production volume chemicals are organic chemicals that can pose ecotoxicological risks for the environment due to the vast amounts used in the industry and their toxicity. Aquatic environments are particularly sensitive to the negative effects caused by these chemicals which can disrupt the delicate balance maintained by marine and freshwater ecosystems. This Doctoral Thesis therefore focuses on the development of new analytical methods to study the presence of high-volume chemicals such as benzotriazoles, benzothiazoles, benzosulfonamides, phthalate diesters and monoesters, and organophosphate diesters in samples from aquatic environments. The methods are based on liquid chromatography coupled to high resolution mass spectrometry. Several extraction, preconcentration and clean-up techniques such as solid-phase extraction, pressurised liquid extraction and QuEChERS have also been used in the development of the methods. Moreover, one of the developed methods has been used for the monitoring of organophosphate diesters in fish and shellfish species widely consumed in Catalunya

Detection and quantitation of frauds in the authentication of cranberry-based extracts by UHPLC-HRMS (Orbitrap) polyphenolic profiling and multivariate calibration methods

UHPLC-HRMS (Orbitrap) polyphenolic profiling was applied to the characterization, classification and authentication of cranberry-based natural and pharmaceutical products. 53 polyphenolic standards were characterized to build a user accurate mass database which was then proposed to obtain UHPLC-HRMS polyphenolic profiles by means of ExactFinderTM software. Principal component analysis results showed a good sample discrimination according to the fruit employed. Regarding cranberry-based pharmaceuticals, discrimination according to the presentation format (syrup, sachets, capsules, etc.) was also observed due to the enhancement of some polyphenols by purification and preconcentration procedures. Procyanidin A2 and homogenistic, sinapic, veratric, cryptochlorogenic and caffeic acids showed to be important polyphenols to achieve cranberry-based products discrimination against the other studied fruits. Partial least square regression allowed the determination of adulterant percentages in cranberry-fruit samples. Very satisfactory results, with adulteration quantification errors lower than 6.0% were obtained even at low adulteration levels

UHPLC-HRMS (Orbitrap) fingerprinting in the classification and authentication of cranberry-based natural products and pharmaceuticals using multivariate calibration methods

UHPLC-HRMS (Orbitrap) fingerprinting in negative and positive H-ESI mode was applied to the characterization, classification and authentication of cranberry-based natural and pharmaceutical products. HRMS data in full scan mode (m/z 100-1500) at a resolution of 70,000 full-width at half maximum was recorded and processed with MSConvert software to obtain a profile of peak intensities in function of m/z values and retention times. A threshold peak filter of absolute intensity (105 counts) was applied to reduce data complexity. Principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) revealed patterns able to discriminate the analyzed samples according to the fruit of origin (cranberry, grape, blueberry and raspberry). Discrimination among cranberry-based natural and cranberry-based pharmaceutical preparations was also achieved. Both, UHPLC-HRMS fingerprints in negative and positive H-ESI modes, as well as the data fusion of both acquisition modes, showed to be good chemical descriptors to address cranberry extracts authentication. Validation of the proposed methodology showed a prediction rate of 100% of the samples. Obtained data was further treated by partial least squares (PLS) regression to identify frauds and quantify the percentage of adulterant fruits in cranberry-fruit extracts, achieving prediction errors in the range 0.17-3.86%

Characterization, classification and authentication of fruit-based extracts by means of HPLC-UV chromatographic fingerprints, polyphenolic profiles and chemometric methods

HPLC-UV was applied to the analysis and characterization of fruit-based and fruit-processed products. A Kinetex C18 reversed-phase column was proposed under gradient elution for the determination of 17 polyphenols. Acceptable sensitivity (LODs below 0.16 mg/L), and good linearity (r2 higher then 0.995), precision (RSD below 6.8%), and method trueness (relative errors below 11%) were obtained. Data corresponding to polyphenolic peak areas and HPLC-UV chromatographic fingerprints were then analyzed by exploratory principal component analysis (PCA) to extract information of the most significant variables contributing to characterization and classification of analyzed samples regarding the fruit of origin. HPLC-UV chromatographic data was further treated by partial least square (PLS) regression to determine the percentages of adulteration in cranberry-fruit extracts. It was found that even mixture samples containing low percentages of adulterants could be distinguished from genuine cranberry extracts. Highly satisfactory results were obtained, with overall errors in the quantification of adulterations below 4.3%

