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SYNTHESIS, KINETIC CONTROL and PROPERTIES ENGINEERING of CERIUM OXIDE NANOPARTICLES for BIOMEDICAL APPLICATIONS Tetyana Yudina

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SYNTHESIS, KINETIC CONTROL and PROPERTIES ENGINEERING of CERIUM OXIDE NANOPARTICLES for BIOMEDICAL APPLICATIONS Tetyana Yudina ADVERTIMENT. Lʼaccés als continguts dʼaquesta tesi queda condicionat a lʼacceptació de les condicions dʼús establertes per la següent llicència Creative Commons: http://cat.creativecommons.org/?page_id=184 ADVERTENCIA. El acceso a los contenidos de esta tesis queda condicionado a la aceptación de las condiciones de uso establecidas por la siguiente licencia Creative Commons: http://es.creativecommons.org/blog/licencias/ WARNING. The access to the contents of this doctoral thesis it is limited to the acceptance of the use conditions set by the following Creative Commons license: https://creativecommons.org/licenses/?lang=en DOCTORAL THESIS SYNTHESIS, KINETIC CONTROL AND PROPERTIES ENGINEERING OF CERIUM OXIDE NANOPARTICLES FOR BIOMEDICAL APPLICATIONS Tetyana Yudina Director: Prof. Dr. Victor Puntes Catalan Institute of Nanoscience and Nanotechnology (ICN2) Universitat Autonoma de Barcelona (UAB) Bellaterra 2016 Tesi Doctoral Programa de Doctorat en Bioquímica, Biología Molecular i Biomedicina “ Synthesis, kinetic control and properties engineering of cerium oxide nanoparticles for biomedical applications ” Memòria presentada per aspirar al Grau de Doctor per Tetyana Yudina Director i supervisor: Víctor F. Puntes Tutor: Jaume Farrés Vicén Institut Català de Nanociència i Nanotecnología (ICN2) Universitat Autònoma de Barcelona (UAB) Facultat de Biociènces Departament de Bioquímica i Biología Molecular Bellaterra, 2016 TABLE OF CONTENTS TABLE OF CONTENTS TABLE OF CONTENTS ............................................................................................................ i ABSTRACT ............................................................................................................................. ii ACKNOWLEDGEMENTS ......................................................................................................... iii CHAPTER 1. Introduction. Research objectives. .................................................................................................... 1 CHAPTER 2. Synthesis and characterization of CeO2 NPs. Design of optimized CeO2 NPs for biomedical applications, based on current limitations and challenges. INTRODUCTION ........................................................................................................... 6 1. The existent methods of CeO2NPs synthesis of optimal size and their problematics for biomedicine ........................................................................................................................... 10 1.1. Understanding of the chemistry of nanoceria formation ................................. 12 1.2. Powdered nanoparticles and biotoxicity of the aggregates ............................. 13 2. The closest environment of colloidal CeO2NPs (surfactant and solvent) and its biocompatibility .................................................................................................................... 17 2.1. The advantage of PVP coating of CeO2NPs .................................................................... 19 2.2. The challenge of BSA coating of CeO2NPs ...................................................................... 20 2.3. Other functionalizations of CeO2NPs .............................................................................. 21 RESULTS AND DISCUSSIONS ........................................................................................ 23 1. Characterization of the designed CeO2NPs ....................................................................... 23 1.1. UV-vis absorption of CeO2NPs ........................................................................... 23 1.2. Electron Microscopy characterization of CeO2NPs ............................................ 24 1.3. X-ray spectroscopy (XRD) characterization of CeO2NPs .................................... 26 2. Monitoring of the CeO2NPs synthesis kinetics ................................................................... 28 2.1. pH monitoring ................................................................................................... 28 i TABLE OF CONTENTS 2.2. XRD spectra monitoring .................................................................................... 29 3. The surface charge and Isoelectric Point of CeO2NPs ....................................................... 30 4. Designing of the optimal CeO2NPs synthesis conditions .................................................. 34 5. Morphological time-evolution of CeO2NPs........................................................................ 41 BIBLIOGRAPHY ........................................................................................................... 45 CHAPTER 3. Antioxidant activity of CeO2NPs. INTRODUCTION ........................................................................................................... 52 1. Reactive oxygen species (ROS) and the electron sponge nature of CeO2NPs ................... 52 RESULTS AND DISCUSSIONS ........................................................................................ 55 1. Size- and coating- dependent reactivity of CeO2NPs ......................................................... 55 2. Concentration-dependent reactivity CeO2NPs .................................................................. 59 BIBLIOGRAPHY ........................................................................................................... 61 CHAPTER 4. In-vivo biodistribution and surface chemistry of CeO2NPs. INTRODUCTION ........................................................................................................... 64 1. Biodistribution of inorganic nanoparticles ....................................................................... 64 2. The importance of the NPs dissolution in physiological environment and toxicity of the generated ions ...................................................................................................................... 68 3. The effects of tissue/organ oxygenation in the chemistry of the NP surface .................... 69 RESULTS AND DISCUSSIONS ........................................................................................ 71 1. The surface charge of CeO2NPs in CCM ............................................................................. 71 2. Oxygen-dependent behavior of CeO2NPs surface under hypoxic, normoxic and hyperoxic conditions ............................................................................................................................. 72 3. The study of the in-vivo biodistribution and biopersistence of CeO2NPs in fibrotic vs healthy rats ........................................................................................................................... 75 4. Visualization of CeO2NPs in rat liver tissue by Electron Microscopy ................................. 78 5. Homogeneity of CeO2NPs biodistribution throughout the rat liver .................................. 79 BIBLIOGRAPHY ........................................................................................................... 82 i TABLE OF CONTENTS ANNEX 1. Materials and methods. METHODS CHAPTER 2 .................................................................................................. 85 1. Characterization techniques .............................................................................................. 85 1.1 UV-Vis (Ultraviolet – Visible) spectroscopy ......................................................... 85 1.2 Zeta Potential (ZP) and Dynamic Light Scattering (DLS) .................................... 86 1.3 Electron Microscopy (HR-TEM, HAADF, EELS, EDX) .......................................... 87 1.4 X-ray diffraction (XRD) ........................................................................................ 88 1.5 ICP-MS ................................................................................................................ 89 2. Designed protocols of CeO2NPs synthesis ......................................................................... 90 2.1 Guideline about the LPS-free synthesis of CeO2NP……………………………..…………. 90 2.2 Synthesis of naked (surfactant-free) CeO2 NPs .................................................. 90 2.3 Synthesis of PVP-coated CeO2 NPs ………………………………………………………………… 91 2.4 Synthesis of BSA-coated CeO2NPs………………………………………………………………….. 92 METHODS CHAPTER 3 .................................................................................................. 92 1. Europium Tetracycline – Hydrogen peroxide (EuTc – H2O2) fluorimetric assay ................ 92 2. Example of the calibration curve preparation……………………………………………………………….. 93 3. Example of the determination of CeO2NPs activity…………………………………………………….... 95 METHODS CHAPTER 4 .................................................................................................. 96 1. Incubation of CeO2NPs in serum-supplemented CCM ...................................................... 96 2. Titration curve for isoelectric point determination ............................................................ 97 3. Spectrophotometric detection of ionic Cerium in solution by Xylenol Orange ................. 97 4. Digestion of organs and biological fluids for the ICP-MS determination of cerium (in-vivo biodistribution study)............................................................................................................. 99 METHODS ANNEX 2 ..................................................................................................... 101 1. Characterization techniques and LAL assay………………………………………………………………….
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