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Analytical Methods for the Determination of Endocrine Disruptors, UV Filters and Plastic Additives in Packaging and Pharmaceuticals

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Analytical Methods for the Determination of Endocrine Disruptors, UV Filters and Plastic Additives in Packaging and Pharmaceuticals TESIS DOCTORAL Título Analytical methods for the determination of endocrine disruptors, UV filters and plastic additives in packaging and pharmaceuticals Autor/es Cristina Moreta Sánchez Director/es María Teresa Tena Vázquez de la Torre Facultad Facultad de Ciencias, Estudios Agroalimentarios e Informática Titulación Departamento Química Curso Académico 2014-2015 Tesis presentada como compendio de publicaciones. La edición en abierto de la misma NO incluye las partes afectadas por cesión de derechos Analytical methods for the determination of endocrine disruptors, UV filters and plastic additives in packaging and pharmaceuticals, tesis doctoral de Cristina Moreta Sánchez, dirigida por María Teresa Tena Vázquez de la Torre (publicada por la Universidad de La Rioja), se difunde bajo una Licencia Creative Commons Reconocimiento-NoComercial-SinObraDerivada 3.0 Unported. Permisos que vayan más allá de lo cubierto por esta licencia pueden solicitarse a los titulares del copyright. © El autor © Universidad de La Rioja, Servicio de Publicaciones, 2015 publicaciones.unirioja.es E-mail: [email protected] Analytical methods for the determination of endocrine disruptors, UV filters and plastic additives in packaging and pharmaceuticals Focused Ultrasound Solid Liquid Extraction Migration Repeatability QToF Delamination Low-cost RSD Drugs Syrups Syrups Fast Sunscreens Packaging DAD PET Softgels Extraction Extraction Recovery LOQ PFCAs Quadrupole Time-of-Flight SPE Polymers Hormones Analytical methods FUSLE UHPLC PFOS PFOS Polyethylene Chromatography Determination Creams Creams Optimization PharmaceuticalsAdditives Ultrasounds MS/MS Slip-agents CCD QqQ Matrix-effect Popcorn bags Popcorn Antioxidants Parabens UV-filters Perfluorinated compounds Validation Endocrine-disruptors Endocrine-disruptors Tablets LOD Spectrometry Multilayer flexible packaging PhD Thesis ----------- -2015 Cristina Moreta Sánchez Department of Chemistry Area of Analytical Chemistry University of La Rioja ANALYTICAL METHODS FOR THE DETERMINATION OF ENDOCRINE DISRUPTORS, UV FILTERS AND PLASTIC ADDITIVES IN PACKAGING AND PHARMACEUTICALS A dissertation presented in candidacy for the degree of International Doctor CRISTINA MORETA SÁNCHEZ July 2015 María Teresa Tena Vázquez de la Torre, Catedrática en Química analítica de la Universidad de La Rioja, Certifica: Que la memoria titulada “Analytical methods for the determination of endocrine disruptors, UV filters and plastic additives in packaging and pharmaceuticals” que presenta Cristina Moreta Sánchez como compendio de publicaciones, ha sido realizada bajo su dirección en el Departamento de Química de la Universidad de La Rioja y reúne las condiciones exigidas para conseguir el título de doctor internacional tras la estancia realizada en Albany (NY) en el Wadsworth Center bajo la dirección del profesor Kurunthachalam Kannan. Logroño a 22 de julio de 2015 Fdo: María Teresa Tena Vázquez de la Torre Financiación Para poder realizar una tesis doctoral es imprescindible contar con apoyo económico. La elaboración de esta tesis no habría sido posible sin la beca de Formación de Personal Investigador y la ayuda para estancias breves en el extranjero que me concedió la Comunidad Autónoma de La Rioja. Asimismo, este trabajo ha sido realizado gracias a la financiación recibida por AMCOR Flexibles a través del contrato OTEM090908 y por el Ministerio de Educación y Ciencia a través del proyecto CTM 2010-16935 dentro del Plan Nacional de Investigación Científica y Desarrollo e Innovación Tecnológica cofinanciada con fondos FEDER (Fondo Europeo de Desarrollo Regional). También quiero agradecer a AMCOR Flexibles y a Constantia el suministro de muestras y ciertos reactivos, así como a la Universidad de La Rioja por las ayudas para la realización de tesis doctorales subvencionadas por el banco Santander. Finalmente, quiero también agradecer a la Universidad de La Rioja, a AMCOR Flexibles y al Wadsworth Center el uso de sus instalaciones y equipos. Agradecimientos / Acknowledgements AGRADECIMIENTOS ACKNOWLEDGEMENTS ¡Hay tantas personas que han formado parte de este proyecto directa o indirectamente! ¡Hay tantas personas que me han ayudado a superar todos los obstáculos, y no han sido pocos, que han ido apareciendo durante la elaboración de esta tesis! Más de uno y una sabéis que realmente llegué a pensar que no podría terminarla. Pero sí, si leéis esto es porque ¡lo conseguí! Quiero dar primero las gracias a mi directora de tesis, Teresa. Siempre he querido trabajar contigo porque eres ante todo trabajadora, rigurosa, metódica, honrada y leal. Gracias por ofrecerme esta