Dissertations / Theses on the topic 'Nanomaterials'

Aquesta tesi es basa en el desenvolupament (síntesi) de diferents nanomaterials per a la seva aplicació com a materials adsorbents per a l'eliminació de contaminants en aigua (anions inorgànics, metalls pesats i pesticides) i per l'adsorció de gas metà. El desenvolupament dels diferents materials s'ha basat en una extensa recerca bibliogràfica de l'estat de l'art dels materials utilitzats actualment per a aquesta aplicació, i s'ha tractat de millorar l'eficiència del procés mitjançant l'ús de nanomaterials. Amb aquest objectiu s’han sintetitzat materials magnètics per diferents mètodes. En alguns casos, aquests han estat funcionalitzats amb grups orgànics per adaptar i/o millorar la seva funció d'adsorció o estabilitzar-los en suports (polímers, zeolites, esponges, etc.) per millorar la seva aplicació a una escala real en un futur. A més, es va desenvolupar un nou mètode per a la formació de nanopartícules core-shell amb un nucli de magnetita. Tots els nanomaterials sintetitzats s'han caracteritzat en profunditat, utilitzant les tècniques més avançades per a la caracterització dels nanomaterials. Tècniques com ara la microscòpia electrònica, difracció de raigs X, entre d'altres, permeten conèixer les característiques i propietats dels materials (mida, dispersió, estructura cristal·lina, etc.) i per tant concloure la seva contribució a l'eficàcia de cada un dels materials adsorbents. Pel que fa als contaminants en aigua, el treball se centra en el fluorur, el fosfat, el nitrat, els metalls cadmi i níquel i pesticides, destacant l'obtenció de resultats excepcionals per a les nanopartícules de Ce-Ti@Fe3O4. En el cas de tractament de gas, per una banda s'ha desenvolupat un nou nanomaterial basat en nanopartícules magnètiques estabilitzades en esponges de poliuretà que ha presentat resultats interessants per a l'adsorció de metà. A més, s'ha col·laborat amb la Institut Català de Nanotecnologia per a l'aplicabilitat dels Metal Organic Frameworks en l'oxidació de CO. Una altra aplicació que s'ha donat a les nanopartícules magnètiques ha estat la seva utilització en la separació de algues procedents de processos de tractament d’aigües, per tal de substituir el procés actual de decantació. Amb tot això, la tesi ofereix una gamma de nanomaterials per a diferents usos en enginyeria ambiental, amb la possibilitat d'investigar i desenvolupar en la seva aplicabilitat a gran escala. Amb aquesta finalitat, es proporcionen diferents solucions per a la millora del medi ambient.
This thesis is based on the development (synthesis) of different nanomaterials for their application as adsorbent materials for the removal of pollutants from water (inorganic anions, heavy metals and pesticides) and for the adsorption of methane gas. The development of the different materials has been based on an extensive bibliographical search of the state of the art of the materials currently used for this application, and it has been tried to improve the efficiency of the process by using nanomaterials. Thus, magnetic (magnetite) nanoparticles are synthesized by different methods. These are functionalized with organic groups to adapt and/or improve their adsorption function or stabilize in supports (polymers, zeolites, sponges, etc.) to improve their application on a real scale. In addition, a new method for the formation of core-shell nanoparticles with a magnetite core is developed. All the synthesized nanomaterials have been characterized in depth, using the most advanced techniques for the characterization of nanomaterials. Techniques such as electron microscopy, X-ray diffraction, among others, allow to know the characteristics and properties of the materials (size, dispersion, crystallinity, structure, etc.) and thus conclude their contribution to the efficiency of their application with adsorbent material. As for the contaminants in water, the work focuses on fluoride, phosphates, nitrates, cadmium, nickel and pesticides, obtaining outstanding results for the nanoparticles of Ce-Ti @Fe3O4. In the case of gas treatment, on the one hand has developed a new nanomaterial based on magnetic nanoparticles stabilized in polyurethane sponges which present interesting results for the adsorption of methane and great applicability on a real scale. In addition, we have collaborated with the Institut Català de Nanotecnologia for the applicability of Metal Organic Frameworks in the oxidation of CO. Another application that has been given to magnetic nanoparticles has been its use to separate algae from wastewater treatment processes, in order to substitute the current sedimentation processes. With all this, the thesis offers a range of nanomaterials for different uses in environmental engineering, with the possibility of investigating and developing on its applicability on a large scale. To this end, different solutions are provided for the improvement of the environment.

Neste trabalho, foi realizado um estudo da obtenção de nanomateriais luminomagnéticos visando potenciais aplicações biológicas, a partir de dois diferentes tipos de estruturas, sendo elas: a formação de heteronanoestruturas luminomagnéticas de NPM de FePt/Fe3O4-CdSe recobertas com sílica; e a formação de nanomateriais luminomagnéticos por ligação covalente entre NPM de FePt/Fe3O4-Dopa-PIMA-PEG-NH2 e pontos quânticos de CdSe/ZnS-LA-PEG-COOH. Para o primeiro tipo de nanomaterial citado, foram testadas duas metodologias para obtenção das heteronanoestruturas: a mudança da estabilidade coloidal pela adição de pequenas quantidades de NaCl no meio contendo as NPM e os pontos quânticos previamente sintetizados; e o método de injeção a quente do precursor de selênio em um meio contendo as NPM como sementes, o precursor de cádmio e os agentes de superfície. O método de injeção a quente foi o que apresentou melhores condições para a formação das heteronanoestruturas. Para providenciar estabilidade coloidal em meio aquoso e superfície com biocompatibilidade, foi realizado o recobrimento com sílica na superfície das heteronanoestruturas luminomagnéticas com melhores condições. Para essa amostra, o tamanho médio obtido foi de 25,0 nm, com polidispersividade de 8,4 %, Ms = 11,1 emu.g-1 e comportamento superparamagnético, além de duas bandas de emissão (com excitação de 400 nm) centradas em 452 nm e 472 nm, respectivamente. Já para o segundo tipo de nanomaterial obtido neste trabalho, foram primeiramente obtidas NPM de FePt/Fe3O4 pelo método do poliol modificado acoplado à metodologia do crescimento, e pontos quânticos luminescentes de CdSe/ZnS pelo método de decomposição térmica de precursores organometálicos, sendo que ambas nanoestruturas apresentaram superfície hidrofóbica. Para a troca de ligantes para transferência das nanoestruturas para a fase aquosa e para providenciar biocompatibilidade visando aplicações biológicas, foram previamente preparados ligantes poliméricos de Dopa-PIMA-PEG-NH2 para recobrimento das NPM e de LA-PEG-COOH para recobrimento dos pontos quânticos. A conjugação química entre as nanoestruturas de FePt/Fe3O4-Dopa-PIMA-PEG-NH2 e CdSe/ZnS-LA-PEG-COOH foi realizada pelo método da carbodiimida em solução aquosa para a formação de uma ligação covalente amida entre os grupos amina e carboxilato em cada uma das nanoestruturas. Os nanomateriais luminomagnéticos obtidos apresentaram estabilidade coloidal em meio aquoso, com estreita distribuição de tamanho, apresentando RH de 79,96 nm, Ms de, aproximadamente, 10 emu.g-1 com coercividade e remanência quase nulos e intensa banda de emissão centrada em 580 nm. Espera-se que os nanomateriais obtidos neste trabalho possam ser promissores nanomateriais com propriedades multifuncionais para potenciais aplicações biológicas.
Here, luminomagnetic nanomaterials were obtained for potential biological applications. We have studied two different types of luminomagnetic nanomaterials, which are: formation of silica-coated FePt/Fe3O4-CdSe heteronanostructures; and formation of luminomagnetic nanomaterials from covalent bond between FePt/Fe3O4-Dopa-PIMA-PEG-NH2 magnetic nanoparticles and CdSe/ZnS-LA-PEG-COOH luminescent quantum dots. For the first type of luminomagnetic nanomaterials obtained, two methodologies were studied for formation of heteronanostructures, which are: modification of colloidal stability by addition of small amounts of NaCl into a solution with hydrophobic magnetic nanoparticles and luminescent quantum dots; and hot injection method of selenium precursor into a solution with magnetic nanoparticles seeds, cadmium precursors and surface agents. The hot injection method obtained better results than the other method studied for formation of heteronanostructures. To provide colloidal stability in aqueous solution and biocompatibility, the heteronanostructures were coated using silica shell. After silica coating, the heteronanostructures showed average diameter of 25 nm and polidispersivity of 8.4%, with Ms = 11.1 emu.g-1 and superparamagnetic behavior. Moreover, these nanomaterials showed two emission peaks centered at 452 and 472 nm. For the second type of nanomaterials obtained, FePt/Fe3O4 magnetic nanoparticles were synthesized by modified polyol method coupled to seeded-mediated growth, and CdSe/ZnS luminescent quantum dots were obtained by thermal decomposition of organometallic precursors. For the ligand exchange to transfer the nanostructures from organic media to aqueous solution, were used Dopa-PIMA-PEG-NH2 and LA-PEG-COOH polymers to provide colloidal stability and biocompatibility on magnetic nanoparticle surface and quantum dot surface, respectively. The chemical conjugation between FePt/Fe3O4-Dopa-PIMA-PEG-NH2 and CdSe/ZnS-LA-PEG-COOH nanostructures was obtained by EDC coupling in aqueous solution, which linked amine and carboxylate groups in each nanostructure to provide the formation of amide bond. The luminomagnetic nanomaterials obtained showed colloidal stability in aqueous solution, narrow size distribution, with RH equal to 79.96 nm, MS around 10 emu.g-1 with low coercivity and remanent magnetization, and intense emission peak centered at 580 nm. We expect these luminomagnetic nanomaterials be promisor nanomaterials with multifunctional properties for potential biological applications.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2011.
This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from PDF version of thesis.
Includes bibliographical references (p. 103-112).
Graphene nanoribbons (GNRs) are quasi one dimensional structures which have unique transport properties, and have a potential to open a bandgap at small ribbon widths. They have been extensively studied in recent years due to their high potential for future electronic and spintronic device applications. The edge structures - including the edge roughness and chirality - dramatically affect the transport, electronic, and magnetic properties of GNRs, and are of the critical importance. We have developed an efficient way of modifying the edges structures, to produce atomically smooth zigzag and armchair edges by using insitu TEM with a controlled bias. This work provides us with many opportunities for both fundamental studies and for future applications. I also report the use of either furnace heating or Joule heating to pacify the exposed graphene edges by loop formation in the graphitic nanoribbons. The edge energy minimization process involves the formation of loops between adjacent graphene layers. An estimation of the temperature during in-situ Joule heating is also reported based on the melting and evaporation of Pt nanoparticles. In this thesis work, I have also investigated the morphological and electronic properties of GNRs grown by chemical vapor deposition. Our results suggest that the GNRs have a surprisingly high crystallinity and a clean surface. Both folded and open edges are observed in GNRs. Atomic resolution scanning tunneling microscopy (STM) images were obtained on the folded layer and the bottom layer of the GNR, which enables clear identification of the chirality for both layers. We have also studied the electronic properties of the GNRs using low temperature scanning tunneling spectroscopy (STS). Our findings suggest that edges states exist at GNR edges which are dependent on the chiral angles of the GNRs.
by Xiaoting Jia.
Ph.D.

En esta tesis doctoral. El dibujo racional de nanomateriales avanzados con propiedades controladas se aplicó para su empleo en biosensing, y condujo al desarrollo de dos plataformas diagnosticas para la determinación de infecciones virales y bacterianas. Primero, se desarrolló un método sintético altamente reproducible y robusto para la producción de nanoshells de una aleación AuAg monodispersas basado en remplazamiento galvánico. El protocolo descrito permite el controlo preciso sobre la morfología de las partículas, en términos de grosor de la capa externa y de tamaño del vacío interior, la composición relativa y distribución topológica de los metales noble constituyentes, y su rugosidad y porosidad superficial. Esta predictibilidad sintética, testeada sobre un rango de tamaños, se ha conseguido a través de un estudio sistemático de la relación entre de cada reactivo, juntos a una detallada caracterización de la composición y estructura del material con diferentes técnicas. Además, el análisis de las propiedades plasmonicas de las NSs de AuAg durante su transformación estructural, que se extiende por casi todo el espectro visible hasta las longitudes de ondas del Near-Infrared, reveló una dependencia estricta con sus características morfológicas y composicionales. Estos resultados, también confirmados con cálculos basados en la teoría de Mie, proveyeron la base para su aplicación como amplificadores de señal en un immunoensayo basado en SERS. Segundo, por la primera vez el comportamiento electroquímico de las NSs de AuAg fe reportado. Causado por la corrosión controlada de átomos de Ag contenidos en los núcleos residuales de las partículas y las capas finas de aleación, el estudio voltametrico de estos nanocristales vacíos se reveló fuertemente dependiente de su composición elemental relativa y, parcialmente, de su tamaño y morfología. Un efecto electrocatalitico peculiar apareció solamente para NSs de AuAg con un ratio Au/Ag suficiente para permitir la electrodeposición catalítica de Ag+ encima de la superficie de las partículas a potenciales menos negativos que el potencial de redacción estándar de Ag. Este comportamiento no previamente reportado está causado solo por el carácter levemente oxidante del electrolito utilizado, sin la necesidad de ningún otro co-reactivo u oxidante. Estos resultados constituyeron la base racional para desarrollar NSs de AuAg con propiedades desiderables para su aplicación en el ensayo electroquímico descrito. Aventajándose de las propiedades plasmonicas de las NSs de AuAg, el desarrollo de un ensayo immunocromatografico basad ene SERS para la detección sensible y cuantitativa de MxA, un biomarcador comúnmente asociado a infecciones virales, fue realizado. Gracias a las intensidades plasmonicas amplificadas enseñadas por las NSs de AuAg, resultante por el efecto de cavidad plasmonica comúnmente observado in nanoestructuras vacias, su superifices se portan como un continuo hot-spot, amplificando cualquier señal Raman emitido por reporters inmovilizados encima. Además, la posibilidad de ajustar precisamente la longitud máxima de LSPR de las NSs de AuAg de manera de coincidir con el láser NIR durante la mesura SERS permitió de mejorar la performance analítica. Entonces, las NSs de AuAg fueron fácilmente conjugadas con anticuerpos anti-MxA e integrados en un ensayo immunocromatografico para revelar su presencia en muestras de suero. Después de atenta optimización de los parámetros de la plataforma point-of-care, al proteína MxA pudo ser detectada a un limite de detección de pocos ng/mL. En fin, la capacidad de modular precisamente la composición elemental de las NSs de AuAg portó al diseño de un ensayo electroquímico para la detección rápida de dos bacterias modelos, Escherichia coli and Salmonella typhimurium. Las NSs de AuAg se utilizaron como reporters electroquímicos por la facilidad de generar la señal electroquímica, causada solamente por el carácter levemente oxidante de la matriz biológica. Por otro lado, el recubrimiento polimérico de las partículas confirió la interacción non específica basada en afinidad con las células bacterianas en solución, evitando de necesitar anticuerpos caros y frágiles. A través de esta estrategia de bajo coste, E.coli puso ser detectado en PBS a concentraciones de 102 CFU/mL, mientras también se consiguió la discriminación semi-selectiva de los perfiles corriente-concentración de las dos bacterias modelos.
In this PhD thesis, the rational design of advanced nanomaterials with controlled properties was applied for their employment in biosensing, leading to the development of two diagnostic platforms for the determination of viral and bacterial infections. Firstly, a highly reproducible and robust synthetic method for the production of monodisperse AuAg alloy NSs based on GRR was developed. The protocol described allows the precise control over the particles’ morphology, in terms of shell thicknesses and void sizes, the relative composition and topological distribution of their constituting noble metals, as well as their surface roughness and porosity. This synthetic predictability, tested over a range of sizes, has been achieved through a systematic study of the convoluted interplay of each co-reagent, together with a detailed characterization of the material’s composition and structure through an array of techniques. Moreover, the analysis of AuAg NSs’ plasmonic properties evolution during their structural transformation, which spanned through almost the whole visible spectrum up to NIR wavelengths, revealed a tight dependence with their morphological and compositional features. These results, also confirmed by calculations based on Mie’s theory, provided the basis for their application as signal enhancers in the SERS-based LFA developed. Secondly, for the first time the electrochemical behavior of AuAg NSs was reported. Triggered by the controlled corrosion of Ag atoms contained in the particles’ residual cores and thin alloy shells, the voltammetric study of these hollow nanocrystals has been found to be strongly dependent on their relative elemental composition and, partially, to their size and morphology. Indeed, a peculiar electrocatalytic effect appeared only for AuAg NSs possessing a high-enough Au/Ag ratio to let the catalytic electrodeposition of Ag+ on the NSs’ surfaces occur at potentials less negative than Ag standard reduction one. Interestingly, this unreported feature was shown to be triggered only by the mild oxidating character of the electrolyte used, without the need of any other co-reagent or oxidizer. These findings constituted the rational basis for developing AuAg NSs with desirable properties to be applied in the electrochemical assay described. Taking advantage of the tunable plasmonic properties of AuAg NSs, the development of a SERS-based LFA for the sensitive and quantitative detection of MxA, a biomarker commonly associated to viral infections, was achieved. Thanks to the enhanced plasmons intensities displayed by AuAg NSs, resulting from the plasmonic cavity effect commonly observed in hollow nanostructures, their surfaces acted as a continuous hot-spot, amplifying any Raman signal emitted by the reporters thereby attached. Moreover, the possibility to precisely adjust AuAg NSs’ LSPR maximum wavelength to match the NIR excitation laser used during SERS measurements allowed to further improve the overall analytical performance. Thus, AuAg NSs were easily conjugated with anti-MxA antibodies and integrated in a LFA in order to reveal its presence in spiked serum samples. After careful optimization of the point-of-care platform parameters, MxA protein could be successfully detected down to the analytically-relevant LOD of few ng/mL. Finally, the capability to precisely modulate AuAg NSs elemental composition lead to the design of a proof-of-concept electrochemical assay for the rapid detection of two model bacterial strains, Escherichia coli and Salmonella typhimurium. AuAg NSs were used as electrochemical reporters because of the ease of generation of the electrochemical signal, triggered by the sole mild oxidating character of the biological sample matrix. Besides, the polymeric coating of the hollow particles provided the non-specific, affinity-based interaction with bacterial cells in solution, avoiding the need for costly and fragile antibodies. With this low-cost strategy, E.coli could be detected in PBS down to 102 CFU/mL, while the semi-selective discrimination of the current-concentration profiles of the two model bacterial strains was also achieved.

