{"id":117740,"date":"2018-03-11T10:47:23","date_gmt":"2018-03-11T10:47:23","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/da%c2%adadas-ferroceno-123-triazol-como-sensores-moleculares-multicanal-de-aniones-cationes-y-pares-ionicos\/"},"modified":"2018-03-11T10:47:23","modified_gmt":"2018-03-11T10:47:23","slug":"da%c2%adadas-ferroceno-123-triazol-como-sensores-moleculares-multicanal-de-aniones-cationes-y-pares-ionicos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/compuestos-heterociclicos\/da%c2%adadas-ferroceno-123-triazol-como-sensores-moleculares-multicanal-de-aniones-cationes-y-pares-ionicos\/","title":{"rendered":"D\u00edadas ferroceno-1,2,3-triazol como sensores moleculares multicanal de aniones, cationes y pares i\u00f3nicos"},"content":{"rendered":"

Tesis doctoral de M\u00aa Carmen Gonz\u00e1lez Valera <\/strong><\/h2>\n

Resumen tesis en espa\u00f1ol. el objetivo principal de la investigaci\u00f3n descrita en esta tesis doctoral consisti\u00f3 en el dise\u00f1o, s\u00edntesis y estudio de las propiedades sensoras de una variedad de receptores en los que se combinan las caracter\u00edsticas coordinantes del anillo de triazol, preparado mediante una reacci\u00f3n de cicloadici\u00f3n 1,3-dipolar de huisgen (reacci\u00f3n "click"), con la demostrada capacidad de la unidad de ferroceno para actuar como unidad de se\u00f1alizaci\u00f3n tanto electroqu\u00edmica como cromog\u00e9nica. Para ello se dise\u00f1aron tres tipos de familias de receptores de diferente topolog\u00eda pero que disponen, fundamentalmente, de una unidad de ferroceno conectada al anillo de 1,2,3-triazol. Posteriormente, se realizaron estudios electroqu\u00edmicos, de espectroscop\u00eda uv-vis, fluorescencia, rmn y espectrometr\u00eda de masas para evaluar la capacidad como sensores moleculares de aniones, cationes y pares i\u00f3nicos de las familias de receptores sintetizados. los resultados m\u00e1s significativos del trabajo realizado se resumen a continuaci\u00f3n: en los cap\u00edtulos 1 y 2 se describe la s\u00edntesis de dos nuevas familias de derivados de ferroceno 1,1'-asim\u00e9tricamente disustituidos mediante la conversi\u00f3n quimioselectiva de una de las agrupaciones azida presente en el 1,1'-bis(azido)ferroceno en una unidad de 1,2,3-triazol-4-sustituida. A continuaci\u00f3n se transform\u00f3 la agrupaci\u00f3n azida existente en esas familias de derivados, en otro tipo de agrupaciones tales como imina, urea, etc., Lo que permiti\u00f3 acceder a nuevas familias de potenciales receptores moleculares. los compuestos descritos en el cap\u00edtulo 1, en los que la unidad de se\u00f1alizaci\u00f3n conectada al c4 del anillo de 1,2,3-triazol es una segunda unidad de ferroceno, han demostrado ser buenos receptores electroqu\u00edmicos, \u00f3pticos y fluorescentes para el reconocimiento de los cationes pb2+ y zn2+, que quedan enlazados a ambos receptores a trav\u00e9s de las unidades de triazol e imina presentes en sus estructuras. en el cap\u00edtulo 2 se describe una nueva familia de derivados de ferroceno 1,1'-asim\u00e9tricamente disustituidos, en los que el sustituyente en posici\u00f3n 1 de la unidad de ferroceno fue una d\u00edada triazol-pireno mientras que en posici\u00f3n 1' se incorporaron unidades de reconocimiento adicionales (imina, amida o urea) conectadas, a su vez, a unidades de se\u00f1alizaci\u00f3n de diferente naturaleza (fluor\u00f3foros y crom\u00f3foros). Todos los compuestos obtenidos pueden actuar como sensores moleculares de aniones con una selectividad elevada aunque diferente en cada caso, mientras que la afinidad por los cationes met\u00e1licos difiere en gran medida de un receptor a otro. Adem\u00e1s, dos receptores de esta familia han demostrado su habilidad para el reconocimiento de pares i\u00f3nicos. Uno de ellos solo reconoce los cationes zn2+, cd2+, ca2+ y mg2+ cuando se coordina simult\u00e1neamente con los aniones h2po4- o aco-. La formaci\u00f3n del complejo con ambas especies da lugar a un gran incremento de la fluorescencia y a cambios significativos en las propiedades electroqu\u00edmicas y colorim\u00e9tricas del receptor. Por otro lado, otro receptor perteneciente a esta familia reconoce de manera selectiva el par i\u00f3nico formado por el cati\u00f3n pb2+ y el ani\u00f3n hp2o73? Dando lugar a un cambio dr\u00e1stico de color y de propiedades fotoemisivas del receptor. en el cap\u00edtulo 3 se han preparado dos receptores tripodales basados en un anillo de benceno central portador de tres anillos de 1,2,3- triazol a los que se encuentran unidos una unidad fotoactiva como el pireno o una unidad electroactiva como el ferroceno. El primero de ellos presenta una gran selectividad hacia el ani\u00f3n citrato cuando se compara con otros aniones carboxilato similares en un entorno acuoso, adem\u00e1s de reconocer los cationes cu2+ y hg2+ lo que produce cambios importantes en los espectros de absorci\u00f3n y de emisi\u00f3n del receptor. El segundo receptor reconoce de manera selectiva el cati\u00f3n pb2+ dando lugar a un cambio de color y a una variaci\u00f3n en el potencial redox del receptor. resumen tesis en ingl\u00e9s. the main objective of the research described in this thesis was the design, synthesis and study of the sensing properties of a variety of receptors in which the coordination properties of the triazole ring, prepared by a 1,3-dipolar huisgen cycloaddition reaction ("click reaction"), with the well known ability of the ferrocene unit to act as both electrochemical unit as chromogenic signaling, are combined. For this purpose three types of receptor families with different topologies were designed. However, these molecules have the common structural feature of heaving a ferrocene unit directly linked to the 1,2,3-triazole ring. Subsequently, electrochemical, uv-vis, fluorescence, nmr, and mass spectrometry studies were performed to evaluate the ability of these new families of receptors as molecular sensors of anions, cations and ion pairs. the most significant results obtained can be summarized as follows: in chapters 1 and 2 the synthesis of two new families of 1,1'-asymmetrically disubstituted ferrocene derivatives has been described. The synthetic methodology used involves the initial chemoselective conversion of one of the azide groups present in the 1,1'-bis(azido)ferrocene into a 1,2,3-triazole-4-substituted unit, followed by the conversion of the remaining azide group into other functionalities such as imine, urea, etc. the compounds described in chapter 1, in which the signaling unit connected to c4 1,2,3-triazole ring is another ferrocene moiety, have proven to be good electrochemical, optical and fluorescent receptors for the recognition of pb2+ and zn2+ cations, which are linked to both receptors through the triazole and imine units present in their structures. in chapter 2 a new family of 1,1'-asymmetrically disubstituted ferrocene derivatives is described. In these compounds,, the substituent at position 1 of the ferrocene moiety was a triazole-pyrene dyad while in position 1' additional recognition units (imine, amide or urea) directly linked to signal units of different nature (fluorophores and chromophores) were incorporated. All compounds obtained can act as highly selective molecular sensors for anions and cations, although such selectivity depends on the specific receptor used. In addition, two receptors of this family have shown ability for recognizing ion pairs. Significantly, one of them only recognizes zn2+, cd2+, ca2+ and mg2+ cations when they are simultaneously coordinated to h2po4- or aco- anions. Complex formation with both species results in a large increase in fluorescence and significant changes in colorimetric and electrochemical properties of the receptor. Furthermore, another member of this family of receptors selectively recognizes the ion pair formed by pb2+ cation and hp2o73- anion, resulting in a dramatic color change and a large change in the photoemisive properties of the receptor as the recognition process takes place. in chapter 3 two receptors based on a tripodal central benzene ring, bearing three of 1,2,3-triazole rings directly linked to a photoactive pyrene unit or to an electroactive ferrocene unit, were prepared. The former has a high selectivity towards the citrate anion, when compared with similar carboxylate anions in an aqueous environment. In addition, this receptor recognizes cu2+ and hg2+ cations, giving rise to important changes in its absorption and emission spectra. The latter, selectively recognizes pb2+ cation resulting in a color change and a change in the redox potential of the host.<\/p>\n