Detection and quantitation of frauds in the authentication of cranberry-based extracts by UHPLC-HRMS (Orbitrap) polyphenolic profiling and multivariate calibration methods

UHPLC-HRMS (Orbitrap) polyphenolic profiling was applied to the characterization, classification and authentication of cranberry-based natural and pharmaceutical products. 53 polyphenolic standards were characterized to build a user accurate mass database which was then proposed to obtain UHPLC-HRMS polyphenolic profiles by means of ExactFinderTM software. Principal component analysis results showed a good sample discrimination according to the fruit employed. Regarding cranberry-based pharmaceuticals, discrimination according to the presentation format (syrup, sachets, capsules, etc.) was also observed due to the enhancement of some polyphenols by purification and preconcentration procedures. Procyanidin A2 and homogenistic, sinapic, veratric, cryptochlorogenic and caffeic acids showed to be important polyphenols to achieve cranberry-based products discrimination against the other studied fruits. Partial least square regression allowed the determination of adulterant percentages in cranberry-fruit samples. Very satisfactory results, with adulteration quantification errors lower than 6.0% were obtained even at low adulteration levels

UHPLC-HRMS (Orbitrap) fingerprinting in the classification and authentication of cranberry-based natural products and pharmaceuticals using multivariate calibration methods

UHPLC-HRMS (Orbitrap) fingerprinting in negative and positive H-ESI mode was applied to the characterization, classification and authentication of cranberry-based natural and pharmaceutical products. HRMS data in full scan mode (m/z 100-1500) at a resolution of 70,000 full-width at half maximum was recorded and processed with MSConvert software to obtain a profile of peak intensities in function of m/z values and retention times. A threshold peak filter of absolute intensity (105 counts) was applied to reduce data complexity. Principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) revealed patterns able to discriminate the analyzed samples according to the fruit of origin (cranberry, grape, blueberry and raspberry). Discrimination among cranberry-based natural and cranberry-based pharmaceutical preparations was also achieved. Both, UHPLC-HRMS fingerprints in negative and positive H-ESI modes, as well as the data fusion of both acquisition modes, showed to be good chemical descriptors to address cranberry extracts authentication. Validation of the proposed methodology showed a prediction rate of 100% of the samples. Obtained data was further treated by partial least squares (PLS) regression to identify frauds and quantify the percentage of adulterant fruits in cranberry-fruit extracts, achieving prediction errors in the range 0.17-3.86%

Characterization, classification and authentication of fruit-based extracts by means of HPLC-UV chromatographic fingerprints, polyphenolic profiles and chemometric methods

HPLC-UV was applied to the analysis and characterization of fruit-based and fruit-processed products. A Kinetex C18 reversed-phase column was proposed under gradient elution for the determination of 17 polyphenols. Acceptable sensitivity (LODs below 0.16 mg/L), and good linearity (r2 higher then 0.995), precision (RSD below 6.8%), and method trueness (relative errors below 11%) were obtained. Data corresponding to polyphenolic peak areas and HPLC-UV chromatographic fingerprints were then analyzed by exploratory principal component analysis (PCA) to extract information of the most significant variables contributing to characterization and classification of analyzed samples regarding the fruit of origin. HPLC-UV chromatographic data was further treated by partial least square (PLS) regression to determine the percentages of adulteration in cranberry-fruit extracts. It was found that even mixture samples containing low percentages of adulterants could be distinguished from genuine cranberry extracts. Highly satisfactory results were obtained, with overall errors in the quantification of adulterations below 4.3%