2014 - 2015
New layered carbon-based materials were prepared and exhaustively characterized exploiting different characterization techniques, such as thermogravimetry (TGA), differential thermal calorimetry (DSC), Fourier transform infrared (FTIR) and wide angle X-ray diffraction (WAXD). Pristine graphite (G) with high surface area and carbon black (CB) samples with different surface areas were selected as starting materials to prepare the corresponding oxidized samples, i.e. graphite oxide (GO) and carbon black oxide (oCB), with the Hummers’ method. Thanks to the strong hydrophilicity and to the lamellar structure of oxidized carbon-based materials, a rich intercalation chemistry is permitted. In fact, after treatments of GO and oCB by strong basis, ordered intercalation compounds have been obtained, not only if the starting material is crystalline like graphite oxide, but also if it is completely amorphous like oxidized carbon black. Starting basified GO, free-standing papers can be obtained by vacuum filtration, as well as by casting procedure, of colloidal dispersions of graphene oxide sheets. The use of basified GO leads to more flexible, solvent resistant and thermally stable GO papers. Spectroscopic analyses of the obtained papers have been conducted aiming to a possible rationalization of the observed behavior. [edited by author]
Per questo lavoro di tesi di dottorato, sono stati preparati nuovi nanomateriali basti su carbonio ed esaustivamente caratterizzati con tecniche quali termogravimetria (TGA), calorimetria a scansione differenziale (DSC), spettroscopia infrarossa (FT-IR) e diffrazione dei razzi X (WAXD). I materiali di partenza utilizzati per questo lavoro di tesi, sono stati la grafite ad alta area superficiale e carbon black con differenti valori di area superficiale, al fine di ottenere i corrispondenti materiali ossidati quali ossido di grafite (GO) e carbon black ossidato (oCB). Il metodo utilizzato per le ossidazioni dei suddetti starting materials è quello di Hummers. Grazie alla forte idrofilicità ed alla struttura lamellare posseduta dai materiali carboniosi ossidati, è possibile ottenere svariati composti di intercalazione trattando il GO (cristallino) e l’oCB(amorfo) con basi forti e con conseguente funzionalizzazione ionica con cationi di natura organica. Inoltre, partendo da dispersioni di GO basificato, sono stati ottenuti fogli di ossido di grafite e di grafene mediante filtrazione e/o per lenta evaporazione del solvente. Utilizzando una base nella procedura di ottenimento dei cosiddetti fogli di ossido di grafite/grafene, sono stati preparati campioni free-standing con elevata flessibilità, resistenza ai solventi e alle alte temperature. [a cura dell'autore]
XIV n.s.

Els nanomaterials (NMs) són considerats contaminants emergents, ja que la seua detecció està creixent en les diferents matrius ambientals, provocant riscos potencials per a la salut humana i per als ecosistemes. En aquest sentit, el principal objectiu d’aquesta Tesi ha estat proporcionar noves aproximacions metodològiques per a l’avaluació del perill dels NMs mitjançant models in vitro i ex vivo avançats, així com nous biomarcadors. En el nostre primer estudi es va desenvolupar un model nou per comprendre el risc d’exposició dels éssers humans a les nanopartícules de poliestirè (NPPS), com a model de micro-nanoplástics (MNPL). Per aconseguir aquest objectiu, les mostres de sang procedents de 5 donants es van exposar ex vivo a diverses dosis de NPPS i es van avaluar diferents biomarcadors en diversos subconjunts de glòbuls blancs perifèrics. Els resultats van mostrar marcades diferències en la internalització de NPPS, amb una absorció molt limitada en els limfòcits i molt alta en els monòcits. A més, l’avaluació del dany genotòxic de l’ADN va revelar una sensibilitat cel·lular específica, sent les cèl·lules polimorfonuclears i monòcits aquelles cèl·lules amb els nivells més significatius de dany genotòxic. A més, l’exposició a NPPS va desencadenar canvis en el secretoma sanguini, amb un augment significatiu en l’expressió de citoquines relacionades amb la resposta inflamatòria i immunitària, l’estrès i la proliferació cel·lular. En el segon estudi es va utilitzar el model ex vivo abans esmentat per avaluar l’impacte al secretoma sanguini de tres nanomaterials diferents basats en grafè (NMBG). Amb aquest objectiu, es va analitzar un gran panell de citoquines i els resultats van mostrar importants canvis en la seva expressió, estant la majoria d’ells relacionats amb la resposta immunitària i inflamatòria. Al mateix temps, es va utilitzar l’assaig del soft-agar indirecte per analitzar les conseqüències funcionals d’aquests canvis de citoquines. Els resultats van mostrar que el secretoma alterat per NMBG pot inhibir la capacitat de creixement cel·lular independent d’ancoratge de les cèl·lules HeLa, utilitzades com a model de línia cel·lular. En el tercer estudi les propietats de transformació cel·lular del nanocerio es van confirmar mitjançant un model in vitro de dosis baixes a llarg termini. Es van analitzar les propietats relacionades amb les cèl·lules mare canceroses, el creixement independent d’ancoratge i les capacitats d’invasió, ja que es consideren característiques oncogèniques importants impulsades per l’exposició als NMs. Així mateix, es van confirmar les seves possibles interaccions amb el condensat de tabac, com a model de contaminant cancerigen ambiental, mostrant una interacció positiva en la inducció de la transformació cel·lular. A més, es va avaluar una bateria de microRNAs relacionats amb l’adquisició del fenotip tumoral, revelant que les nanopartícules de diòxid de ceri i la coexposició produïen una toxicitat potencial al transcriptoma. Finalment, en el nostre quart estudi es van avaluar les possibles conseqüències epigenètiques de l’exposició a llarg termini a nanopartícules de titani i nanotubs de carboni de múltiples capes, específicament els canvis en l’expressió de microRNAs. La bateria de microRNAs analitzada va revelar un gran impacte en el perfil d’expressió de les cèl·lules exposades als dos nanomaterials. A més, a partir de la nostra bateria inicial, es va seleccionar un petit conjunt de cinc microRNAs com a possibles biomarcadors d’efecte després de l’exposició als NMs. Aquest conjunt va ser provat en les línies cel·lulars BEAS-2B i MEF, prèviament exposades a llarg termini a diferents NMs, mostrant efectes positius en totes les mostres provades, confirmant la idoneïtat d’aquesta bateria.
Los nanomateriales (NMs) son considerados contaminantes emergentes cuya detección está creciendo en las diferentes matrices ambientales, provocando riesgos potenciales para la salud humana y para los ecosistemas. En este sentido, el principal objetivo de esta Tesis ha sido proporcionar nuevas aproximaciones metodológicas para la evaluación del peligro de los NMs a través de modelos in vitro y ex vivo avanzados, así como de nuevos biomarcadores. En nuestro primer estudio se desarrolló un modelo novedoso para comprender el riesgo de exposición de los seres humanos a las nanopartículas de poliestireno (NPPS), como modelo de micro-nanoplásticos (MNPL). Para ello, las muestras de sangre procedentes de 5 donantes se expusieron ex vivo a varias dosis de NPPS y se evaluaron diferentes biomarcadores en diversos subconjuntos de glóbulos blancos periféricos. Los resultados mostraron marcadas diferencias en la internalización de NPPS, con una absorción muy limitada en los linfocitos y muy alta en los monocitos. Además, la evaluación del daño genotóxico del ADN reveló una sensibilidad celular específica, siendo las células polimorfonucleares y monocitos aquellas células con los niveles más significativos de daño genotóxico. Además, la exposición a NPPS desencadenó cambios en el secretoma sanguíneo, con un aumento significativo en la expresión de citoquinas relacionadas con la respuesta inflamatoria e inmunitaria, el estrés y la proliferación celular. En el segundo estudio, se utilizó el modelo ex vivo antes mencionado para evaluar el impacto a nivel del secretoma sanguíneo de tres nanomateriales diferentes basados en grafeno (NMBG). Para ello, se analizó un gran panel de citoquinas y los resultados mostraron importantes cambios en su expresión, estando la mayoría de ellos relacionados con la respuesta inmunitaria e inflamatoria. Al mismo tiempo, se utilizó el ensayo de soft-agar indirecto para analizar las consecuencias funcionales de estos cambios de citoquinas. Los resultados mostraron que el secretoma alterado por NMBG puede inhibir la capacidad de crecimiento celular independiente del anclaje de las células HeLa, utilizadas como modelo de línea celular. En el tercer estudio, las propiedades de transformación celular del nanocerio se confirmaron mediante un modelo in vitro de dosis bajas a largo plazo. Se analizaron las propiedades relacionadas con las células madre cancerosas, el crecimiento independiente del anclaje y las capacidades de invasión, ya que se consideran características oncogénicas importantes impulsadas por la exposición a los NMs. Asimismo, se confirmaron sus posibles interacciones con el condensado de tabaco, como modelo de contaminante cancerígeno ambiental, mostrando una interacción positiva en la inducción de la transformación celular. Además, se evaluó una batería de microARNs relacionados con la adquisición del fenotipo tumoral, revelando que las nanopartículas de dióxido de cerio y la co-exposición producían una toxicidad potencial a nivel del transcriptoma. Finalmente, en nuestro cuarto estudio se evaluaron las posibles consecuencias epigenéticas de la exposición a largo plazo a nanopartículas de titanio y nanotubos de carbono de múltiples capas, específicamente los cambios en la expresión de microARNs. La batería de microARNs analizada reveló un gran impacto en el perfil de expresión de las células expuestas a ambos nanomateriales. Además, a partir de nuestra batería inicial, se seleccionó un pequeño conjunto de cinco microARNs como posibles biomarcadores de efecto después de la exposición a los NMs. Este conjunto fue probado en las líneas celulares BEAS-2B y MEF, previamente expuestas a largo plazo a diferentes NMs, mostrando efectos positivos en todas las muestras probadas, confirmando la idoneidad de esta batería.
Nanomaterials (NMs) are considered emerging pollutants that are increasingly detected in different environmental matrices, with potential risks for human health and the ecosystems. In this sense, the focus of this Thesis has been directed to provide new approach methodologies for hazard assessment of NMs via advanced in vitro and ex vivo models, as well as novel biomarkers. From our first study, a novel approach was developed to understand the risk of polystyrene nanoparticles (PSNPs) exposure for humans, as a model of micro-nanoplastics (MNPLs). Thus, ex vivo whole blood samples from 5 donors were exposed to several doses of PSNPLs and different end-points were evaluated in diverse subsets of white peripheral blood cells (WBCs). The results showed sharp differences in PSNPLs internalization with very limited uptake in lymphocytes and high uptake in monocytes. Moreover, the genotoxic DNA damage evaluation revealed a specific cellular sensitivity, being polymorphonuclear cells (PMNs), and monocytes those cells with the most significant levels of genotoxic damage. Additionally, PSNPLs exposure triggered changes in the whole blood secretome, with a significant increase in the expression of cytokines related to the inflammatory, immune, and stress response, as well as cell proliferation. In the second study, the before-mentioned whole blood ex vivo model was used to evaluate the impact of three different graphene-based nanomaterials (GBNMs) at the level of the blood secretome. For that purpose, a large panel of cytokines was analysed, and the results showed important cytokine expression changes, most of them related with the immune and inflammatory response. At the same time, the indirect soft-agar assay, was used to unravel the functional consequences of these cytokine changes. The results showed that the GBNMs-altered secretome can inhibit the anchorage-independent cell growth capacity of HeLa cells, used as a model cell-line. In the third study, the cell-transforming properties of nanoceria were confirmed through a long-term low-dose in vitro model. Stem-like properties, anchorage-independent growth, and invasion abilities were analysed as they are considered important oncogenic features driven by NMs exposure. Also, their potential interactions with cigarette smoke condensate (CSC), as a model of environmental carcinogenic pollutant were confirmed, showing a positive interaction in the induction of cell transformation. Besides, a battery of microRNAs related to the acquisition of the tumoral phenotype was assessed, revealing that cerium dioxide nanoparticles (CeO2NPs) and the co-exposure produced potential toxicity at the transcriptome level. Finally, our fourth study evaluated the potential epigenetic consequences of long-term exposure to titanium nanoparticles (TiO2NPs) and multi-walled carbon nanotubes (MWCNT), specifically the microRNAs expression changes. The analysed microRNA battery revealed a big impact on the expression profiling in cells exposed to both nanomaterials. Moreover, from our initial battery, a small set of five microRNAs were selected as potential biomarkers of effect after NMs’ exposures. This set was tested in BEAS-2B and MEF cells previously long-term exposed to different NMs, showing positive effects in all the tested samples, confirming the suitability of this battery.
Universitat Autònoma de Barcelona. Programa de Doctorat en Genètica

