Endémicas Canarias De Los Géneros Tolpis Y Pulicaria: Aplicaciones Quimiotaxonómicas Y De

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Endémicas Canarias De Los Géneros Tolpis Y Pulicaria: Aplicaciones Quimiotaxonómicas Y De “ESTUDIO DE METABOLITOS SECUNDARIOS DE ESPECIES ENDÉMICAS CANARIAS DE LOS GÉNEROS TOLPIS Y PULICARIA: APLICACIONES QUIMIOTAXONÓMICAS Y DE ACTIVIDAD BIOLÓGICA” MEMORIA Presentada para obtener el grado de Las Palmas de Gran Canaria, Marzo 2008 Doctor en Ciencias Químicas por Francisco Javier Pérez Galván 2008 universitaria, Biblioteca ULPGC. por Dedicada con cariño a mi familia, especialmente a mi madre, mis hermanos y mis tíos Boro y Alicia realizada Digitalización autores. los de documento, Del © AGRADECIMIENTOS A los miembros del Grupo Química Orgánica I del Departamento de Química de la Universidad de Las Palmas de Gran Canaria, en especial a los directores de tesis, el Dr. D. Jorge Triana Méndez y la Dra. Dña. Mariana López Sánchez, sin cuya experiencia, ayuda y consejos no habría sido posible la culminación de esta Memoria de 2008 Tesis, y al Dr. D. José Luis Eiroa Martínez por su ayuda en la recolección de las especies del Género Pulicaria, por los consejos en el terreno de la quimiotaxonomía y por sus constantes apoyo y ánimos. Asimismo, a los miembros del Departamento de universitaria, Química que, de algún modo, me han ayudado y apoyado en la culminación de este trabajo. Biblioteca Al Dr. D. Jaime Bermejo Barrera y a los miembros del Instituto de Productos ULPGC. Naturales y Agrobiología, C.S.I.C. de Tenerife, en especial a los Dres. D. Juan por Francisco León Oyola y D. Juan Carlos Hernández Pérez por su ayuda en la obtención de los datos de RMN y Masas, así como a los técnicos encargados de dichos equipos realizada pertenecientes al C.S.I.C. e I.U.B.O. Igualmente a los Dres. D. Javier González-Platas del Departamento de Física Fundamental de la Universidad de La Laguna y D. Matías López Rodríguez del I.U.B.O., por la realización de los espectros de difracción de rayos Digitalización X (ORTEP). autores. Al Dr. D. Francisco Estévez Rosas del Departamento de Bioquímica y Biología los de Molecular, Fisiología, Genética e Inmunología, de la Universidad de Las Palmas de Gran Canaria, por la realización de las pruebas de actividad citotóxica. documento, Al Dr. D. Pedro Luis Pérez de Paz del Departamento de Biología Vegetal Del (Botánica) en la Facultad de Farmacia de la Universidad de La Laguna, por la © recolección y clasificación botánica de las especies del género Tolpis estudiadas. A la Dra. Dña. Rosa Febles Hernández del Jardín Botánico Canario Viera y Clavijo de Las Palmas de Gran Canaria, por la clasificación botánica de las especies del género Pulicaria estudiadas. A mi madre y a mis hermanos Olga, Juani y Cristóbal por soportar estoicamente mis problemas y por ser un punto de apoyo incondicional en todo el proceso seguido en estos años de trabajo. Sin ellos no estaría al final de este proceso. Igualmente a mis tíos Boro y Alicia por el ánimo y el apoyo recibido durante la realización del trabajo. 2008 universitaria, Biblioteca ULPGC. por realizada Digitalización autores. los de documento, Del © ÍNDICE 1. Introducción……………………………………………………………... 1 2. Objetivos………………………………………………………………… 19 3. Estudio químico de especies del Género Tolpis 3.1. Introducción al Género Tolpis……………………………………… 25 3.2. Tolpis webbii Sch. Bip. ex Webb et Berth. Parte Teórica………….. 35 2008 3.3. Tolpis webbii Sch. Bip. ex Webb et Berth. Parte Experimental……. 65 3.4. Tolpis sp. Parte Teórica…………………………………………… 91 3.5. Tolpis sp. Parte Experimental…………………………………….. 115 universitaria, 4. Estudio químico de especies del Género Pulicaria Biblioteca 4.1. Introducción al Género Pulicaria………………………………….. 139 4.2. Pulicaria burchardii A. Hans. & Sund. ssp. burchardii. ULPGC. Parte Teórica………………………………………………………. 175 por 4.3. Pulicaria burchardii A. Hans. & Sund. ssp. burchardii. Parte Experimental………………………………………………… 187 realizada 4.4. Pulicaria canariensis Bolle ssp. canariensis. Parte Teórica……… 199 4.5. Pulicaria canariensis Bolle ssp. canariensis. Parte Experimental... 253 4.6. Pulicaria canariensis Bolle ssp. lanata (Font Quer & Svent.) Digitalización Bramwell & G. Kunkel. Parte Teórica……………………………. 291 autores. 4.7. Pulicaria canariensis Bolle ssp. lanata (Font Quer & Svent.) los de Bramwell & G. Kunkel. Parte Experimental……………………… 307 5. Estudio de actividades biológicas 5.1. Parte Teórica……………………………………………………..... 327 documento, Del 5.2. Parte Experimental………………………………………………… 335 © 6. Técnicas generales e Instrumentación………………...………………... 341 7. Abreviaturas y acrónimos………………………………………………. 347 8. Conclusiones……………………………………………………………. 