Publication: Diseño, síntesis y aplicaciones de rotaxanos de amidas bencílicas: liberación controlada de aromas, síntesis de β-lactamas y desarrollo de compuestos luminiscentes
Authors
López Sánchez, Jorge
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Escuela Internacional de Doctorado
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Pastor Vivero, Aurelia ; Berná Cánovas, José
Publisher
Universidad de Murcia
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DOI
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info:eu-repo/semantics/doctoralThesis
Description
Abstract
Las moléculas entrelazadas mecánicamente (MEMs) mantienen sus componentes unidos a través del enlace mecánico, lo que les confiere propiedades únicas e interesantes. Concretamente, con el desarrollo de metodologías sintéticas y la gran amplitud de movimiento de sus componentes, los rotaxanos se han convertido en una de las MEMs más utilizadas en diferentes ámbitos como la ciencia de los materiales, la nanotecnología y la maquinaria molecular.
Objetivos
Este trabajo se centra en el diseño, síntesis y estudio de nuevas moléculas entrelazadas mecánicamente basadas en rotaxanos de amidas bencílicas, con aplicaciones en liberación controlada, catálisis y materiales luminiscentes.
1. Desarrollar sistemas de liberación controlada de aromas utilizando rotaxanos, donde la liberación se active mediante estímulos como luz, temperatura o hidrólisis enzimática.
2. Ampliar la cavidad del macrociclo para evaluar su capacidad como catalizador en la obtención de β-lactamas entrelazadas a partir de N-bencilfumaramidas.
3. Sintetizar rotaxanos que incorporen carbenos N-heterocíclicos coordinados con Au(I) y estudiar sus propiedades luminiscentes.
Metodología
Para cumplir con el primer objetivo, se han sintetizado un conjunto de [2]pseudorotaxanos que incorporan un alcohol volátil (aroma) en la estructura del eje unido mediante una función éster y se ha estudiado la estabilidad térmica, así como la liberación controlada del aroma mediante hidrólisis enzimática.
Para alcanzar el segundo objetivo, se ha desarrollado una ruta sintética para la obtención de [2]rotaxanos con un anillo extendido usando fumaramidas como plantillas. Además, se ha estudiado la reacción de ciclación de las N-bencilfumaramidas entrelazadas y obtención de las correspondientes β-lactamas.
Para completar el tercer objetivo, se ha llevado a cabo la síntesis de alquinilcarbeno-complejos de oro(I) a partir de los [2]rotaxanos funcionalizados con unidades (NHC)AuX (X = Cl, Br). También se han estudiado las propiedades fotoluminiscentes de los rotaxanos funcionalizados con dos unidades (NHC)AuCCAr en disolución.
Conclusiones
1. Se han desarrollado [2]pseudorotaxanos para la liberación controlada de aromas, donde el desenhebrado y la hidrólisis enzimática permiten liberar el aroma de forma lenta. Factores como la demanda estérica, la polaridad y la temperatura influyen en el proceso, así como el papel protector del macrociclo.
2. Se han sintetizado [2]rotaxanos con macrociclos extendidos mediante metodología clipping. Estos presentan una conformación flexible que facilita el deslizamiento del eje y favorece la ciclación con alta regio- y diastereoselectividad, generando β-lactamas con buenos rendimientos.
3. Se han preparado rotaxanos con fragmentos NHC-Au(I). La introducción de unidades etiniloro(I) les confiere fosforescencia en disolución, abriendo posibilidades en el campo de materiales funcionales.