In the last decades, the interest to adopt new sustainable industrial processes and to find new eco-friendly ways to convert and store energy with a lower impact on the environment is growing due to the devastating consequences of our actions. In this Ph.D. project are investigated new sustainable catalysts based on carbon nanostructures for photocatalytic and electrocatalytic applications. In the first part of this thesis, 3 electrocatalyst for the oxygen reduction reaction (ORR) are proposed: Raspberry-like FeOx nanoparticles were covered with graphitized polydopamine (SNC@PDA500). Subsequently the inorganic core was removed in order to form an hollow N,O co-doped carbon nanoshell (g-PDA500). The elimination of the inorganic core leaves low doses of Fe that migrates on the surface of the carbon nanoshell and form ultrasmall FeOx nanoparticles when g-PDA500 is treated at 700 °C (g-PDA700), following an ex-solution process. SNC@PDA500 and g-PDA500 are active for the O2-to-H2O process (that finds application in fuel cells) while g-PDA700 is active for the O2-to-H2O2 process (that could be relevant as a sustainable alternative to the traditional H2O2 industrial production). In the second part graphitic carbon-based nanomaterials are explored for light-mediated perfluoroalkylation reaction. In particular, the structure/activity relationship was studied in order to determine relevant mechanistic aspects. Graphitic carbon nitride (g-CN) was prepared by conventional thermal polymerization of melamine. Subsequently, post-synthetic structural modifications of g-CN were performed applying 3 different protocols to obtain amorphous carbon nitride (am-CN), reduced carbon nitride (red-CN) and oxidized carbon nitride (ox-CN). am-CN revealed high performance for the perfluorobutylation of 1,3,5 trimethoxy-benzene (model reaction) and showed high performances for 2 classes of reactions: homolytic aromatic substitution (HAS) and atom transfer radical addition (ATRA). Subsequently, the amorphization treatment was investigated: 4 superamorphed carbon nitrides (SACNs) were proposed: 4h-SACN, 6h-SACN, d-SACN and t-SACN. Similarly, the oxidation treatment was explored preparing 3 different oxidized carbon nitrides (OCNs): 2M-OCN, 8M-OCN and OW-OCN. In the last part, 3 different CN-based nanomaterials are prepared: 1) mesoporous graphitic carbon nitride (mpg-CN) using an eco-friendly protocol that involves CaCO3 as hard template, 2) poly heptazine imides (PHIs). The proposed PHIs are prepared following 2 approaches: using a eutectic mixture of LiCl and KCl (PHIK) and using both NaOH and KOH (PHIK-Na).

This experimental PhD thesis presents the results of research performed in five different facilities: in the Laboratory of Bio-inspired Nanomechanics “Giuseppe Maria Pugno” at the Politecnico of Torino, the “Nanofacility Piemonte” at the INRIM Institute in Torino, the Division of Dental Sciences and Biomaterials of the Department of Biomedicine at the University of Trieste, the Physics Department of the Politecnico of Torino, the Toscano- Buono Veterinary Surgery in Torino and the Department of Human and Animal Biology at the University of Torino. The adhesive abilities of insects, spiders and reptiles have inspired researchers for a long time. All these organisms present outstanding performance particularly for force, adhesion and climbing abilities, especially considering their size and weight. Scientists have focused attention on the gecko’s adhesive paw system and climbing abilities, and its adhesion mechanism has been an important topic of research for nearly 150 years. However, certain phenomena about geckos are still not completely understood and nowadays these still represent the main challenge of several scientific discussions which aim to better understand the gecko’s adhesive ability. This thesis deals first with the influence of surface roughness on the gecko’s adhesion on the inverted surface of Poly(methyl meth-acrylate) (PMMA) and glass in Chapter 1, of PMMA with different surface roughness in Chapter 2, while Chapter 3 deals with the gecko’s maximum normal adhesive force and Chapter 4 looks at the optimal adhesion angle at different hierarchical levels. The gecko’s moult (Appendix 1) is examined in a preliminary way. The Tokay gecko (Gekko gecko) is the most studied gecko among more than 1050 Gekkonid lizard species in the world, due to its strong adhesive ability. Because this thesis reports clear experimental measurements on two living Tokay geckos, it is comparable to scientific results reported in the literature. It is well known how small insects can carry many times their own weight and can walk quickly, but their most interesting ability is their extremely high adhesion. In recent decades, many scientists have studied a number of insects in order to understand and measure their adhesive abilities. Biological adhesion can be obtained through different adhesive mechanisms (e.g. claw, clamp, sucker, glue, friction). In particular, this thesis focuses on living specimens of the non-climbing cockroach (Blatta Orientalis Linnaeus) by evaluating its maximum shear safety factor on artificial surfaces using a centrifuge machine, see Chapter 5. In general, the adhesive structure and mechanism of an animal could be connected to the micro-structured roughness of natural substrata (e.g. plant surfaces), which animals usually find when they move around in the natural environment. In nature, plants show an extraordinary variety of morphologies and surface structures. Some plants possess two special properties; superhydrophobicity (or water-repellency) and self-cleaning (or dirt-freedom). These two related phenomena were observed for the first time by Aristotle more than 2,000 years ago but it was only in the 20th century that scientists examined them accurately on some natural leaves, e.g. the lotus (Nelumbo nucifera) on which “raindrops take a clear, spherical shape without spreading, which probably has to be ascribed to some kind of evaporated essence”, as Goethe described in 1817. Accordingly to scientific literature, a strong influence of surface roughness on wettability and self-cleaning behaviour clearly emerges. This well-defined problem was of particular interest (for the Indesit Company) since we wanted to find an industrial solution which would leave the internal sides of refrigerators clean from condensed water or dirt. For this reason, a collaborative project started. Two industrial processes, plasma and thermoforming treatments, were applied to polystyrene surfaces. The Indesit refrigerator box is made of polystyrene. The influence of these industrial treatments on the surface wettability were analysed, see Chapter 6. The focus of the Indesit Company was to understand the role of roughness and to produce a superhydrophobic and self-cleaning surface. Thus, this thesis reports the method which we developed in order to design an artificial biomimetic superhydrophobic polystyrene surface, copying the natural lotus leaf (Chapter 7). In addition, surface roughness implies a modification of the tribological and frictional properties, so it assumes a crucial role when designing two contacting surfaces, in particular at nano-scale (Chapter 8). The nanometer scale characterises this thesis and is involved in everything from gecko spatulae to the waxy nanotubules of the lotus leaf, to the fibroin protein materials which constitute spider silks. In general, spider silks display superior mechanical properties but, only in the last few decades, reserachers have studied various types of silks and have evaluated their very different mechanical properties. The fact that the mechanical behaviour of spider silks varies accordingly to their type is well-known, since silk properties have been demonstrated to be species-specific and are linked to silk-based peptide fibrils or protein aggregates, with different structural and mechanical properties. The dragline silk (or radial silk) and the flag silk (or circumferential silk) of orb weaving spiders have been characterized in scientific literature while, to our knowledge, few studies have been conducted on bundles, which connect the cocoons of Meta menardi to the ceiling of caves. These were tested to determine their mechanical properties in terms of stress, strain and toughness (Chapter 9).

Magnetism of carbon-based materials is a challenging area for both fundamental research and possible applications. We present studies of low-dimensional carbon-based magnetic systems (fullerene-diluted molecular magnets, carbon nanotubes, graphite fluoride, and nanoporous carbon) by means of SQUID magnetometer, X-ray diffraction and vibrational spectroscopy, the latter techniques used as complementary instruments to find a correlation between the magnetic behaviour and the structure of the samples.In the first part of the thesis, characteristic features of the magnetization process in aligned films of carbon nanotubes with low concentration of iron are discussed. It is shown that the magnetism of such structures is influenced by quantum effects, and the anisotropy behaviour is opposite to what is observed in heavily doped nanotubes.In the second part, Mn12-based single molecular magnets with various carboxylic ligands and their 1:1 fullerene-diluted complexes are studied. We prove that magnetic properties of such systems strongly depend on the environment, and, in principle, it is possible to design a magnet with desirable properties. One of the studied compounds demonstrated a record blocking temperature for a single molecular magnet. Both fullerene-diluted complexes demonstrated “magnetization training” effect in alternating magnetic fields and the ability to preserve magnetic moment.The third and the fourth parts of the thesis are dedicated to the analysis of various contributions to the magnetic susceptibility of metal-free carbon-based systems – intercalated compounds of graphite fluorides and nanoporous oxygen-eroded graphite. The magnetic properties of these systems are strongly dependent on structure, and can be delicately tuned by altering the π-electron system of graphite, i. e. by degree of fluorination of intercalated compounds and by introduction of boron impurity to the host matrix of nanoporous graphite.
Magnetism av kolbaserade material är ett utmanande område för både grundforskning och möjliga tillämpningar. Vi presenterar studier med låg-dimensionella kolbaserade magnetiska system (fulleren-utspädda molekylära magneter, kolnanorör, grafit fluorid och nanoporösa kol) med hjälp av SQUID magnetometer, röntgendiffraktion och vibrerande spektroskopi, de senare tekniker som används som komplement instrument för att finna sambandet mellan den magnetiska uppträdande och strukturen hos proven. I den första delen av avhandlingen är egenheter från magnetisering processen i linje filmer av kolnanorör med låg koncentration av järn diskuteras. Det visas att magnetism av sådana strukturer påverkas av kvantmekaniska effekter och anisotropin beteende är motsatsen till vad som observerats i kraftigt dopade nanorör. I den tvåa delen är Mn12-baserade enda-molekyl magneter med olika karboxylsyror ligander och deras 1:1 fulleren-utspädda komplex studeras. Vi visar att magnetiska egenskaperna hos sådana system beror i hög grad på miljön, och i princip är det möjligt att utforma en magnet med önskvärda egenskaper. En av de studerade föreningarna visade en post blockeringstemperaturen för en enda molekylär magnet. Både fulleren-utspädda komplex visade "magnetisering utbildning" effekt i alternerande magnetfält och möjligheten att bevara magnetiskt moment. Den tredje och fjärde delarna av avhandlingen är avsedda för inneboende magnetism av analys av olika bidrag till magnetisk susceptibilitet av metall-fritt kol-baserade system -inskjutna föreningar grafit fluorider och nanoporösa O2-eroderade grafit. Magnetiska egenskaperna hos dessa system är starkt beroende av strukturen, och kan fint avstämmas genom att man ändrar π-elektronsystem av grafit, i. e. med graden av fluorering av inskjutna föreningar och genom införandet av bor föroreningar till värd matris av nanoporösa grafit.

The development of materials with tailored functionalities and with continuously shrinking linear dimensions towards (and below) the nanoscale is not only going to revolutionize state of the art fabrication technologies, but also the computational methodologies used to model the materials properties. Specifically, atomistic methodologies are becoming increasingly relevant in the field of materials science as a fundamental tool in gaining understanding on as well as for pre-designing (in silico material design) the behavior of nanoscale materials in response to external stimuli. The major long-term goal of atomistic modelling is to obtain structure-function relationships at the nanoscale, i.e. to correlate a definite response of a given physical system with its specific atomic conformation and ultimately, with its chemical composition and electronic structure. This has clearly its pendant in the development of bottom-up fabrication technologies, which also require a detailed control and fine tuning of physical and chemical properties at sub-nanometer and nanometer length scales. The current work provides an overview of different applications of atomistic approaches to the study of nanoscale materials. We illustrate how the use of first-principle based electronic structure methodologies, quantum mechanical based molecular dynamics, and appropriate methods to model the electrical and thermal response of nanoscale materials, provides a solid starting point to shed light on the way such systems can be manipulated to control their electrical, mechanical, or thermal behavior. Thus, some typical topics addressed here include the interplay between mechanical and electronic degrees of freedom in carbon based nanoscale materials with potential relevance for designing nanoscale switches, thermoelectric properties at the single-molecule level and their control via specific chemical functionalization, and electrical and spin-dependent properties in biomaterials. We will further show how phenomenological models can be efficiently applied to get a first insight in the behavior of complex nanoscale systems, for which first principle electronic structure calculations become computationally expensive. This will become especially clear in the case of biomolecular systems and organic semiconductors.

The results presented in this thesis demonstrate the first synthesis of several nanostructured transition metal oxides and lithium containing transition metal oxides. Their uses in lithium-ion batteries and/or as magnetic materials have been investigated. The first example of two and three dimensional mesoporous Fe₂O₃ has been prepared by using the soft templating (surfactant) method. The materials have amorphous walls and exhibit superparamagnetic behaviour. By using a hard template route, a mesoporous α-Fe₂O₃ with highly crystalline walls has been synthesized. Its unique magnetic behaviour, distinct from bulk α-Fe₂O₃, nanoparticulate α-Fe₂O₃, and mesoporous Fe₂O₃ with disordered walls, has been demonstrated. The hard template method was also used to prepare nanowire and mesoporous Co₃O₄, β-MnO₂ and MnO₃ with crystalline walls. Their electrochemical properties as electrodes in Li-ion batteries have been investigated. Mesoporous β-MnO₂ can accommodate 0.9 Li/Mn in stark contrast to bulk β-MnO₂ which cannot accommodate Li. To prepare mesoporous materials which cannot be obtained directly by the hard template method, a post-templating route has been developed. Mesoporous Fe₃O₄, γ-Fe₂O₃, and Mn3O4 with ordered mesostructures and highly crystalline walls have been obtained by post-synthesis reduction/oxidation treatments. All the materials show unique magnetic properties compared with nanoparticulate and bulk materials. Also, the first example of lithium containing mesoporous material, LT-LiCoO₂, was synthesized by first preparing mesoporous Co₃O₄, then reacting this with LiOH to form LT-LiCoO₂, with retention of the ordered nanostructure. The nanostructured LT-LiCoO₂ compounds demonstrate superior performance compared with normal or nanoparticulate LT-LiCoO₂, when used as intercalation electrodes in lithium batteries. Finally, monodispersed Mn₃O₄ nanoparticles (diameter ~ 8 nm) with a core-shell structure (a highly crystalline Mn₃O₄ core encased in a thin MnO₂ shell) have been prepared for the first time. Ordered three-dimensional arrays form by spontaneous self-assembly. Magnetic measurements demonstrated that the self-assembled three-dimensional arrays exhibit spin-glass behaviour, rather than the anticipated superparamagnetic behaviour for isolated nanoparticles. Such behaviour is interpreted as arising from strong interactions between the core (crystallized Mn₃O₄) and shell (MnO₂).

