Novel ᴫ-Functional Components of Micro- and Nanoparticles for Nanomedicine

[eng] The present thesis is included in the area of Nanomedicine and supramolecular chemistry, focused on the design and preparation of different nano and microtools for delivery, therapy and sensing. Initially, the synthesis and characterization of structures derived from gemini-type pyridinium amp...

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Detalles Bibliográficos
Autor: Alea Reyes, María Elisa
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2017
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/114352
Acceso en línea:https://hdl.handle.net/2445/114352
http://hdl.handle.net/10803/404880
Access Level:acceso abierto
Palabra clave:Nanomedicina
Nanopartícules
Terapèutica
Nanomedicine
Nanoparticles
Biosensors
Therapeutics
Descripción
Sumario:[eng] The present thesis is included in the area of Nanomedicine and supramolecular chemistry, focused on the design and preparation of different nano and microtools for delivery, therapy and sensing. Initially, the synthesis and characterization of structures derived from gemini-type pyridinium amphiphiles were reported. They have the ability to play multiple roles such as transfer agent and stabilizer, as well as ionophores, and also are responsible for the preparation, stability, and delivery properties of the gold nanoparticles (AuNPs), which gold core is stabilized by the anions present in the bis-pyridinium salts. The gold nanoparticles synthesized proved stable and to have low polydispersity and showed the ability to incorporate piroxicam. Therefore, the in vitro release of 3·AuNPs and 4·AuNPs at two different pH values (7.4 and 5.5) proves a faster release profile at pH 7.4, indicating their suitability as promising materials for delivery in physiological conditions. On the other hand, this report also includes the synthesis and characterization of porphyrin derivatives as photosensitizers in particular metalloporphyrins and their subsequent incorporation to different vehicles such as gold nanoparticles, microparticles (polysilicon-gold) and gold nanorods for their use in photodynamic therapy, due to their capacity to produce reactive oxygen species after irradiation, inducing the cell death. The successfully functionalization of this vehicles were followed by UV-visible absorption spectroscopy, High-Resolution Transmission Electron Microscopy (HRTEM) or Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), X-ray Photoelectron Spectroscopy (XPS), Thermogravimetric analysis (TGA), Fluorescence Spectroscopy, contact angle measurements and fluorescence microscopy. Additionally, the formation of self-assembled monolayers (SAMs) on polysilicon substrates (wafers and microparticles) was investigated, using different immobilization methodologies (covalent and non-covalent) in order to obtain a functionalization protocol which can be easily repetitive and effective. Firstly, this substrates were functionalized with two groups of compounds (pyridinium and imidazolium salts) used as host in the subsequent incorporation of the Zn(II) porphyrin with a high potential to be used in PDT. The immobilization of the different hosts was following by contact angle, while the presence of the Zn(II) porphyrin was confirmed by fluorescence microscopy. The concentration of the photosensitizer incorporated on the polysilicon microparticles was found in the range of 2.2-2.6 µM. On the other hand, a release study of the incorporated porphyrin during a week was performed, resulting in a very low percentage of the total incorporated porphyrin. This result indicates that a stable interaction is established between the porphyrin and the host on the surface. Finally, we describe the non-covalent functionalization of polysilicon substrates (wafers and microparticles) with gemini-type amphiphilic bipyridinium salts (1·4PF6- 3·4PF6), witch act as host for the subsequent incorporation of the neurotransmitters Dopamine hydrochloride (Dop), Serotonin hydrochloride (Ser), Adrenaline hydrochloride (Adr) and Noradrenaline hydrochloride (Nor), in order to obtain the optimum system potentially suitable for sensors of compounds with electron rich groups. The successfully functionalization of the polysilicon substrates was followed by contact angle measurements. Additionally, fluorescence microscopy was used to detect the complex bis-bipyridinium salt-neurotransmitter in both substrates showed an increase on the fluorescence intensity on the substrates functionalized with the bis- bipyridinium salts and subsequent incorporation of the neurotransmitters respect to the controls. Polysilicon surfaces functionalized with 1·4PF6 and subsequent incorporation of Dop or Ser showed the higher values of fluorescence intensity of 71 and 72%, respectively. In this context the bis-bipyridinium 1·4PF6 and neurotransmitters Dop or Ser were selected to functionalize polysilicon microparticles. 1·4PF6 was neither cytotoxic nor genotoxic to the cell lines studied 3T3/NIH, HepG2 and CaCo-2 at the maximum concentration tested of 500 µg/mL. With our work, we set up the non- covalent functionalization methodology to develop a microsystem potentially useful for drug sensors purposes.