351 2008 universitaria, Biblioteca ULPGC. por realizada Digitalización autores. los de “El Alquimista”, de William Fettes Douglas documento, Del © 1. INTRODUCCIÓN —————————————————————— 1. Introducción La flora de la región Macaronésica pone de manifiesto un cierto número de características típicas de las islas oceánicas como es el caso de un alto grado de endemismos (40% en el caso de las Islas Canarias) y un predominio de formas leñosas entre los endemismos (el 70% de los endemismos de las Islas Canarias son leñosos). Sin embargo, aunque la región Macaronésica es representante típica de los sistemas insulares oceánicos en diferentes aspectos, la región en general, y las Islas Canarias en particular, difieren de forma marcada de otros grupos de islas más aisladas (como el 2008 caso de las islas Hawaii en el Pacífico) en la relativa proximidad a las potenciales áreas fuente del continente. universitaria, Las islas más orientales de Canarias están aproximadamente a 95 km de las costas del norte de África, y en los últimos 20 millones de años probablemente han Biblioteca podido llegar a estar a 65 km de distancia de esas costas. Además, se han localizado más de 20 montañas volcánicas submarinas situadas entre las Islas Canarias, Madeira, Islas ULPGC. Salvajes, y el continente, muchas de las cuales están a profundidades inferiores a los por 100 metros por debajo del nivel del mar. Estudios más recientes ponen de manifiesto que algunas de estas montañas submarinas tienen al menos una antigüedad de 60 realizada millones de años, por lo cual es posible que pudieran haber facilitado la dispersión entre el continente y las islas, actuando como una especie de trampolín durante los periodos glaciales, cuando los niveles marinos eran más bajos y esas montañas podían emerger Digitalización por encima del nivel del mar. autores. los La relativa proximidad de las islas de la Macaronesia al continente, la existencia de de estos posibles trampolines y la edad de las islas, hacen posible la hipótesis de que algunos géneros puedan haber provocado múltiples colonizaciones independientes en esta región. La retrocolonización hacia el continente desde la Macaronesia podría haber documento, Del tenido lugar de igual forma, por lo que las islas actuarían como un área fuente para los © endemismos continentales. Dichas relaciones entre la flora de las islas y el continente son mucho más complejas que aquellas que constituyen las hipótesis que se han planteado para otras islas de sistemas oceánicos insulares, tales como las islas Hawaii y las Galápagos. 3 Tesis Doctoral Francisco Javier Pérez Galván Por todo ello, y para una mejor comprensión del proceso de formación de la flora de la Macaronesia, es necesario conocer cuál ha sido la sucesión de eventos que han dado origen a las islas, partiendo de la consideración de las teorías de la Tectónica de Placas y la Deriva Continental, pues precisamente la explicación más aceptada acerca del origen y la formación de los archipiélagos que constituyen la Macaronesia radica en los movimientos de las masas continentales. La formación del Océano Atlántico se inicia hace unos 180 millones de años, 2008 cuando lo que hoy es América del Norte empieza a separarse de Europa (África se separa un poco más tarde), alcanzando su actual forma durante el periodo Cretácico, universitaria, aproximadamente hace unos 65 millones de años, y continuando en la actualidad con su expansión a una velocidad de unos 2 cm por año. Desde un punto de vista puramente geológico, las de la Macaronesia son unas islas oceánicas de origen volcánico, y Biblioteca teniendo en cuenta su proceso de génesis podemos dividirlas en dos grupos, que son: ULPGC. Las Azores. por Resto de los archipiélagos. realizada En el caso de las islas Azores, los estudios geológicos ponen de manifiesto que cada una de ellas se corresponde con un afloramiento de la dorsal mesoatlántica, mientras que el resto de los archipiélagos de la Macaronesia se encuentran en una zona Digitalización media de la placa africana (situación intraplaca) que se corresponde con una región relativamente próxima a la zona de contacto entre la corteza oceánica y la corteza autores. continental. los de En lo que respecta a las Islas Canarias su origen ha dado lugar a diferentes polémicas entre los geólogos, con dos grandes hipótesis predominantes: la de la documento, procedencia continental y la del origen volcánico independiente. En el primer caso se Del propone que las islas son fragmentos del vecino continente africano, que con el © transcurso del tiempo quedaron separadas al romperse los puentes terrestres que las unían entre sí, o que las conectaban con el continente1. En el segundo caso la existencia de pruebas de tipo geológico como son la presencia de calizas fosilíferas y playas levantadas, parecen indicar su formación en función de un origen volcánico a ––––––––––––––––––––––––––––––––––––––––––––– 1. Sunding, P. “Origins of the Macaronesian flora”. In Plants and Islands. Bramwell Ed. (1979), London, 13-40. 4 1. Introducción partir del fondo marino, estando sumergidas durante
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