Point of care (POC) is a powerful tool as a diagnostic test because of its advantage of being small, portable device and rapid results obtained. One major class of POC is the lateral flow assay (LFA), which is widely used for protein determinations. A home pregnancy test is the most successful example of the LFAs. A limitation of being quantitative or at best semi quantitative assay leads to improve the assay performance and to enhance its sensitivity. Hence, for this project, a switch from visual detections to electrochemical measurements is the primary goal, which occurred by developing the assay’ concept with keeping the ease and robustness of the traditional LF assay. The integration of streptavidin lateral flow with electrochemical measurements (in particular voltammetric techniques) is the key element to introduce an electrochemical lateral flow assay (ELFA). This concept was based on the amplification of the polymer nanoparticles. A pH responsive eudragit S- 100 was synthesized by nanoprecipitation process. These PNPs are encapsulated with redox active probe such as hydroxylmethyl ferrocene. Eudragit S-100 is dissolved at pH > 7 and it is insoluble in an acidic condition. This dissolution mechanism is preferable since the release of entrapped probe can be controlled until it is being detectable at the test line. Our findings summarized as follows; nanoprecipitation process is able to synthesis PNPs encapsulated both hydroxylmethyl ferrocene and methylene blue. These small-sized particles (~200 nm and ~300 nm) have a highly value negative zeta potentials (-34 mV and -29 mV). These two proprieties respectively, are important in enhancing the probe loading efficiency and in efficient adsorption with the antibody. From our data, it was found that more than 50% of the probes were encapsulated. Further characterizations were performed to investigate the probes’ electroactivity as well as their electrochemical behavior. These voltammetric techniques include cyclic voltammetry and square wave voltammetry, the results suggested good electrochemical behaviors of both probes in respect of their release form the PNPs in immobilized format as well as in the aqueous phase. Importantly, an electrochemical lateral flow assay (ELFA) was investigated the FcMeOH-PNPs and was successfully demonstrated in the presence of varied concentrations of hCG compared to the control (absence of hCG). This indicates that the applied approach was proven. However, further improvements are needed. This led to move toward the screen-printed technology to realize a point of care device.

Nanotubes (inner diameter of 8nm and outer diameter of 10nm with a length of up to several hundred nm) and nanowires (diameter 20 – 50nm and up to several μm in length) of TiO₂-B have been synthesised and characterised for the first time. These exhibit excellent properties as a host for lithium intercalation and are able to accommodate lithium up to a composition of Li₀.₉₈TiO₂-B for the nanotubes and Li₀.₈₉TiO₂-B for the nanowires. Following some irreversible capacity on the first cycle, which could be reduced to 4% for the nanowires, capacity retention for the nanowires is 99.9% and for the nanotubes is 99.5% per cycle. In both cases, the cycling occurs at ~1.6V versus lithium. The cycling performance was compared with other forms of bulk and nano-TiO₂, all of which were able to intercalate less lithium. Nanowires of VO₂-B (50 – 100nm in diameter and up to several μm in length) were synthesised by a hydrothermal reaction and characterised. By reducing the pressure inside the hydrothermal bomb, narrower VO₂-B nanowires with a diameter of 2 – 5nm and length of up to several hundred nm were created - some of the narrowest nanowires ever made by a hydrothermal reaction. These materials are isostructural with TiO₂-B and were also found to perform well in rechargeable lithium ion batteries, being able to intercalate 0.84Li for the ultra-thin nanowires and 0.57Li for the standard nanowires. The standard VO₂-B nanowires have a capacity retention of 99.8% and the ultra-thin nanowires have 98.4% per cycle after some irreversible capacity on the first cycle. This was found to improve markedly when different electrolytes were used. Macroporous Co₃O₄ (pore size 400nm with a surface area of 208m²/g) was prepared and cycled in rechargeable lithium cells with capacities of 1500mAh/g being achieved. The structure was found to break down on the first cycle and after this the material behaved in the manner of Co₃O₄ nanoparticles. Finally a new candidate for next generation rechargeable lithium batteries was examined; Li/O₂ cells. The cathode is composed of porous carbon in which Li⁺, e⁻ and O₂ meet to form Li₂O₂ on discharge. The reaction is reversible on charge. Capacities of 2800mAh/g can be achieved when 5%mole of αMnO₂ nanowires catalyst is used. Fade is high at 3.4% per cycle meaning that there is much work to do to develop these into a commercial prospect.

The optical schemes of high numerical aperture spectrographs based on concave holographic diffraction gratings are described. A calculations of an optical schemes using flat field spectrograph method for analyzing the fluorescence of all kinds of Quantum dots in a wide range of wavelengths with spectral resolution of 6,3 nm are submitted. A special calculation of spectrographs for investigating CdSe/ZnS, InP Quantum dots with high resolution of 1 nm are given because of their wide uses. An experimental mounting for analyzing Raman scattering in carbon nanotubes is described. Experimental results are given. On the basis of these results the requirements for optical characteristics of a compact specialized spectrograph for analyzing Raman scattering in carbon nanotubes are developed. The calculation of an optical scheme using flat field spectrograph method with spectral resolution of 3.5 cm-1 is submitted. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/20724

La cellulose étant l'un des biopolymères les plus abondants, elle est employée dans ce travail de thèse sous sa forme nano-fibrille (2 à 5nm de diamètre et plusieurs microns de long) pour préparer des nanomatériaux durables. Les microfibrilles de cellulose (MFC) chargées positivement ou négativement sont assemblées en couches minces dans ces nanomatériaux par la méthode « Layer by Layer » (LbL) par trempage, pulvérisation ou spin assisté. Les différences entre ces films LbL à base de MFC et les films LbL à base de polymères standards sont discutées brièvement et sont reliées à la forme nanofibrillaire de la cellulose. Les MFC réagissent comme des nano-objets anisotropes et rigides. Les films LbL de MFC sont ensuite intégrés à des membranes de séparation, entre la couche polymérique de séparation et le support poreux, pour améliorer le débit à travers ces membranes. Ces films minces sont également déposés sur des aérogels de cellulose pour améliorer la stabilité de ces aérogels en milieu aqueux. Dans les deux applications, les résultats était encouragent et montre une validation de principe
Cellulose, one of the most abundant biopolymers, is used in this PhD work in its nanofibrillated form, 2-5 nm in diameter and microns long, to prepare sustainable nanomaterials. Both positively and negatively charged microfibrillated celluloses (MFC) are assembled in these nanomaterials using the versatile Layer by Layer (LbL) assembly methods: dipping, spray assisted-deposition and spin-assisted deposition. A brief comparison between the MFC based LbL assembled films and the standard polymeric LbL films is carried out. Thedifferences between the two species are related to the fibrillar form of cellulose. MFC behaves like rigid anisotropic nano-objects. MFC LbL assembled films are then integrated in separation membranes between active polymeric separation layers and a mechanically stable porous support to improve the flux through these membranes. MFC LbL assembled films are also coated on cellulosic aerogels to improve the wet stability of these aerogels. In both cases, results were encouraging and showed a proof of concept

Orientador: Oswaldo Luiz Alves
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica
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Resumo: Esta dissertação visa à obtenção de nanoestruturas partindo do óxido misto Ti1-xZrxO2. O óxido precursor foi preparado pelo método de precipitação homogênea, via tetracloreto de titânio e oxicloreto de zircônio, usando uréia como reagente precipitante. Esses óxidos foram submetidos ao tratamento hidrotérmico em autoclave, em solução de NaOH, empregando temperatura de 140 e 170°C com intervalo de tempo de 2 a 7 dias. De acordo com as caracterizações físico-químicas feitas foi observado que os produtos obtidos via tratamento hidrotérmico com x < 0,50 apresentaram morfologia de nanotubos, nanoplacas e nanobastões. Entretanto, para x acima de 0,05 mostraram a existência de duas fases cristalinas, titanato de sódio e ZrO2 tetragonal. Para x > 0,50 não apresentaram mudanças morfológicas, tendo como fase formada o ZrO2 tetragonal. Quando o precursor com x = 0,50 (fase ZrTiO4) é observado no produto do tratamento hidrotérmico manutenção da estrutura cristalina e presença de nanotubos. Foi também mostrado, para x = 0,15, que o aumento de volume da solução na autoclave promove aumento da cristalinidade e destruição da organização das partículas. O aumento do tempo e da temperatura de reação proporcionou maior cristalinidade aos produtos hidrotérmicos com x = 0,15 e 0,50; para x = 0 aumento de nanotubos e para x = 0,15 diminuição das nanoplacas e para x = 0,80 e 1 não apresentaram mudanças nem na morfologia, nem na cristalinidade. Foi avaliada a reatividade dos nanotubos (x=0) e nanobastões/nanoplacas (x = 0,15) frente às moléculas orgânicas. Foi observado que os nanotubos interagem melhor com moléculas ácidas, e que tais moléculas promovem a destruição da morfologia e mudança da estrutura cristalina, sendo estas mais drásticas quando com aquecimento. Os nanobastões/nanoplacas interagem mais fortemente com as moléculas ácidas, porém sem perda de morfologia e estrutura cristalina
Abstract: The main of this Dissertation is the preparation of nanostructures from T1-xZrxO2 mixed oxide. The precursor oxide was prepared by the homogeneous precipitation method, from titanium tetrachloride and zirconium oxichloride, using urea as the precipitating agent. The oxides were hydrothermally treated in autoclave, in NaOH solution, at temperatures of 140 and 170 °C, for period of 2 to 7 days. According to the physical-chemical characterizations, it was observed that the products prepared by the hydrohermal treatment with x < 0.50 presented morphologies like nanotubes, nanosheets and nanorods. However, for x > 0.05, it was observed the presence of two crystalline phases, sodium titanate and tetragonal ZrO2. For x > 0.50, it was not observed morphological changes, being tetragonal ZrO2 the obtained phase. Starting from the mixed oxide with x = 0.50, ZrTiO4 phase, it was observed nanotubes with the same crystalline phase. For x = 0.15, it was also observed that the increase of solution volume in the autoclave causes a crystallinity increase and destruction of the particles organization. The increase in time and temperature of reaction caused an increase in the crystallinity of the hydrothermal products for x = 0.15 e 0. 50; for x = 0, it was observed more quantity of nanotubes; and for x = 0.15, fewer nanosheets; for x = 0.80 and 1, it was not observed either morphological neither crystalline changes. The reactivity of the nanotubes (x = 0) and nanorods/nanosheets (x = 0.15) with organic molecules, which promote the morphology destructions and changes in the crystalline structure. These effects were increased with heating. The nanorods/nanosheets strongly interact with acid molecules, without loosing of morphology or the original crystalline structures
Mestrado
Quimica Inorganica
Mestre em Química

This thesis deals with the engineering of novel nanomaterials, particularly nanocomposites and nanostructured surfaces with enhanced functionalities. The study includes two parts; in the first part, an in situ sol-gel polymerization approach is used for the synthesis of polymer-inorganic hybrid material and its exceptional transparent UV-shielding effect has been investigated. In the second part, electrodeposition process has been adapted to engineer surfaces and the boiling performance of the fabricated nanostructured surfaces is evaluated.

In the first part of the work, polymer-inorganic hybrid materials composed of poly(methylmethacrylate) (PMMA) and zinc compounds were prepared by in situ sol-gel transition polymerization of zinc complex in PMMA matrix. The immiscibility of heterophase of solid organic and inorganic constituents was significantly resolved by an in situ sol-gel transition polymerization of ZnO nanofillers within PMMA in the presence of dual functional agent, monoethanolamine, which provided strong secondary interfacial interactions for both complexing and crosslinking of constituents.

In the second part of the work, nanoengineering on the surface of copper plates has been performed in order to enhance the boiling heat transfer coefficient. Micro-porous surfaces with dendritic network of copper nanoparticles have been obtained by electrodeposition with dynamic templates. To further alter the grain size of the dendritic branches, the nanostructured surfaces underwent a high temperature annealing treatment.

Comprehensive characterization methods of the polymer-inorganic hybrid materials and nanoengineered surfaces have been undertaken. XRD, 1H NMR, FT-IR, TGA, DSC, UV-Vis, ED, SEM, TEM and HRTEM have been used for basic physical properties. Pool boiling tests were performed to evaluate the boiling performance of the electrodeposited nanostructured micro-porous structures.

The homogeneous PZHM exhibited enhanced UV-shielding effects in the entire UV range even at very low ZnO content of 0.02 wt%. Moreover, the relationship between band gap and particle size of incorporated ZnO by sol-gel process was in good agreement with the results calculated from the effective mass model between bandgap and particle size. The fabricated enhanced surface has shown an excellent performance in nucleate boiling. At heat flux of 1 W/cm2, the heat transfer coefficient is enhanced over 15 times compared to a plain reference surface. A model has been presented to explain the enhancement based on the structure characteristics.

Carbon can be in several forms. Amorphous, graphite and diamond. Fullerenes are accepted as the fourth form of solid carbon. They are basically, large carbon cage molecules. By far the most common one is C60. Nanotubes are actually longer forms of fullerenes. If a voltage is applied between two carbon rods, an arc will develop between them. If the arc is maintained in helium or argon (instead of air) clouds of black carbon powder is produced. Although many studies have been performed on cathodic deposits, (i.e. nanotubes first seen in this section) very few studies on the carbon sooth are found in the literature. Only around 10% of the black soot is fullerene, the composition of the remainder varies depending on the working conditions. But it is assumed to contain parts of various fullerene particles even higher fullerenes up to C300. This fraction is abbreviated as FES through the thesis. This work comprises the production of FES (fullerene extracted soot), soot, cathodic deposit produced under nanotube conditions and cathodic deposit produced under fullerene conditions and characterization of these in terms of their specific surface areas
pore volume distribution, porosity and as a second part, adsorption capacity of gases H2 and NH3 have been found. Both physical and chemical adsorption analyses were done using Quantichrome Autosorb 1-C surface analyzer. Obtained isotherms for nitrogen adsorption were found to be in between type II and type IV. BET surface areas for the samples of FES and soot prepared under nanotube conditions and cathodic deposit prepared under fullerene and nanotube conditions were found 240, 180, 14.6 and 29.7 m2/g of surface area respectively. Micropore volumes were calculated from Horwath - Kowazoe and Saito - Foley methods were found 0.045, 0.034, 2.38*10-3 and 1.19*10-3 cc/g respectively. Active surface areas for NH3 adsorption were found for FES, soot and Norit active carbon sample are found to be 39.2, 49.6, 32.5 m2/g at 300 C and 6.35, 14.65, 6.59 m2/g at 3000 C respectively. As a result of this work, it is concluded that although not superior to NORIT CN1 active carbon sample, FES is as active as that material and able to adsorb as much hydrogen as active carbon. This is important because FES is already a side product of the arc-evaporation fullerene production technique and has no known uses at all.

