{"id":81850,"date":"2018-03-10T00:05:45","date_gmt":"2018-03-10T00:05:45","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/reacciones-de-nitrosacion-precursoras-de-mecanismos-de-alquilacion-nitrosacion-de-aminoacidos-y-potencial-alquilante-de-los-productos\/"},"modified":"2018-03-10T00:05:45","modified_gmt":"2018-03-10T00:05:45","slug":"reacciones-de-nitrosacion-precursoras-de-mecanismos-de-alquilacion-nitrosacion-de-aminoacidos-y-potencial-alquilante-de-los-productos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/ciencias-medicas\/reacciones-de-nitrosacion-precursoras-de-mecanismos-de-alquilacion-nitrosacion-de-aminoacidos-y-potencial-alquilante-de-los-productos\/","title":{"rendered":"Reacciones de nitrosaci\u00f3n precursoras de mecanismos de alquilaci\u00f3n: nitrosaci\u00f3n de amino\u00e1cidos y potencial alquilante de los productos"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Mar\u00eda Del Pilar Garc\u00eda Santos <\/strong><\/h2>\n<p>Se ha  estudiado el mecanismo de las reacciones de nitrosaci\u00f3n de nueve amino\u00e1cidos con grupo amino primario en medio \u00e1cido: seis   -amino\u00e1cidos(glicina, alanina, acido   -aminobut\u00edrico, \u00e1cido   -aminoisobut\u00edrico, valina y norvalina), dos b-amino \u00e1cidos(b-alanina y \u00e1cido b-aminobut\u00edrico) y un y-amino\u00e1cido (\u00e1cido y-aminobut\u00edrico).  el mecanismo de nitrosaci\u00f3n propuesto implica al tri\u00f3xido de dinitr\u00f3geno como agente nitrosante de las formas neutra y b\u00e1sica del amino\u00e1cido, y conduce a la ecuaci\u00f3n de velocidad:  v=ka k m ke [aa][nit]2 [h+]2    + kb ki kii km      [aa][nit]2[h+]  &#8212;&#8212;&#8212;&#8212;&#8212;-                        &#8212;&#8212;&#8212;&#8212;&#8211;  (ki+[h+])(ka+[h+])2                     (ki+[h+])(ka+[h+])2  k m es la constante de formaci\u00f3n de n2o3, ki y kii son las constantes macrosc\u00f3picas de disociaci\u00f3n del amino\u00e1cido, ke la constante de disociaci\u00f3n del \u00e9ster del amino\u00e1cido y ka es la constante de desprotonaci\u00f3n del \u00e1cido nitroso.  todas las reacciones estudiadas satisfacen relaciones isocin\u00e9ticas, apoyando la idea de un mecanismo com\u00fan.  el orden de magnitud(10 7-10 8 m-1 s-1) encontrando para los coeficientes de velocidad de nitrosaci\u00f3n, es propio de mecanismos controlados por difusi\u00f3n. la secuencia de reactivadas es :   -amino\u00e1cidos&lt; b-amino\u00e1cidos &lt; y-amino\u00e1cidos. los resultados se han interpretado a trav\u00e9s del efecto -i del grupo carboxilo sobre el sitio nucle\u00f3filo- nh2 del amino\u00e1cido.  se ha estudiado el mecanismo de las reacciones de alquilaci\u00f3n de la mol\u00e9cula 4-(p-nitrobencil)piridina(nbp) en medio neutro por los productos de nitrosaci\u00f3n de cada uno de los amino\u00e1cidos indicados y del \u00e1cido asp\u00e1rtico. en todos los casos se comprob\u00f3 la formaci\u00f3n del aducto nbp-productos de nitrosaci\u00f3n.  mediante espectograf\u00eda de rmn e ir se ha demostrado que los agentes alquilantes son las correspondientes lactonas. La secuencia de potencial alquilante observada es:   -lactonas&gt; b-lactonas&gt; y-lacto<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Reacciones de nitrosaci\u00f3n precursoras de mecanismos de alquilaci\u00f3n: nitrosaci\u00f3n de amino\u00e1cidos y potencial alquilante de los productos<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Reacciones de nitrosaci\u00f3n precursoras de mecanismos de alquilaci\u00f3n: nitrosaci\u00f3n de amino\u00e1cidos y potencial alquilante de los productos <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Mar\u00eda Del Pilar Garc\u00eda Santos <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Salamanca<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 18\/12\/1999<\/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>Julio Casado Linarejos<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: salvador Senent p\u00e9rez <\/li>\n<li>Jos\u00e9 Mar\u00eda Leal villalba (vocal)<\/li>\n<li>licesio Rodriguez hernandez (vocal)<\/li>\n<li>Jorge  Francisco Dias rodrigues gaspar (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Mar\u00eda Del Pilar Garc\u00eda Santos Se ha estudiado el mecanismo de las reacciones de nitrosaci\u00f3n de nueve 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