 <\/p>\n

Datos acad\u00e9micos de la tesis doctoral \u00abD\u00edadas ferroceno-1,2,3-triazol como sensores moleculares multicanal de aniones, cationes y pares i\u00f3nicos<\/strong>\u00ab<\/h3>\n
    \n
  • T\u00edtulo de la tesis:<\/strong>\u00a0 D\u00edadas ferroceno-1,2,3-triazol como sensores moleculares multicanal de aniones, cationes y pares i\u00f3nicos <\/li>\n
  • Autor:<\/strong>\u00a0 M\u00aa Carmen Gonz\u00e1lez Valera <\/li>\n
  • Universidad:<\/strong>\u00a0 Murcia<\/li>\n
  • Fecha de lectura de la tesis:<\/strong>\u00a0 29\/06\/2015<\/li>\n<\/ul>\n

     <\/p>\n

    Direcci\u00f3n y tribunal<\/h3>\n
      \n
    • Director de la tesis<\/strong>\n
        \n
      • Alberto Tarraga Tomas<\/li>\n<\/ul>\n<\/li>\n
      • Tribunal<\/strong>\n
          \n
        • Presidente del tribunal: Antonio Arques adame <\/li>\n
        • rosario Mart\u00ednez romera (vocal)<\/li>\n
        • Jos\u00e9 Manuel Villalgordo soto (vocal)<\/li>\n
        • L\u00f3pez l\u00f3pez Juan Luis (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n

           <\/p>\n","protected":false},"excerpt":{"rendered":"

          Tesis doctoral de M\u00aa Carmen Gonz\u00e1lez Valera Resumen tesis en espa\u00f1ol. el objetivo principal de la investigaci\u00f3n descrita en esta […]<\/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":[1412,8235],"tags":[8264,93761,48741,80720,231852,137480],"class_list":["post-117740","post","type-post","status-publish","format-standard","hentry","category-compuestos-heterociclicos","category-murcia","tag-alberto-tarraga-tomas","tag-antonio-arques-adame","tag-jose-manuel-villalgordo-soto","tag-lopez-lopez-juan-luis","tag-ma-carmen-gonzalez-valera","tag-rosario-Martinez-romera"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/117740","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=117740"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/117740\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=117740"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=117740"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=117740"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}