Le travail de cette thèse intitulée "Nanomatériaux luminescents pour des applications en diagnostic" consiste en la synthèse, la caractérisation et les applications en bioimagerie des nanomatériaux. Des nanoparticules de silicium ont été synthétisées et modifiées avec des groupements fonctionnels (amino, carboxylate, sucre et complexes de platine(II)) sur la surface et appliquées dans l'imagerie cellulaire avec des cellules HeLa. En outre, l'ensemble des nanoparticules de silicium modifiées avec des complexes de platine(II) présentent un effet d’émission d’agrégation induite (AIE) intéressant. Par ailleurs, une série de complexes d'iridium(III) ont été synthétisés permettant d’obtenir une émission allant du jaune au rouge. Ces complexes d'iridium(III) ont en outre été utilisés pour une application en électrochimiluminescence (ECL). L’ECL est un outil d'imagerie qui génère des émissions sans excitation lumineuse et qui attire de plus en plus l’attention dans les analyses biologiques. Des nanosytèmes de « carbon dots » et des nanoparticules de silicium modifiés avec des complexes métalliques ont également été étudiés pour des propriétés en ECL
The work of this thesis titled “Luminescent Nanomaterials for diagnostic applications” is synthesis, characterization and bioimaging applications of nanomaterials. Silicon nanoparticles were synthesized and modified with different functional groups such as amino, carboxylate, sugar and platinum(II) complex on the surface, and applies for cellular imaging at HeLa. Moreover, the assembly platinum(II) complexes modified silicon nanoparticles exhibit an interesting aggregation induced emission (AIE) effect. In addition, a series of iridium(III) complexes were synthesized with tunable emission color from yellow to red. Those iridium(III) complexes were further used for electrochemiluminescence (ECL) application. ECL is an imaging tool that generate emission without light excitation and has gained more attention in many bioassays. Besides, nanosystem of metal complex modified carbon dots and silicon nanoparticles were also investigated the ECL properties

Structural applications in transportation necessitate materials with high specific strength and stiffness. With its low density, aluminum (Al) is an interesting candidate, but further strengthening would be beneficial. In this work, the benefits and limitations of nanoreinforcements for aluminum strengthening has been assessed through the addition of carbon nanotube (CNTs) and nanometric alumina (n-Al2O3) to an aluminum matrix by powder metallurgy. It has been found that mechanical milling can homogeneously disperse n-Al2O3 in aluminum. Furthermore, mechanical milling offers the advantages of strengthening the aluminum powder through grain refinement, cold working, solid solution and precipitation. However, CNTs are damaged by mechanical milling, and their homogeneous dispersion cannot be achieved with a chemical dispersant. Nanocomposite consolidation has presented several challenges as hot pressing resulted in a lack of bonding, grain growth and the formation of Al4C3 from damaged CNTs. Cold spraying of Al2O3/Al has resulted in a porous coating with decreased hardness. The microhardness and compression properties of an Al2O3/Al nanocomposite produced by mechanical milling followed by hot pressing were measured. Comparison with modeled values and literature results indicates that higher experimental yield strength obtained with the addition of n-Al2O3 versus micron size Al2O3 is due to in-situ matrix strengthening. Modeling shows that CNTs offer high potential gains in stiffness due to their high aspect ratio and their high Young modulus. On the other hand, as yield gains associated with the addition of nanoreinforcement are mainly due to matrix strengthening, discontinuous nanocomposites do not benefit from the CNT's exceptional strength. In this case, n-Al2O3 would be selected over CNTs as it is cheaper and more easily dispersed.
Les applications structurales du secteur des transports nécessitent des matériaux avec des résistances mécaniques et des rigidités spécifiques élevées. Avec sa faible densité, l'aluminium s'avère un candidat de choix. Par contre, pour favoriser son utilisation, l'augmentation des propriétés spécifiques est nécessaire.Dans ce projet, le potentiel et les limitations des nanorenforts pour l'augmentation de la résistance mécanique de l'aluminium ont été évalués. Pour ce faire, des composites à matrice d'aluminium renforcés par nanotubes de carbone (CNTs) et alumine nanométrique (n-Al2O3) ont été fabriqués par métallurgie des poudres. Il a été constaté que le broyage mécanique disperse de manière homogène l'alumine nanométrique dans l'aluminium. En plus, le broyage mécanique offre l'avantage de renforcer la matrice d'aluminium par affinement des grains et écrouissage en plus de procurer un durcissement par solution solide et par précipitation. Par contre, les nanotubes de carbone sont endommagés par le broyage et il n'est pas possible d'obtenir une dispersion homogène des nanotubes dans l'aluminium par l'utilisation d'un dispersant chimique.La consolidation des nanocomposites présente aussi de nombreux défis puisque le pressage à chaud ne permet pas un bon frittage, provoque la croissance des grains et mène à la formation de carbures à partir des nanotubes endommagés. La pulvérisation à froid des poudres composites Al2O3/Al a quant à elle produit un revêtement poreux avec une dureté réduite.La microdureté et les propriétés mécaniques en compression du nanocomposite Al2O3/Al produit par broyage mécanique suivi d'un pressage à chaud ont été mesurées. La comparaison de ces résultats avec les valeurs modélisées et celles provenant de la littérature indique que le gain en limite d'élasticité obtenu expérimentalement avec l'addition d'alumine nanom

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2006.
Includes bibliographical references.
This thesis focuses on microfluidics based approaches for synthesis and surface-engineering of colloidal particles. Bottom-up assembly through colloidal nucleation and growth is a popular route to the controlled synthesis of nanomaterials. Standard bench-scale synthetic chemistry techniques often involve non-uniform spatial and temporal distributions of concentration and temperature, and are not readily scalable. Photolithography-based microfabrication enables the application of classical techniques of chemical reaction engineering to design chemical reactors that cannot be realized easily at the macroscale, and that closely approach theoretical 'idealized' reactor configurations. In addition, the microfluidic format allows precisely controlled reaction conditions such as rapid mixing, and concentration and temperature uniformity. The goal of this thesis was to design microfluidic reactors for synthesis of core-shell colloidal particles with tunable sizes. Microscale segmented gas-liquid flows overcome the large axial dispersion effects associated with single-phase laminar flows. Microchannel devices that yielded uniform, stable gas-liquid segmented flows over three orders of magnitude in flow velocity were first developed.
(cont.) Extensive experimental studies of the transport, dynamics and stability of such flows were then conducted with pulsed-laser fluorescent microscopy, optical stereomicroscopy and micro particle image velocimetry (-PIV). Flow segmentation not only reduces axial dispersion, but also allows rapid micromixing of miscible liquids through internal recirculations in the liquid phase. This added functionality is especially useful in syntheses involving colloidal particles that, due to inherently low diffusivity, cannot be rapidly mixed by laminar diffusive techniques. Continuous segmented flow reactors were then developed for the synthesis of colloidal silica and titania particles by sol-gel chemistry. Particle sizes could be tuned by varying the rates of flow of reactants, or by varying the chip temperature. Particle size distributions comparable to or narrower than the corresponding stirred-flask synthesis, with little agglomeration or shape distortion were obtained. Coating of colloidal particles with one or more layers of different materials is used to modify their optical, chemical or surface properties. Core-shell particles are often prepared by controlled precipitation of inorganic precursors onto core particles.
(cont.) Synthesis of such structures requires precise control over process parameters to prevent precipitation of secondary particles of shell material and agglomeration of primary particles. Particles coated with titania are exceptionally difficult to synthesize due to the high reactivity of the titania precursors, which makes controlled precipitation difficult. A novel continuous flow microfluidic reactor with sequential multi-point precursor addition was developed for colloidal overcoating processes. Silica particles were coated with uniform titania layers of tunable thickness by the controlled hydrolysis of titanium ethoxide, with no secondary particle formation or agglomeration. An integrated reactor for continuous silica synthesis and in-situ series overcoating with titania was then developed using a two-level stacked reactor fabrication process. Finally, multi-step nanomaterials synthesis and surface coating with incompatible chemistries requires the development of microfluidic 'unit operations' equivalent to particle filtration. In this context, rapid, continuous microfluidic particle separation was demonstrated using transverse free-flow electrophoresis.
by Saif A. Khan.
Ph.D.

The integration of nanomaterials between biological and electronic world has revolutionized the way of understanding how to generate functional bioelectronic device and open a new horizon for the future of bioelectronics. The use of nanomaterials as a versatile interface in the area of bioelectronics offers many practical solutions and recently outshines as an alternative method to overcome technical challenges to control and regulate the mean of communication between biological and electronics systems. Therefore, the interfacing nanomaterials yields broad platform of functional units for the integration as bioelectronic interfaces and starts to have a great importance to many fields within the life science. In parallel with the advancements for the successful combination of biological and electronic worlds using nanotechnology in a conventional way, a new branch of switchable bioelectronics based on signal-responsive materials and related interfaces have been emerged. The switchable bioelectronics consists of functional interfaces equipped with molecular cue that able to mimic and adapt their natural environment and change physical and chemical properties on demand. These switchable interfaces are essential to develop a range of technologies to understand function and properties of biological systems such as bio-catalysis, control of ion transfer and molecular recognition used in bioelectronics systems. This thesis focuses on both the integration of functional nanomaterials to improve electrical interfacing between biological system and electronics and also the generation of a dynamic interface having ability to respond real-life physical and chemical changes. The developing of such a dynamic interface allows one to understand how do living system probe and respond their changing environment and also help control and modulate bio-molecular interactions in a confined space using external physical and chemical stimuli. First, the integration of various nanomaterials is described to understand the effect of different surface modifications and morphologies using different materials on the basis of enzyme-based electrochemical sensing of biological analytes. Then, various switchable interfaces including temperature, light and pH, consist of graphene-enzyme and responsive polymer, are developed to control and regulate enzymebased biomolecular reactions. Finally, physically controlled programmable bio-interface which is described by “AND” and “OR” Boolean logic operations using two different stimuli on one electrode, is introduced. Together, the findings presented in this thesis lay the groundwork for the establishment switchable and programmable bioelectronics. The both approaches are promising candidates to provide key building blocks for future practical systems, as well as model systems for fundamental research.

Nanomaterials such as graphene oxide and carbon nanotubes, have demonstrated excellent properties for membrane desalination, including decrease of maintenance, increase of flux rate, simple solution casting, and impressive chemical inertness. Here, two projects are studied to investigate nanocarbon based membrane desalination. The first project is to prepare hybrid membranes with amyloid fibrils intercalated with graphene oxide sheets. The addition of protein amyloid fibrils expands the interlayer spacing between graphene oxide nanosheets and introduces additional functional groups in the diffusion pathways, resulting in increase of flux rate and rejection rate for the organic dyes. Amyloid fibrils also provide structural assistance to the hybrid membrane, which supresses cracking and instability of graphene oxide sheets. The second project is to fabricate polymer nanocomposite membranes with carbon nanotubes encapsulated by polymerized surfactants. The designed polymerizable surfactant forms lyotropic liquid crystalline mesophases in an aqueous medium with hexagonal packing of cylindrical micelles. The adsorption of surfactants on the surface of carbon nanotubes allows a stable dispersion of carbon nanotubes encapsulated in the cylindrical micelles, resulting in the ordered structure. After photo-polymerization, the composite membranes display enhanced dye rejection. Both projects have shown promising ways to improve membrane filtration by using nanomaterials.

Strontium titanate (SrTi03) is a perovskite material with diverse physical properties. Many of its properties are associated with its atomic structure, such as quantum paraelectricity, structural phase transitions, and extrinsically induced ferroelectricity. Accordingly, many structural investigations have been performed on bulk and thin film samples of SrTi03 . At the same time, many syntheses of SrTi03 nanoparticles and nanowires have been reported. Despite these factors, however, the structure and properties of SrTi03 nanoparticles and nanowires are not well understood. The aim of this thesis is to better understand such SrTi03 nanoparticles and nanomaterials using a combination of theoretical and experimental methods. Density-functional calculations were performed of bulk SrTi03 and (100) SrTi03 surfaces, with a focus towards nanomaterials applications. The outer layers of both SrO and Ti02 terminated (100) surfaces relaxed inward, and the subsequent layers alternately moved outwards and inwards. Furthermore, surface rumpling was observed. Both the interlayer distances and rumpling were determined as a function of depth. Tests of different exchange-correlation functionals were performed throughout. Next, the first-ever density-functional calculations were performed of the structural and electronic properties of SrTi03 nanowires. No ferroelectric states were found for the nanowires, despite active searching. Compressive axial and lateral strain was observed for all the nanowires, and the extent of this strain varied with diameter and surface termination. Furthermore, surface rumpling was found to occur on and within the nanowires; subsequent plots of the local polarization revealed that every nanowire possessed a radial polarization texture. Finally, electronic band structure calculations revealed that all the SrTi03 nanowires were metallic. Finally, experimental studies were performed on SrTi03 nanoparticles, with the longterm aim of determining and understanding their local atomic structure. Transmission electron microscopy showed that the nanoparticles were polydisperse, and powder x-ray diffraction measurements showed that they were composed of mostly SrTi03.

In this study, CO2 adsorption in the presence and absence of co-adsorbed H2O was investigated on different nanomaterials including nanocrystalline NaY zeolite (nano NaY), ZnO, MgO and λ-Al2O3 nanoparticles as well as mixed phase aluminum nanowhiskers. In the case of nano NaY, FTIR spectra show that a majority of CO2 adsorbs in the pores of these zeolites in a linear complex with the exchangeable cation. Most interesting is the formation of carbonate and bicarbonate on the external surface of nano NaY zeolites, suggesting unique sites for CO2 adsorption on the surface of these small nanomaterials. Adsorption of 18O-labeled carbon dioxide and theoretical quantum chemical calculations confirms the assignment of these different species. For aluminum oxyhydroxide nanowhiskers and gamma alumina in the absence of co-adsorbed water, CO2 reacts with surface hydroxyl groups to yield adsorbed bicarbonate as well as some carbonate. C18O2 adsorption confirms these assignments. In the case of nanoparticulate ZnO, CO2 adsorption under dry conditions results in formation of carbonate, bicarbonates as well as carboxylates. However, in the presence of co-adsorbed water, only carbonate species is formed. 18O-labeled carbon dioxide adsorption and theoretical quantum chemical calculations confirm the vibrational assignment for these different species. Mixed isotope studies with H216O + C18O2 and H218O + C16O2 suggest that there is extensive exchange between oxygen in adsorbed water and oxygen atoms in gas-phase carbon dioxide. CO2 adsorption on MgO surfaces, under dry conditions results in formation of carbonate and bicarbonates. Implications for the use of these nanomaterials in carbon dioxide uptake and storage are discussed.

