{"id":112735,"date":"2018-03-11T10:39:53","date_gmt":"2018-03-11T10:39:53","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/mecanismo-catala%c2%adtico-de-la-aril-alcohol-oxidasa-de-pleurotus-eryngii\/"},"modified":"2018-03-11T10:39:53","modified_gmt":"2018-03-11T10:39:53","slug":"mecanismo-catala%c2%adtico-de-la-aril-alcohol-oxidasa-de-pleurotus-eryngii","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/mecanismo-catala%c2%adtico-de-la-aril-alcohol-oxidasa-de-pleurotus-eryngii\/","title":{"rendered":"Mecanismo catal\u00edtico de la aril-alcohol oxidasa de pleurotus eryngii"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Aitor Hern\u00e1ndez Ortega <\/strong><\/h2>\n<p>Durante la degradaci\u00f3n de la lignina por pleurotus eryngii la enzima extracelular aril-alcohol oxidasa (aao) genera el h2o2 que act\u00faa como sustrato oxidante de las peroxidasas ligninol\u00edticas y para la formaci\u00f3n del radical hidroxilo. El poder reducto r para la activaci\u00f3n del o2 a h2o2 proviene de la oxidaci\u00f3n de alcoholes arom\u00e1ticos a los correspondientes aldeh\u00eddos, siendo el alcohol p-metoxibenc\u00edlico el sustrato natural de la aao de p. Eryngii. Esta oxidasa es una flavoenzima que contiene como c ofactor una mol\u00e9cula de fad unida de forma no covalente. Durante el presente trabajo se han estudiado en profundidad el mecanismo catal\u00edtico y las relaciones estructura-funci\u00f3n de la aao. Todo ello ha sido posible gracias a la disponibilidad de la es tructura cristalogr\u00e1fica de esta oxidasa y de un protocolo de expresi\u00f3n heter\u00f3loga en escherichia coli y activaci\u00f3n in vitro de la enzima. el mecanismo catal\u00edtico de la aao se estudi\u00f3 empleando sustratos alpha-deuterados y agua deuterada como solvent e de la reacci\u00f3n. Durante la semi-reacci\u00f3n de reducci\u00f3n tiene lugar un proceso concertado (es decir, sin formaci\u00f3n un intermediario estable) de transferencia de hidruro, desde el carbono-alpha del alcohol al n5 de la flavina, y de prot\u00f3n, desde el hi droxilo del alcohol a la base catal\u00edtica. Este mecanismo es diferente del mecanismo secuencial (no-concertado) observado en otras oxidorreductasas de la superfamilia gmc. Empleando las formas alpha-monodeuteradas del alcohol p-metoxibenc\u00edlico se enco ntr\u00f3 que la transferencia de hidruro es un proceso estereoselectivo, que viene determinado por la posici\u00f3n del sustrato en el centro activo de la aao. debido a que se hab\u00eda observado previamente que la aao es tambi\u00e9n capaz de oxidar algunos aldeh\u00eddos  arom\u00e1ticos, se estudi\u00f3 en detalle la oxidaci\u00f3n de estos compuestos combinando diferentes t\u00e9cnicas experimentales. Se observ\u00f3 que la enzima \u00fanicamente es capaz de oxidar aldeh\u00eddos arom\u00e1ticos en su forma gem-diol. Esta caracter\u00edstica explic\u00f3 por qu\u00e9 l a presencia de sustituyentes electrof\u00edlicos en el anillo arom\u00e1tico (que promueven la hidrataci\u00f3n del carbonilo) favorec\u00eda la oxidaci\u00f3n, y as\u00ed mismo, explic\u00f3 la diferente especificidad de la aao por ambos tipos de sustratos (alcohol vs aldeh\u00eddo). Adem \u00e1s, se postul\u00f3 que el mecanismo de oxidaci\u00f3n de la forma gem-diol de los aldeh\u00eddos es similar al mecanismo de oxidaci\u00f3n de los alcoholes, donde participa una base catal\u00edtica, activando el sustrato a trav\u00e9s de la abstracci\u00f3n del prot\u00f3n de uno de los g<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Mecanismo catal\u00edtico de la aril-alcohol oxidasa de pleurotus eryngii<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Mecanismo catal\u00edtico de la aril-alcohol oxidasa de pleurotus eryngii <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Aitor Hern\u00e1ndez Ortega <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Complutense de Madrid<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 25\/05\/2012<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<h3>Direcci\u00f3n y tribunal<\/h3>\n<ul>\n<li><strong>Director de la tesis<\/strong>\n<ul>\n<li>Patricia Ferreira Neila<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: jos\u00e9 Mart\u00ednez peinado <\/li>\n<li>Miguel \u00e1ngel De la rosa acosta (vocal)<\/li>\n<li>willem j.h. Van berkel (vocal)<\/li>\n<li>Carlos G\u00f3mez-moreno calera (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Aitor Hern\u00e1ndez Ortega Durante la degradaci\u00f3n de la lignina por pleurotus eryngii la enzima extracelular aril-alcohol oxidasa [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"site-sidebar-layout":"default","site-content-layout":"","ast-site-content-layout":"","site-content-style":"default","site-sidebar-style":"default","ast-global-header-display":"","ast-banner-title-visibility":"","ast-main-header-display":"","ast-hfb-above-header-display":"","ast-hfb-below-header-display":"","ast-hfb-mobile-header-display":"","site-post-title":"","ast-breadcrumbs-content":"","ast-featured-img":"","footer-sml-layout":"","theme-transparent-header-meta":"","adv-header-id-meta":"","stick-header-meta":"","header-above-stick-meta":"","header-main-stick-meta":"","header-below-stick-meta":"","astra-migrate-meta-layouts":"default","ast-page-background-enabled":"default","ast-page-background-meta":{"desktop":{"background-color":"var(--ast-global-color-4)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"tablet":{"background-color":"","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"mobile":{"background-color":"","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""}},"ast-content-background-meta":{"desktop":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"tablet":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"mobile":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""}},"footnotes":""},"categories":[986,17],"tags":[224164,15142,2604,3403,85461,224165],"class_list":["post-112735","post","type-post","status-publish","format-standard","hentry","category-complutense-de-madrid","category-quimica","tag-aitor-hernandez-ortega","tag-carlos-gomez-moreno-calera","tag-jose-Martinez-peinado","tag-miguel-angel-de-la-rosa-acosta","tag-patricia-ferreira-neila","tag-willem-j-h-van-berkel"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/112735","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/comments?post=112735"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/112735\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=112735"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=112735"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=112735"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}