oportunidad, por confiar en mí, por ser exigente, por enseñarme tantas cosas, por “rescatarme” de aquella empresa que tanto me estaba minando. Gracias a eso comprendí que el doctorado me podía ofrecer todo lo que en aquel momento necesitaba. Muchas gracias porque has conseguido que me sienta mucho más segura de lo que hago, porque aunque al principio considero que fuiste muy dura conmigo, me has ayudado y levantado siempre que lo he necesitado, porque me has inculcado valores y principios de trabajo muy valiosos para mí como química analítica. Gracias. Gracias a David y a Álvaro. Vosotros estuvisteis conmigo en mis primeros pasos. David, trabajador, dulce, constante, SIEMPRE dispuesto a ayudarte y con la mayor paciencia que haya visto jamás. Contigo aprendí que la investigación requiere mucho amor y que da muchos quebraderos de cabeza, pero que cuando sale bien, vale la pena, y todos los agobios y malos ratos parecen lejanos. Álvaro, siempre contento y con mil y una bromas para amenizar el día. Tú me enseñaste lo que no está escrito en los libros, y aunque estemos de acuerdo en mayor o menor medida, el concepto de practicidad que me inculcaste ha sido muy valioso. Sin embargo, la persona que más aparece en mi mente cuando recuerdo este intenso periodo, es Pilar. Sólo la gente que ha estado contigo, codo con codo, puede llegar a imaginar lo grande que eres. Sin ti no habría superado tantas dificultades. Siempre me has trasmitido tranquilidad y alegría. Tú has sido un pilar indispensable. Asimismo, Ernesto ocupa también un lugar muy importante. Resolutivo, audaz, positivo y paciente. Siempre me has ayudado y has estado ahí cuando algún equipo se “revelaba”. ¡Qué fea manía que a veces tienen de pararse, no estabilizarse, dar cosas raras...! En fin… ¡Qué habría sido de mí sin ti! Yo te hacía doctor honoris causa . Agradecimientos / Acknowledgements Por el laboratorio y el despacho han pasado también muchas más personas, y con todas ha habido momentos de risas inolvidables, así como momentos duros o de debilidad en los que tanto unos como otros nos hemos desahogado recibiendo siempre palabras de aliento. No voy a decir que esto no suceda en “la empresa”, pero este apoyo desinteresado que he visto muchas veces entre los becarios no es tan habitual “ahí fuera”. Pilar (necesitaba repetirte), José Miguel, Patricia, Ana J., David, Diego, María, Sofía, Cristina, Nuria, Marivel, Laura, Elisa, Crespo, Ana G., Marcela y Tao. Muchas gracias a todos. Otros muy buenos momentos que siempre me han alegrado el día han sido con el gran equipo multidisciplinar químico analítico-físicos : Rodrigo, Txino, Judith, Puri y Mayte. Muchas gracias. Asimismo, siempre los becarios de cualquier área nos hemos unido cuando ha hecho falta, sobre todo en reuniones nocturnas… Y eso es también de agradecer . Quiero mencionar en especial a Víctor. Juntos comenzamos el doctorado y hemos luchado por nuestros derechos como becarios FPI-CAR y estudiantes de doctorado. No nos harán ni caso, pero sabemos que no estamos solos . No podía olvidarme de Pilar Blanco y de todo el servicio de laboratorios: Montse, Amaya, Jorge, Arturo y Sara. Habéis sido también esenciales durante todo el proceso. Vuestra organización y efectividad es de admirar. I also want to thank to all lab mates from the Wadsworth Center (Albany, NY), and especially to Prof. Dr. Kannan. Thank you for welcoming me into your lab group and for the opportunity you gave me to work with you. It was a complete honor. You are a great person and a great scientist. Thanks also to Ariana, Masato, Xiaohua, Karl, Ying and Ethan (JungKeun) for your friendship and these nice conversations. Finalmente, también quiero agradecer de forma especial a todos aquellos que fuera del ámbito universitario me han apoyado y motivado durante este trayecto. Muchas gracias a mi familia, en especial a mi padre. Eres la definición de apoyo incondicional. Y también a Roberto. Cariño, tu optimismo y concepto de la vida me han sido imprescindibles. Creo que vosotros dos sois los que más habéis sufrido mis malos momentos y preocupaciones. Gracias por vuestra infinita paciencia. Gracias también a mis amigos. Por suerte sois muchos pero todos habéis sufrido mi falta de tiempo. En especial quiero mencionar a “mis niñas”, porque no habéis entendido “una mierda” de lo que he hecho, pero casi ha parecido que era también triunfo vuestro que yo llegara a acabar esto. También a Andrea, eras tú la que siempre me Agradecimientos / Acknowledgements decía lo “bueno” que era hacer un doctorado cuando empezamos la carrera. ¡Quién me lo iba a decir en ese momento! Gracias a todos. Ahora empezaré una nueva etapa y quiero que sigáis formando parte de ella. Y repito una vez más… ¡GRACIAS! … y nos vemos en los bares … Index INDEX Acronyms/Abbreviations …………………………………………………...….. 1 Summary ……………………………………………………………………....... 7 List of papers …………………………………………………………………… 13 Objectives ……………………………………………………………………….
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