The thesis consists of two major research topic i.e. Porphyrin and Nano crystalline cellulose. The porphyrin project started with the production of porphyrin chromophores for dye sensitized solar cells. These derivatives were required as references for an ongoing project of the research group that hosted me. In addition, some porphyrin-porphyrin tweezers were prepared using a one pot synthetic methodology developed in our lab, based on the use of trichloro triazine as a linker. These derivatives were necessary for collaboration with Professor Nina Berova at Columbia University that studies their use for the determination of the absolute configuration of chiral molecules by circular dichroism. After this training period, the thesis project continued with an original research based on the use of click-chemistry for porphyrin functionalization. The nanocellulose project started with the production of nanocrystalline cellulose from microcrystalline cellulose by acid hydrolysis. The nanocellulose has chemically modifiable OH groups on the surface. This allows the use of a wide range of chemical reactions for its functionalization. The linking of a pH sensitive dye on the surface of NCC was studied. In addition, several strategies were being employed for the functionalization of NCC with other groups such as cationic substituents (using (2,3-epoxypropyl)trimethylammonium chloride), amino (using epichlorohydrin and 3-aminopropyltrimethoxysilane), carboxy (using ammonium persulfate and TEMPO). Out of various chemical modifications carried out on NCC, the TEMPO mediated carboxylation for introduction of carboxyl group on NCC was proved to be easy, convenient and even resulted in high degree of functionalization. Using these material and typical carbodiimide chemistry, functional groups such as porphyrins (that acts as a sensitizer for singlet oxygen production) and a nitro-derivative (capable of producing NO upon irradiation) were prepared. These features are under study to verify their potential in various therapeutic applications.
La Tesi si compone di due principali temi di ricerca che riguardano le porfirine e la nano-cellulosa. Il progetto sulle profirine è iniziato con la produzione cromofori per celle solari a sensibilizzatore organico. Questi derivati sono stati usati come riferimento per un progetto sulla conversione della luce solare in energia che coinvolge il gruppo di ricerca che mi ha ospitato. Inoltre, sono stati preparati dei dimeri porfirina-porfirina, basati sull’uso di una procedura “one-pot” che impiega la triclorotriazina come linker. Questi derivati sono stati preparati nell’ambito di una collaborazione con la Professoressa Nina Berova (Columbia University) che studia il loro uso per la determinazione della configurazione assoluta di molecole chirali mediante dicroismo circolare. Dopo questo periodo di formazione, il progetto di tesi è proseguito con una ricerca originale, basato sull'uso di click -chemistry per la funzionalizzazione del macrociclo profirinico. Il progetto che riguarda la nanocellulosa, è iniziato con la produzione di cellulosa nanocristallina da cellulosa microcristallina mediante idrolisi acida. La nanocellulosa possiede dei gruppi OH modificabili chimicamente sulla superficie che consentono l'utilizzo di una vasta gamma di reazioni chimiche per la sua funzionalizzazione. Si è quindi studiata la funzionalizzazione della nanocellulosa con un colorante sensibile al pH sulla superficie dei nanocristalli. Inoltre, sono state valutate diverse strategie per la funzionalizzazione superficiale con gruppi cationici (utilizzando 2,3-epossipropil cloruro di trimetil ammonio), ammino (con epicloridrina e 3-amminopropiltrimetossisilano), carbossi (utilizzando persolfato di ammonio e TEMPO). Tra le varie strategie di funzionalizzazione esaminate, la carbossilazione mediata dal TEMPO si è dimostrata efficace e robusta. L'utilizzo di questi materiali e la chimica tipica delle carbodiimidi, ha permesso di legare covalentemente alla nanocellulosa gruppi funzionali come porfirine (che agisce come un sensibilizzatore per la produzione ossigeno singoletto) e un nitro- derivato (in grado di produrre NO sotto illuminazione). Questi materiali sono in fase di studio per verificare il loro potenziale in varie applicazioni terapeutiche.

Els amiloides presenten una estructura fibril·lar molt ordenada. Molts d’aquests conjunts de proteïnes apareixen associats a malalties humanes. No obstant això, es pot aprofitar la naturalesa controlable, estable, ajustable i robusta de les fibres amiloides per crear nanomaterials amb una àmplia gamma d’aplicacions. Els prions funcionals constitueixen una classe particular d’amiloides. Aquestes proteïnes transmissibles presenten una arquitectura modular, amb un domini prió desordenat responsable del assemblatge i d’un o més dominis globulars que proporcionen l’activitat. És important destacar que la proteïna globular original es pot substituir per qualsevol proteïna d’interès, sense comprometre el potencial de fibril·lació. Aquestes fusions genètiques formen fibres en les quals el domini global roman plegat, formant nanoestructures funcionals. Tot i això, en molts casos, els impediments estèrics poden restringir l’activitat d’aquestes fibres. Aquesta limitació es pot solucionar disseccionant els dominis priònics en seqüències més curtes que mantenen les seves propietats d’auto-assemblatge alhora que permeten un millor accés a la proteïna en estat fibril·lar. En aquesta tesi doctoral, vam aprofitar el “soft amyloid core” (SAC) del prió de llevat Sup35p com una unitat de muntatge modular, que recapitula la propensió a l’agregació del domini priònic complet. Vam fusionar el SAC amb diferents proteïnes globulars d’interès que difereixen en la conformació i la mida, creant un mètode genètic general i senzill per generar nanofibres dotades de les funcionalitats desitjades. El modelatge computacional ens va permetre conèixer la relació entre la mida dels dominis globulars i la longitud del enllaç que els connecta al SAC, proporcionant les bases per al disseny de nanomaterials amb diferents propietats mesoscòpiques, ja siguin nanofibres o nanopartícules. Sobre aquesta base, hem dissenyat i produït, per primera vegada, nanopartícules amiloides esfèriques altament actives, no tòxiques, de mida definida, i s’han produït nanoestructures bifuncionals amb aplicació en el subministrament específic de fàrmacs. Les lliçons apreses en aquests exercicis van donar lloc a la construcció d’una nanofibrilla similar a un anticòs biespecífic amb potencial per la immunoteràpia. En resum, els nanomaterials funcionals de tipus priònic descrits aquí aprofiten l’enfocament de la fusió genètica per crear un nou conjunt d’estructures amb aplicacions en biomedicina i biotecnologia.
Los amiloides muestran una estructura fibrilar altamente ordenada. Muchos de estos ensamblajes aparecen asociados a enfermedades humanas. No obstante, la naturaleza controlable, estable, modulable y robusta de las fibras amiloides se puede emplear para construir nanomateriales notables con una amplia gama de aplicaciones. Los priones funcionales constituyen una clase particular de amiloides. Estas proteínas transmisibles exhiben una arquitectura modular, con un dominio priónico desordenado responsable del ensamblaje y uno o más dominios globulares que dan cuenta de la actividad. Cabe destacar que la proteína globular original se puede reemplazar con cualquier proteína de interés sin comprometer el potencial de fibrilación. Estas fusiones genéticas forman fibrillas en las que el dominio globular permanece plegado, lo que genera nanoestructuras funcionales. Sin embargo, en muchos casos, el impedimento estérico restringe la actividad de estas fibrillas. Esta limitación puede resolverse diseccionando los dominios de priones en secuencias más cortas que mantengan sus propiedades de autoensamblado mientras permiten un mejor acceso a la proteína en el estado fibrilar. En esta tesis doctoral, exploramos el "soft amyloid core" (SAC) del prion de levadura Sup35p como una unidad modular de autoensamblaje, que recapitula la propensión a la agregación del dominio priónico completo. Fusionamos el SAC con diferentes proteínas globulares de interés que difieren en conformación y tamaños, creando un enfoque genético general y directo para generar nanofibrillas dotadas de las funcionalidades deseadas. El modelado computacional nos permitió obtener información sobre la relación entre el tamaño de los dominios globulares y la longitud del conector que los une con el SAC, proporcionando la base para el diseño de nanomateriales con diferentes propiedades mesoscópicas, ya sean nanofibrillas o nanopartículas. Sobre esta base, diseñamos y producimos, por primera vez, nanopartículas amiloides esféricas, altamente activas, no tóxicas, de tamaño definido, y diseñamos nanoestructuras bifuncionales con aplicación en la administración dirigida de fármacos. Las lecciones aprendidas en estos ejercicios permitieron la construcción de una nanofibrilla similar a un anticuerpo biespecífico con potencial para su uso en inmunoterapia. En resumen, los nanomateriales funcionales similares a los priones descritos aquí aprovechan la metodología de fusión genética para generar un nuevo conjunto de estructuras con aplicación en biomedicina y biotecnología.
Amyloids display a highly ordered fibrillar structure. Many of these assemblies appear associated with human disease. However, the controllable, stable, tunable, and robust nature of amyloid fibrils can be exploited to build up remarkable nanomaterials with a wide range of applications. Functional prions constitute a particular class of amyloids. These transmissible proteins exhibit a modular architecture, with a disordered prion domain responsible for the assembly and one or more globular domains that account for the activity. Importantly, the original globular protein can be replaced with any protein of interest, without compromising the fibrillation potential. These genetic fusions form fibrils in which the globular domain remains folded, rendering functional nanostructures. However, in many cases, steric hindrance restricts the activity of these fibrils. This limitation can be solved by dissecting prion domains into shorter sequences that keep their self-assembling properties while allowing better access to the protein in the fibrillar state. In this PhD thesis, we exploited the "soft amyloid core (SAC)" of the Sup35p yeast prion as a modular self-assembling unit, which recapitulates the aggregation propensity of the complete prion domain. We fused the SAC to different globular proteins of interest differing in conformation and sizes, building up a general and straightforward genetic approach to generate nanofibrils endowed with desired functionalities. Computational modeling allowed us to gain insights into the relationship between the size of the globular domains and the length of the linker that connects them to the SAC, providing the basis for the design of nanomaterials with different mesoscopic properties, either nanofibrils or nanoparticles. On this basis, we designed and produced, for the first time, highly active, non-toxic, spherical amyloid nanoparticles of defined size and engineered bifunctional nanostructures with application in targeted drug delivery. The lessons learned in these exercises resulted in the construction of a bispecific antibody-like nanofibril, showing potential in immunotherapy. In summary, the prion-like functional nanomaterials described here take profit of the genetic fusion approach to render a novel set of structures with application in biomedicine and biotechnology.

In recent decades, there has been a rapid expansion in the use of manufactured nanoparticles (MNPs). Experimental evidence and material flow models predict that MNPs enter wastewater treatment plants and partition to sewage sludge and majority of that sludge is land applied as biosolids. During wastewater treatment and after land application, MNPs undergo biogeochemical transformations (aging). The primary transformation process for silver MNPs (Ag-MNPs) is sulfidation, while zinc oxide MNPs (ZnO-MNPs) most likely undergo phosphatation and sulfidation. Our overall goal was to assess bioavailability and toxicogenomic impacts of both pristine, defined as-synthesized, and aged Ag- and ZnO-MNPs, as well as their respective ions, to a model organism, the soil nematode Caenorhabditis elegans. We first investigated the toxicity of pristine Ag-MNPs, sulfidized Ag-MNPs (sAg-MNPs), and AgNO3 to identify the most sensitive ecologically relevant endpoint in C. elegans. We identified reproduction as the most sensitive endpoint for all treatments with sAg-MNPs being about 10-fold less toxic than pristine Ag-MNPs. Using synchrotron x-ray microspectroscopy we demonstrated that AgNO3 and pristine Ag-MNPs had similar bioavailability while aged sAg-MNPs caused toxicity without being taken up by C. elegans. Comparisons of the genomic impacts of both MNPs revealed that Ag-MNPs and sAg-MNPs have transcriptomic profiles distinct from each other and from AgNO3. The toxicity mechanisms of sAg-MNPs are possibly associated with damaging effects to cuticle. We also investigated the effects pristine zinc oxide MNPs (ZnO-MNPs) and aged ZnO-MNPs, including phosphatated (pZnO-MNPs) and sulfidized (sZnO-MNPs), as well as ZnSO4 have on C. elegans using a toxicogenomic approach. Aging of ZnO-MNPs reduced toxicity nearly 10-fold. Toxicity of pristine ZnO-MNPs was similar to the toxicity caused by ZnSO4 but less than 30% of responding genes was shared between these two treatments. This suggests that some of the effects of pristine ZnO-MNPs are also particle-specific. The genomic results showed that based on Gene Ontology and induced biological pathways all MNP treatments shared more similarities than any MNP treatment did with ZnSO4. This dissertation demonstrates that the toxicity of Ag- and ZnO-MNPs to C. elegans is reduced and operates through different mechanisms after transformation during the wastewater treatment process.

Los proceso térmicos y por microondas, se utilizan para sintetizar nanopartículas de diferentes óxidos metálicos tales como magnetita (Fe3O4) y óxido de cerio (CeO2). Mediante la modificación de los precursores Fe(R2diket)3 (R = Ph, tBu y CF3), Ce(acac)3 y Ce(OAc)3, y siguiendo la misma ruta de síntesis, es posible controlar el tamaño y la forma de los nanocristales obtenidos. La ruta general se lleva a cabo en trietilenglicol (TREG) o benzylalcohol (BnOH), debido a su alto punto de ebullición y que además puede actuar como estabilizante de las nanopartículas en disolventes polares. Las nanopartículas se han caracterizado por varias técnicas de laboratorio comunes: Alta Resolución Microscopía Electrónica de Transmisión (HR TEM), espectroscopia infrarroja (IR), Rayos X (XRPD), magnetometría tal como Superconducting Quantum Interference Device (SQUID), Resonancia Magnética Nuclear (RMN), Cromatografía de Gases-Espectroscopía de Masas (GC-MS), Espectroscopia de fotoelectrones emitidos por rayos X (XPS) y Análisis Termogravimétrico (TGA). Con todas estas técnicas, el tamaño final, la forma, la composición, la estructura cristalina, el comportamiento magnético y la interacción del ligando con la superficie de las nanopartículas han sido estudiadas y caracterizadas. Además, se demuestra la alta eficiencia de los das dos metodologías que se han optimizado para sintetizar nanopartículas de diferentes familias. Las soluciones coloidales estables obtenidas en etanol se han utilizado para generar capas superconductoras de YBa2Cu3O7-δ (YBCO) debido a que la corriente crítica se puede aumentar cuando se incrustan las nanopartículas. Finalmente, una nueva aplicación como comportamiento antioxidante en células humanas se ha llevado a cabo para el caso de las nanopartículas de CeO2 debido a sus específicas propiedades que las hacen muy interesantes en este nuevo campo.
Thermal and microwave methodologies are used to synthesize different metal oxides nanoparticles such as magnetite (Fe3O4), cerium oxide (CeO2). By modifying the precursors (Fe(R2diket)3 (R= Ph, tBu and CF3), Ce(acac)3 and Ce(OAc)3), and following the same synthetic route, it is possible to control the size and shape of the nanocrystals obtained. The general route is carried out in triethylene glycol (TREG) or benzyl alcohol (BnOH) media, due to its high boiling point and, which acts also as a capping ligand of the nanoparticles, stabilizing them in polar solvents. Nanoparticles have been characterized by several common physical laboratory techniques: High Resolution Transmission Electron Microscopy (HR TEM), infrared spectroscopy (IR), X-ray Powder Diffraction (XRPD), magnetometry via Superconducting Quantum Interference Device (SQUID), Nuclear Magnetic Resonance (RMN), Gas Chromatography-Mass Spectroscopy (GC-MS), X-ray Photoelectron Spectroscopy (XPS) and Thermogravimetric Analysis (TGA). With all these techniques, the final size, shape, composition, crystal structure, magnetic behaviour and capping ligand interaction have been studied, showing the high quality crystals generated. In addition, we demonstrate the high efficiency of all two one-pot methodologies that have been optimized to synthesize different families of nanoparticles. The stable colloidal solutions obtained in ethanol have been used to generate ex-situ hybrid YBa2Cu3O7-δ (YBCO) superconducting layers because the critical current can be increased when the nanoparticles are embedded. Finally, a new application as an antioxidant behaviour in human cells is tested for the case of CeO2 nanoparticles due to their specifically properties that make them really interested in this new field.