Mechanically interlocked molecules (MEMs) hold their components together through mechanical bonding, which gives them unique and interesting properties. Specifically, with the development of synthetic methodologies and the large range of motion of their components, rotaxanes have become one of the most widely used MEMs in different fields such as materials science, nanotechnology and molecular machinery. Objectives This work focuses on the design, synthesis, and study of new mechanically interlocked molecules based on benzyl amide rotaxanes, with applications in controlled release, catalysis, and luminescent materials. 1. Develop controlled fragrance delivery systems using rotaxanes, where release is activated by stimuli such as light, temperature, or enzymatic hydrolysis. 2. Enlarge the macrocycle cavity to evaluate its capacity as a catalyst in obtaining interlocked β-lactams from N-benzylfumarimides. 3. Synthesize rotaxanes that incorporate N-heterocyclic carbenes coordinated with Au(I) and study their luminescent properties. Methodology To achieve the first objective, a set of [2]pseudorotaxanes incorporating a volatile alcohol (fragance) into the thread structure linked by an ester function has been synthesized, and their thermal stability and controlled release of the fragance through enzymatic hydrolysis has been studied. For the second objective, a synthetic route was developed to obtain [2]rotaxanes with an extended ring using fumarimides as templates. In addition, the cyclization reaction of interlocked N-benzylfumarimides and the obtaining of the corresponding β-lactams were studied. To complete the third objective, the synthesis of alkynylcarbene-gold(I) complexes was carried out from [2]rotaxanes functionalized with (NHC)AuX units (X = Cl, Br). The photoluminescent properties of rotaxanes functionalized with two (NHC)AuCCAr units in solution have also been studied. Conclusions 1. Pseudorotaxanes have been developed for the controlled release of aromas, where dethreading and enzymatic hydrolysis allow the fragance to be released slowly. Factors such as steric demand, polarity, and temperature influence the process, as does the protective role of the macrocycle. 2. [2]Rotaxanes with extended macrocycles have been synthesized using clipping methodology. These have a flexible conformation that facilitates thread slipping and promotes cyclization with high regio- and diastereoselectivity, generating β-lactams with good yields. 3. Rotaxanes with NHC-Au(I) fragments have been prepared. The introduction of ethynyl gold(I) units confers phosphorescence in solution, opening possibilities in the field of functional materials.
Mechanically interlocked molecules (MEMs) hold their components together through mechanical bonding, which gives them unique and interesting properties. Specifically, with the development of synthetic methodologies and the large range of motion of their components, rotaxanes have become one of the most widely used MEMs in different fields such as materials science, nanotechnology and molecular machinery. Objectives This work focuses on the design, synthesis, and study of new mechanically interlocked molecules based on benzyl amide rotaxanes, with applications in controlled release, catalysis, and luminescent materials. 1. Develop controlled fragrance delivery systems using rotaxanes, where release is activated by stimuli such as light, temperature, or enzymatic hydrolysis. 2. Enlarge the macrocycle cavity to evaluate its capacity as a catalyst in obtaining interlocked β-lactams from N-benzylfumarimides. 3. Synthesize rotaxanes that incorporate N-heterocyclic carbenes coordinated with Au(I) and study their luminescent properties. Methodology To achieve the first objective, a set of [2]pseudorotaxanes incorporating a volatile alcohol (fragance) into the thread structure linked by an ester function has been synthesized, and their thermal stability and controlled release of the fragance through enzymatic hydrolysis has been studied. For the second objective, a synthetic route was developed to obtain [2]rotaxanes with an extended ring using fumarimides as templates. In addition, the cyclization reaction of interlocked N-benzylfumarimides and the obtaining of the corresponding β-lactams were studied. To complete the third objective, the synthesis of alkynylcarbene-gold(I) complexes was carried out from [2]rotaxanes functionalized with (NHC)AuX units (X = Cl, Br). The photoluminescent properties of rotaxanes functionalized with two (NHC)AuCCAr units in solution have also been studied. Conclusions 1. Pseudorotaxanes have been developed for the controlled release of aromas, where dethreading and enzymatic hydrolysis allow the fragance to be released slowly. Factors such as steric demand, polarity, and temperature influence the process, as does the protective role of the macrocycle. 2. [2]Rotaxanes with extended macrocycles have been synthesized using clipping methodology. These have a flexible conformation that facilitates thread slipping and promotes cyclization with high regio- and diastereoselectivity, generating β-lactams with good yields. 3. Rotaxanes with NHC-Au(I) fragments have been prepared. The introduction of ethynyl gold(I) units confers phosphorescence in solution, opening possibilities in the field of functional materials.
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6-dic-2026
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