Analytical disciplines are an important field for the progress of healthcare and medicine. In fact the technologies related to analytical disciplines may reveal important information for early diagnosis, treatment of diseases, food safety and environmental monitoring. In this regard, novel advances in analytical disciplines are highly desired. As a promising tool, biosensors are useful systems that enable the detection of agents with diagnostic interest. Since nanotechnology enables the manipulation and control at the nanoscale, biosensors based on nanotechnology offer powerful capabilities to diagnostic technology. In this dissertation, the advantages of the integration of nanomaterials into microarray technology are widely studied, generally in terms of sensitivity. Particularly, the performance of cadmium-selenide/zinc-sulfide (CdSe@ZnS) quantum dots (QDs) and the fluorescent dye Alexa 647 as reporter in an assay designed to detect apolipoprotein E (ApoE) has been compared. The assay is a sandwich immunocomplex microarray that functions via excitation by visible light. ApoE was chosen for its potential as a biomarker for Alzheimer's disease. The two versions of the microarray (QD or Alexa 647) were assessed under the same experimental conditions. The QDs proved to be highly e¿ective reporters in the microarrays, although their performance strongly varied in function of the excitation wavelength. At 633 nm, the QD microarray, at an excitation wavelength of 532 nm, provided a limit of detection (LOD) of ~62 pg mL-1, ¿ve times more sensitive than that of the Alexa microarray (~307 pg mL-1). Finally, serial dilutions from a human serum sample were assayed with high sensitivity and acceptable precision and accuracy (Anal. Chem. 2012, 84:6821). Since graphene oxide (GO) is a recently discovered nanomaterial and microarray technology relies on optical signals, the photonic properties of GO are discussed and the state-of-the-art of GO in optical biosensing has been widely documented (Adv. Mater. 2012, 24:3298). Furthermore, GO has been studied as a highly efficient quencher of QDs, reporting a quenching efficiency of nearly 100%. Finally, such interaction between GO and QDs has been proposed as a highly sensitive transduction system for microarray-based biodetection (Carbon 2012, 50:2987). This research aims at demonstrating how the endeavour of the fusion between nanomaterials and microarray technology exhibits enormous possibilities towards biomarker screening, food safety and environmental monitoring.
Las tecnologías relacionadas con el diagnóstico son un campo importante para el progreso de la medicina y el cuidado de las salud. Por ejemplo, estas tecnologías pueden aportar valiosa información para el tratamiento y diagnóstico temprano de enfermedades, seguridad en alimentos y monitoreo del medio ambiente. En este contexto, los sistemas de biosensado son una herramienta muy prometedora que permite la detección de agentes con interés diagnostico. Dado que la nanotecnología facilita la manipulación y control a la nanoescala, los sistemas de biodetección basados en nanotecnología poseen poderosas capacidades que pueden ser explotadas en las tecnologías relacionadas con el diagnóstico. En esta tesisis se han estudiado las ventajas que aporta la integración de nanomateriales a la tecnología de microarrays, generalmente en términos de sensibilidad. Particularmente, se ha estudiado el desempeño de la integración de nanocristales semiconductores (NS) para la detección de un biomarcador relacionado con Alzheimer en formato microarray. En dicho microarray se ha observado un importante rendimiento, mostrando un excelente limite de detección de 62 pg mL-1, el cual supera a otros metodos convencionales de detección como el ELISA (470 pg mL-1). También se ha analizado un banco de diluciones de una muestra de suero humano con precisión y exactitud aceptables (Anal. Chem. 2012, 84:6821). Por otra parte, ya que el óxido de grafeno (OG) es un material muy novedoso y la tecnología de microarrays depende de señales ópticas, se ha documentado ampliamente el estado del arte sobre el uso de (OG) en en el campo del biosensado óptico (Adv. Mater. 2012, 24:3298). Adicionalmente, se ha estudiado al OG como un desactivador de fluorescencia de NS altamente eficiente, presentando una eficiencia en la desactivación de NS de casi el 100%. Finalmente se ha aplicado dicha interacción entre NS y OG para diseñar un sistema de transducción altamente sensible (Carbon 2012, 50:2987 ). Esta investigación tiene por objetivo demostrar las ventajas y el potencial que posee la fusión entre los nanomateriales y la tecnología de microarrays como un sistema aplicado al campo del diagnóstico

El monitoreig ambiental basat en sistemes de biosensors té molta rellevància, no només en el camp de la investigació sinó també en aplicacions reals a nivell industrial. Això és degut als avantatges d’aquestes plataformes analítiques com, especialment, la seva simplicitat i alta rendibilitat pel seu cost. A més, els avenços recents en nanociència i nanotecnologia incrementen donen lloc a nous nanomaterials que tenen propietats elèctriques interessants com ara la seva capacitat de millorar la conductivitat dels elèctrodes. Aixó té un interès particular de cara al desenvolupament de sistemes de biosensors electroquímics. La combinació de nanomaterials amb biosensors electroquímics permeten construir eines d’anàlisi poderoses per al monitoreig mediambiental. Aquest és l’objectiu principal d’aquesta tesi, que descriu el desenvolupament i l’aplicació de tres nous biosensors pel monitoreig mediambiental mitjançant l’ús de nanomaterials. El primer capítol de la tesi proporciona una introducció general sobre el monitoreig mediambiental de contaminants i dona una breu descripció i classificació d’aquests components nocius. També dona una visió de la rellevància de l’ús de nanomaterials en sistemes de biosensors pel monitoreig mediambiental amb una detallada revisió dels últims treballs publicats que descriuen aspectes innovadors així com possibles inconvenients. Al capítol 3 es descriu una plataforma de monitoreig mediambiental basada en la inhibició de l’enzim acetilcolinesterasa. El sistema desenvolupat utilitza partícules magnètiques i l’enzim acetilcolinesterasa sobre elèctrodes de diamant dopats amb Bor. Gràcies a l’ús de partícules magnètiques i a les característiques de la superfície de l’elèctrode, aquesta plataforma és utilitzada com a sistema multi ús amb una alta reproducibilitat que és capaç de mesurar el pesticida chlorpyrifos en mostres reals d’aigua de riu (riu Yokoama, Japó). Al capítol 4 s’explica el desenvolupament de d’un sistema de detecció simultània de contaminants, el catecol (un derivat fenòlic) i el chlorpyrifos (un pesticida del grup dels organofosfats). Aquesta detecció s’aconsegueix utilitzant elèctrodes serigrafiats de carboni (screen printed carbon electrodes, SPCE) modificats amb nanopartícules d’òxid d’Iridi i amb tirosinasa. El biosensor proposat millora la sensibilitat en la detecció del catecol si es compara amb altres biosensors ja descrits en la bibliografia. Aquest biosensor mostra també una elevada sensibilitat en la detecció de chlorpyrifos quan s’utilitza el mode d’operació d’inhibició de la tirosinasa. Finalment, s’ha explorat l’eficiència del biosensor per aplicacions reals en aigua de riu i aigua de l’aixeta mostrant grans possibilitats per futures aplicacions com a plataforma de baix cost. El tercer biosensor desenvolupat s’explica al capítol 5. En aquest capítol es proposa un sistema de biosensors sense enzims basat en nanopartícules d’òxid de coure (CuO) per la detecció de components fenòlics i d’un herbicida altament tòxic, el Diuron. La detecció es fa mitjançant SPCE on les nanopartícules de CuO formen un complex estable amb els components fenòlics que es mesuren a partir de la reacció electroquímica que té lloc a la superfície de l’elèctrode. Val a dir que és una de les primeres aplicacions que s’utilitzen pel monitoreig mediambiental mitjançant l’ús de nanopartícules de CuO. Aquestes nanopartícules mimetitzen el centre actiu de la tirosinasa obtenint resultats comparables a altres plataformes enzimàtiques. Aquesta plataforma analítica pot ser utilitzada en aplicacions amb mostres reals donat que el límit de detecció obtingut es troba en els nivells que demana el monitoreig establerts per la legislació vigent.
Environmental monitoring based on biosensing systems has increased its relevance not only in the research field but also in the real industrial application. This is due to the advantages of such analytical platforms especially their simplicity and their cost/efficiency. Moreover, the recent advances in nanoscience and nanotechnology increase the emerging of new nanomaterials which have interesting electrical properties such as their capacity to improve the electrode conductivity. This has a particular interest in the development of electrochemical biosensing systems. The combination of nanomaterials with electrochemical biosensing platforms can build up powerful analytical tools for the environmental monitoring. This represents the main objective of this PhD Thesis, that divided in six chapters describes the development and application of three new biosensing platforms for environmental monitoring using nanomaterials. The first chapter of the thesis gives a general introduction on environmental monitoring of pollutants and offers a brief description and classification of these compounds. This chapter also gives an overview of the relevance of the use of nanomaterials in biosensing systems for environmental monitoring with a detailed review of the last published works describing also their innovation aspects and also the possible drawbacks. In Chapter 3 the biosensing platform for environmental monitoring based on the inhibition of acetylcholinesterase is described. The developed system uses magnetic beads and acetylcholinesterase enzyme over Boron Doped Diamond Electrode. Moreover, through the use of magnetic beads and the surface characteristics of the electrode, this platform is used as multi use system with high reproducibility able also to measure the pesticide chlorpyrifos in real sample (Yokoama river, Japan). In Chapter 4 a simultaneous detection system of pollutants for catechol (a phenol derivative) and chlorpyrifos (an organophosphate pesticide), is developed. Such sensing is achieved through a SPCE modified with IrOx NPs and tyrosinase. The proposed biosensor reports improvement in the sensitivity for catechol compared to previously reported biosensors. This biosensor shows also a high sensitivity for chlorpyrifos while being used in a tyrosinase inhibition mode operation. Finally the efficiency of this biosensor is explored for real applications in river and tap water showing great possibilities for future application as a low cost platform. In Chapter 5 a free enzymatic bio-sensing system based on CuO nanoparticles for detection of phenols compounds and for a high toxic herbicide (Diuron) is proposed. Such sensing is achieved through a SPCE where CuO NPs create a stable complex with phenolic compounds that are measured through electrochemical reaction at electrode surface. Moreover it is one of the first applications using CuO NPs for environmental monitoring. CuO NPs have the function to mimic the active centre of tyrosinase obtaining results comparable with other enzymatic platforms. This analytical platform can be used for real sample applications due to the fact that the detection limit is within the requested levels of monitoring established by the legislation. Annex A shows a very interesting review over the biosensing systems inenvironmental monitoring using nanomaterials. This review was published in a very high impact factor journal (Chemical Review Impact factor of 46.658).

This thesis focuses on the preparation of nanomaterials made of proteins and polymers. Even though the technology has advanced in the last decades to design new devices at the atomic scale, researchers are still inspired by what Nature has produced and optimized for millions of years. Following this concept, this work uses proteins forming water-filled channels, called porins, which regulate the flow of ions and biomolecules in cellular life. Two proteins were studied: Omp2a and VDAC36. The first part of the dissertation is the thermomechanical properties study of the latest hybrid membrane developed by the IMEM group: an thin nanoperforated poly(lactic acid) (PLA) film with the Omp2a porin immobilized onto the surface . For this purpose, a new equipment based on the microcantilever technology was used. The SCAnning LAser analyzer (SCALA) characterizes the coated cantilevers which allows the following of the cantilever bending induced by the compression/expansion of the sample coating (i.e. proteins or polymers). In this study, the intermolecular reorganization of Omp2a aggregates was evidenced as well as the protein secondary structure stability against temperature. The same method was employed to study the impact of nanofeatures (perforations and drugs domains) on films of PLA. They affected the glass transition and the cold crystallization temperatures. The changes were dependent on the size and abundance of the nanofeatures, which can modulate the properties of future materials. Moreover, this work established a protocol for the study of biomolecules and polymers attached to microcantilevers, allowing an accurate study of the thermomechanical properties using very low amounts of sample. The second part of the thesis is the development of new hybrid nanomaterials composed of VDAC36, PLA and poly(3,4-ethylenedioxythiophene) (PEDOT). An efficient protocol was established for the production of VDAC36 and its subsequent refolding was achieved. The beta-barrel nature of the protein was revealed and its tendency to form oligomers was demonstrated. Finally, the size of the protein inner channel could be determined. The VDAC36 was added to the polymer material made of three alternating layers of PLA and PEDOT. The electrical properties of the material were modified by the addition of the protein: the overall resistance was reduced and the supercapacitive behaviour was enhanced. The description of the electrical equivalent circuit also revealed that the protein induced the diffusion of ions. To improve the material, the number of layers was increased and the conducting polymer was modified by incorporating a monomer bearing a dodecyl chain. The modifications were proved useful as the protein content and the electrical properties increased. Finally, the new hybrid material could provide an adaptive electrical response according to the concentration of biomolecules.
Esta tesis se centra en la preparación de nanomateriales basados en proteínas y polímeros. A pesar de los avances realizados en las últimas décadas en el diseño de nuevos dispositivos a escala nanométrica, los investigadores aún se inspiran en lo que la Naturaleza ha producido y ha optimizado durante millones de años. A partir de esta premisa, en este trabajo se han usado proteínas, que constituyen canales de agua y cuya función es regular el paso de iones y biomoléculas en organismos celulares. Las proteínas involucradas son Omp2a y VDAC36. La primera parte de esta disertación se centra en el estudio de las propiedades termo-mecánicas de los componentes una novedosa membrana híbrida desarrollada per el grupo IMEM: una película ultra-delgada de ácido poli(láctico) (PLA) nano-perforada y funcionalizada en la superficie con moléculas de Omp2a. Para su caracterización se usó un nuevo equipo basado en la tecnología de micro-palancas. Un analizador laser de barrido (SCALA, el acrónimo de dicho aparato en inglés) permite caracterizar palancas recubiertas de muestra polimérica mediante la reflexión de un rayo de luz láser sobre la superficie del soporte revestido. Mediante su acoplado a una cámara termo-controlada, SCALA permite seguir la deformación del soporte inducida per la compresión/expansión de la muestra en forma de recubrimiento (ya sean polímeros como proteínas). Mediante esta técnica se evidenció la reorganización intermolecular en agregados de la proteína Omp2a, así como la alta estabilidad de su estructura secundaria en frente de la temperatura. El mismo método fue usado para estudiar el impacto de las nano-características sobre las películas de PLA. Nano-poros, nano-perforaciones y nano-dominios fueron añadidos a los films de PLA. Dichas modificaciones afectan tanto a su transición vítrea como a la cristalización en frío de dichas películas. Los cambios observados dependen del tamaño y la abundancia de las nano-modificaciones, lo cual va a permitir modular las propiedades de futuros nano-materiales. Más aún, este trabajo ha establecido las bases para un protocolo general de uso de micro-palancas para estudiar proteínas y polímeros unidos a ellas, permitiendo la caracterización de sus propiedades termo-mecánicas usando cantidades ínfimas de material. Se pudo establecer un protocolo eficiente para la producción de VDAC36 i su subsecuente re-naturalización por medio de una combinación de detergentes y alcoholes. Per medio de experimentos de dicroísmo circular se puso de manifiesto su naturaleza de barril beta y se mostró su tendencia a formar oligómeros mediante entrecruzamientos químicos. El tamaño del poro se pudo determinar mediante ensayos de hinchado. A continuación, VDAC36 se incorporó al material polimérico constituido por tres capas de polímero, alternando PLA y PEDOT. Las propiedades eléctricas de este material quedaron visiblemente modificadas por la adición de la proteína sobre los films de polímero: se redujo su resistancia mientras que su comportamiento como supercondensador, consecuencia la presencia de PEDOT, aumentó. La descripción del circuito eléctrico equivalente reveló a su vez que la proteína inducía la difusión de iones. Para mejorar la retención de proteínas y la integridad mecánica del material, las capas de polímero de la membrana se aumentaron hasta cinco. A su vez, el monómero de EDOT se modificó para incorporar una cadena de dodecilo y poder así imitar una membrana celular. Estas últimas modificaciones se mostraron de gran utilidad puesto que el contenido en proteína aumentó y los cambios eléctricos se hicieron más pronunciados. Finalmente, este nuevo material híbrido fue capaz de proporcionar una respuesta eléctrica adaptativa como respuesta a cambios en la concentración de biomoléculas.

In this dissertation, BaTiO3 nanocrystals, Bi4Ti3O12 nanostructured microspheres, and cosubstituted Bi4Ti3O12 nanoparticles and ceramics were prepared using solvothermal, hydrothermal and citrate-gel methods. The ferroelectric properties of the prepared cosubstituted Bi4Ti3O12 ceramics were studied using P–E hysteresis loop, leakage, and polarization fatigue measurements. A two-phase solvothermal synthesis approach for the preparation of hydrophobic BaTiO3 nanocrystals was developed. The two-phase method is based on the growth of nanocrystals at the oil/water interface by the reaction between metal surfactant complexes in the oil phase and a mineralizer in the water phase. Three kind of organic solvents, hexadecene, toluene, and heptane were used as the oil phase and compared to each other with respect to the product quality. The BaTiO3 particles are crystalline with a mean size of 3.7 nm and can be dispersed in a variety of organic solvents forming highly transparent dispersions. A hydrothermal method was developed for the synthesis of Bi4Ti3O12 nanostructured microspheres consisting of granular nanoparticles and nano-platelets. The precursor powder was prepared using a diethylene glycol mediated coprecipitation method. Tailoring of the morphology was achieved by changing the precursor quantity, sodium hydroxide concentration, and reaction time. The formation mechanism of the nanostructured microspheres probably involves aggregation, followed by dissolution and recrystallization. Bi3.25Pr0.75Ti2.97V0.03O12 (BPTV) and Bi3.25La0.75Ti3-xMxO12, (BLTMx, M = Mo, W, Nb, V, x = 0.0–0.12) ferroelectric nanoparticles and ceramics were synthesized using a modified citrate-gel method that has a crystallization temperature as low as 450 °C. The synthesized nanoparticles were spherical ranging from 30 to 100 nm. Except Nb5+, other donor cations were introduced using the corresponding oxides that have advantages in terms of high purity, low cost, and availability. The Bi3.25Pr0.75Ti2.97V0.03O12 ceramic is orthorhombic and its 2Pr and 2Ec values measured at 300 kV/cm were 35 μC/cm2 and 148 kV/cm respectively. The texture, microstructure, and ferroelectric properties of the prepared Bi3.25La0.75Ti3-xMxO12, (BLTMx, M = Mo, W, Nb, V, x = 0.0–0.12) ceramics depend on x. The maximum 2Pr (30–32 μC cm−2) was achieved at an optimum cosubstitution level (x = 0.025 for M6+, x = 0.03 for M5+). The high remanent polarization, low leakage current, and low polarization fatigue render the prepared ceramics promising for practical applications.

Nanomaterials because of their small size, may have special properties unlikely to be seen in ordinary types of materials. Nanomaterials like nanotubes,nanowires and nanoparticles are best studied at the nanoscale, vital but also problematic. In this thesis we use a transmission electron microscope (TEM)combined with a scanning tunneling microscope probe. This system allows TEM images to be captured and recorded into a movie together with recordedelectrical data for real time analysis. Using this method we found that the electrical conductivity of molybdenumbased nanowires Mo6S3I6 can be improved by current induced transformation. This might be a general method of improving nanowires which is of high valueif the wires are to be used in electrical circuits or field emission devices. The bending modulus for these nanowires were also determined, by an electromechanical resonance method, to 4.9 GPa. The sintering phase of silver nanoparticles, used in electrical conductive ink for printing electrical circuits, were studied by the in-situ TEM probing method. We observed that percolation path ways are formed and that the dispersive agent of the particles can be pyrolysed into a net of carbon with characteristics similar to graphite. We also developed a method for decorating nanowires and nanotubes with gold nanoparticles. Nanowire particle composites are often used in assembling more complex devices (electronic circuits) or for linking to organic molecules (biosensor applications) and existing particle decoration methods are either difficult or with low yield. By in situ TEM probing we found that carbon nanocages can be grown onto these gold nanoparticles. The size of the gold nanoparticles is controllable an thus the size of the nanocages. These nanocages may be used in medicine- or hydrogen storage-applications.
Nanomaterial har givits stort intresse under det senaste årtiondet, detta på grund av deras unika egenskaper som gör att de i många hänseenden överträffar traditionella material. Egenskaperna beror till största del på storlek och därför är det nödvändigt att studera dessa material på nanonivå, något som är problematiskt. För sådana studier krävs ett instrument med tillräckligt hög upplösning på nanonivå samt ett system med en prob som möjligör selektion och karakterisering utav individuella byggstenar. I denna avhandling används ett transmissionselektronmikroskop (TEM) tillsammans med ett sveptunnelmikroskop (STM) där det senare används som prob. Systemet medger studier på nanonivå och karakterisering av enskilda byggstenar under realtids avbildning (in situ). Metoden medger en bättre överblick och hanterbarhet vid nanomanipulering än vad till exempel atomkraftmikroskopi medger. Piezodrivna probar kan även användas i svepelektronmikroskop men dessa medger inte samma upplösning som transmissionselektronmikroskopet. Nanotrådar av Mo6S3I6 är ett alternativt material till kolnanorör och överträffar dessa i form av löslighet i båda organiska såväl som polära lösningsmedel. De är enkla att syntetisera men deras elektriska konduktivitet är låg. Mo6S3I6 nanotrådar studerades med in situ TEM probing. Vi fann att genom att driva en tillräckligt hög elektrisk ström genom nanotråden så resulterade detta i en omvandling till en solid metallisk molybden nanotråd med en konduktivitet nära värdet för bulkmaterialet. Resultat är intressant då nanotrådar kan användas i t.ex. fältemission, men resultatet visar också på att det kan vara en generell metod för att förbättra nanotrådar överlag. På dessa nanotrådar har även en elektromekanisk resonans studie utförts där böjmodulen för materialet bestämdes till 4.9 GPa. Med in situ-TEM-probing metoden har även silvernanobläck studerats under en sintringsprocess. Studien visade att vid sintringen så bildas perkulativa vägar genom bläckets silvernanopartiklar samt att vid hög sinteringstemperatur förkolnades det lösningsmedel som silvernanopartiklarna är lösta i. Förkolningen av lösningsmedlet resulterade i ett kolnät med liknande egenskaper som för grafit. Förståelse utav sinteringsprocessen är nödvändig eftersom vid tryckning av elektriskt ledande banor på papper används sintring för att höja ledningsförmågan. Genom att växa nanopartiklar på nanotrådar förändras deras egenskaper och tillämpningar. Existerande metoder är endera komplicerade eller ger dåligt ut- byte. Ett enkelt recept för att växa guldnanopartiklar på kolnanorör och Mo6S3I6 nanotrådar har därför tagits fram. Dessa kolnanorör och nanotrådar har sedan studerats med in-situ-TEM-probing metoden som visade att utanpå dessa guldnanopartiklar kan burar av kol skapas. Eftersom partiklarnas storlek kan kontrolleras kan även kolnanoburarnas storlek kontrolleras. Burarna har användningsområden t.ex. inom medicin och vid lagring av vätgas.
The thesis covers six scientific papers

As existing energy sources have been depleting at a fast pace, thermoelectric (TE) materials have received much attention in recent years because of their role in clean energy generation and conversion. Thermoelectric materials hold promise in terrestrial applications such as waste heat recovery. Bismuth selenide (Bi2Se3), lead telluride (PbTe), skutterudites CoSb3, and Bi-Sb alloys are among the widely investigated thermoelectric materials. Synthesis of above mentioned thermoelectric materials in nanostructured form and their characterization were investigated. Highly crystalline Bi2Se3, undoped and indium (In) doped PbTe, unfilled and ytterbium (Yb) filled CoSb3 nanomaterials were synthesized using hydrothermal/solvothermal technique and Ca-doped Bi-Sb alloy was synthesized using ball milling method. The mechanism of indium doping to the PbTe matrix was investigated using X-ray diffraction, laser-induced breakdown spectroscopy (LIBS) and a first principle calculation. It was found that indium doping, at a level below 2%, is substitution on Pb site. The effects of the amount of sodium borohydride (NaBH4) as the reducing agent and the annealing treatment on the phase transition of CoSb3 were investigated. It was found that a sufficient amount of NaBH4 along with the specific annealing condition was needed for the formation of pure phase CoSb3. Thermoelectric properties of Bi2Se3 and Ca-doped Bi85Sb15 were also investigated. A lower thermal conductivity and a higher Seebeck coefficient were achieved for a Bi2Se3 sample prepared in dimethyl formamide (DMF) at 200ºC for 24 h as compared to bulk Bi2Se3. The decrease in thermal conductivity can be attributed to the increased phonon scattering at the interfaces of the nanostructures and at the grain boundaries in the bulk nanocomposite. The increase in the Seebeck coefficient of Bi2Se3 nanostructures is likely the result of the quantum confinement of the carriers in nanostructures. The effect of calcium doping on Bi85Sb15 nanostructures were investigated. It was found that 2% calcium doped Bi-Sb alloy showed the best TE efficiency due to the enhanced power factor and reduced thermal conductivity.

Understanding the electrochemical stability or corrosion behaviour of metallic nanoparticles in aqueous environments is of central importance in the fields of catalysis, sensing and nano-electronics. The electrochemical stability of silver nanoparticles (AgNPs) was investigated as a function of applied potential, pH and particle size. The direct voltammetric measurements of the Ag oxidation potential indicate that the electrochemical stability of nanoparticles (NPs) is different from their bulk metal, suggesting that theoretically derived energy diagrams for a bulk material might not always be accurate for NPs. In order to understand interactions of nanomaterials (NMs) with biological systems, the cellular environment can be considered as an electrochemical cell, since metal ion release is a major pathway underlying their potential toxicity. NPs inhaled from the air into the deep lung first contact with the lung lining fluid where they have the potential to translocate into other organs like the brain, liver, spleen and heart via blood circulation. Here, this thesis specifically focuses on the impact of AgNMs on two major organs, the lung and brain. AgNMs as potential occupational and environmental hazards may raise health and safety concerns. For this reason, there is a need to assess the interaction of NMs with biological systems for early prediction of their cytotoxicity. The stability of AgNPs in dipalmitoylphosphatidylcholine (DPPC), the major component of lung surfactant, was investigated as a function of pH. TEM images revealed that the AgNPs were coated with a DPPC layer serving as a semi-permeable layer, improving their dispersion and delaying ions release in the lung. Furthermore, these studies suggested that size, stability and chemical composition of NP have to be taken into account in the evaluation of NP cytotoxicity. These observations have important implications for predicting the potential reactivity of AgNPs in the lung and the environment. In response to potential neurotoxicity, studies have shown that AgNPs can cross the blood brain barrier (BBB) via the systemic blood supply and then localise inside the brain, causing neurodegeneration, but much less is known about the distribution of AgNMs and their interaction with protein complexes inside the brain cells. Interaction of microglia with AgNMs, as well as their uptake, cytotoxicity and processing inside cells were investigated. The findings demonstrate that Ag2S formation acts as an ion trap for free Ag+, significantly limiting short term toxicity effects with important consequences for the neuro safety of AgNMs. In order to manipulate particular NPs features with favourable bio-availability and bio-distribution, not only NP uptake into cells, but also a fundamental understanding of the NPs-protein complex is necessary.

Coordination polymers have many attractive properties but the development of applications has been hampered by the challenges associated with their processing and the preparation of nanosized analogues. In this thesis, the synthesis and characterization of new coordination polymer nanomaterials with previously inaccessible morphologies and compositions are reported. Prussian blue analogues (PBAs) were investigated as model compounds. Mesostructured PBAs were fabricated via a ligand-assisted liquid-crystal templating approach. Molecular surfactants having a charged iron cyanide complex as hydrophilic head group and metal-coordinated hydrophobic tails were synthesized. In formamide, the metal-containing template formed liquid-crystalline phases that were crosslinked into PBA mesostructures with the addition of transition metals. PBAs with well-ordered lamellar, hexagonal and cubic structures were obtained with a wide range of compositions. The materials made of iron(II) and iron(III) exhibited mixed-valency and ferromagnetic interactions in the PBA framework. A synthetic approach to attach a PBA precursor onto polymer-based structure-directing agents was developed. A preformed macromolecular backbone was functionalized with ionic pendent groups that can coordinate iron cyanide complexes. Metal-containing homopolymers and block copolymers were synthesized. In organic solvents, the ionic block copolymers behaved as a block ionomer and self-assembled into stable wormlike and toroidal reverse micelles whose cores were metallated with the iron cyanide complex or used as an ion confinement region for different cyanometallate compounds to be crosslinked into PBA-type frameworks. The soluble PBA nanomaterials are stable in solution, assemble into arrays on surfaces and were used as precursors for metal oxide nanostructures. Soluble hollow polymer capsules with PBA inner-shells were fabricated via emulsion-induced assembly of the iron cyanide block ionomer. The metal-containing amphiphilic macromolecules stabilized nanosized water droplets dispersed in organic solvent by assembling at the water-oil interface. The hydrophilic iron cyanide inner-shells were crosslinked into PBAs with zinc ions. The hollow capsules have selective permeability, are tunable in size, organize into hexagonal arrays in the solid state and were used as nanocontainers to encapsulate molecular compounds. A rigid structure-directing ligand was incorporated into the network of a PBA under solvothermal conditions to engineer the connectivity of a coordination polymer. A crystalline triptycene-scaffolded copper PBA was obtained.