The increased deployment for renewable energy sources to mitigate the climate crisis has accelerated the need to develop efficient energy storage devices. Batteries are at the top of the list of the most in-demand devices in the current decade. Nowadays, research is in full swing to develop a battery that meets the needs of today’s renewable energy systems, which are intermittent by nature. Within the framework of improving the performance of batteries, there are parameters in the composition of the battery that play an important role in its performance: electrode materials, electrolytes, separators, and other factors. The key to battery development is the manufacture of electrode materials with optimal properties. Two-dimensional (2D) materials have led to advances in this field, firstly, using graphite as the anode in lithium-ion batteries (LIBs). However, when using the standard graphite as the anode for sodium-ion batteries (NIBs), the large ionic size and energetic instability of Na+ limit intercalation, resulting in a low storage capacity. Therefore, other 2D materials with large interlayer spacing need to be identified for use as electrodes. In this dissertation, our approach is focus on optimizing anode electrode materials by in situ conversion of 2D materials to obtain hybrid materials. These hybrids materials will synergistically improve the performance of LIBs and NIBs by combining the advantages of individual 2D materials. Starting with converted Ti0.87O2 nanosheets to the TiO2/TiS2 hybrid nanosheets. Then, taking advantage of the properties of MXene, we developed hybrid electrodes based on MXenes by converted V2CTx MXene into V2S3@C@V2S3 heterostructures. Finally, we boosted the redox kinetics and cycling stability of Mo2CTx MXene by using a laser scribing process to construct a multiple-scale Mo2CTx/Mo2C-carbon (LS-Mo2CTx) hybrid material.

Partículas e filmes híbridos de polímeros e compostos de amônio quaternário (CAQ) foram caracterizados quanto a propriedades físicas e atividade contra cepas de Pseudomonas aeruginosa ATCC 27853 e Staphylococcus aureus ATCC 25923. Partículas híbridas foram obtidas a partir de fragmentos de bicamada (BF) de brometo de dioctadecildimetilamônio (DODAB), adicionados consecutivamente de soluções de carboximetilcelulose (CMC) e cloreto de poli (dialildimetilamônio) (PDDA) e, a seguir, caracterizadas por espalhamento de luz dinâmico para determinação de distribuições de tamanho, diâmetro médio (Dz) e potencial-zeta (ζ). Filmes híbridos foram obtidos por revestimento rotacional de lamínulas de vidro a partir de uma solução clorofórmica de poli (metil metacrilato) (PMMA) e CAQ onde [PMMA] = 10 mg/mL e [CAQs] = 0,03 4 mM de DODAB, brometo de cetiltrimetilamônio (CTAB) ou brometo de tetrapropilamônio (TPAB). Molhabilidade dos filmes e difusibilidade dos CAQs nos filmes imersos em água foram avaliadas por determinação de ângulo de contato e de tensão superficial na interface ar-água, respectivamente. Atividade antimicrobiana foi avaliada por plaqueamento e contagem de viáveis, tanto para os filmes quanto para as partículas. Para os filmes, também foram determinados halos de inibição. Partículas de DODAB BF/ CMC/ PDDA exibiram Dz e ζ dependentes da concentração dos componentes. A 0,1 mM de DODAB, 0,1 mg/mL de CMC e 0,1 mg/mL de PDDA, foram obtidas partículas pequenas (Dz = 100 nm; ζ = 30 mV). Com 0,5 mM de DODAB, 0,5 mg/mL de CMC e 0,5 mg/mL de PDDA foram obtidas partículas grandes (Dz = 470 nm; ζ = 50 mV). Contra 107 UFC/mL, 1 - 2 µg/mL de PDDA, sozinho em solução ou em forma de partículas, matou 99 % das células de P. aeruginosa. O mesmo ocorreu contra S. aureus (107 UFC/mL) em 10 µg/mL de PDDA. A ação antimicrobiana mostrou-se dependente da quantidade de cargas positivas nas partículas e independente do tamanho da partícula. Filmes de PMMA/ CAQ apresentaram maior molhabilidade do que aqueles de PMMA puro. Filmes de PMMA/ DODAB e PMMA/ TPAB submersos em água não causaram alterações de tensão superficial na interface ar-água, indicando baixa difusibilidade destes CAQs a partir dos filmes. Filmes de PMMA/ CTAB submersos em água reduziram a tensão superficial até aproximadamente 60 mN/m, mostrando a difusibilidade do CTAB no filme e sua organização na interface ar-água. O efeito antimicrobiano dos filmes PMMA/ DODAB e PMMA/ CTAB foi dependente da concentração do CAQ utilizada no preparo do filme. Viabilidade celular de 0% contra 107 UFC/mL de ambas as bactérias ocorreu com 4 mM de DODAB ou, com 2 ou 0,2 mM de CTAB contra P. aeruginosa ou S. aureus, respectivamente. Filmes de PMMA/ TPAB não apresentaram atividade antimicrobiana. Com a emergência de micro-organismos resistentes aos antibióticos, os novos nanomateriais antimicrobianos híbridos de polímeros e compostos de amônio quaternário podem representar uma alternativa de fácil obtenção e baixo custo. / Hybrid particles and films from polymers and quaternary ammonium compounds (QAC) were characterized regarding its physical properties and antimicrobial activity against strains of Pseudomonas aeruginosa ATCC 27853 or Staphylococcus aureus ATCC 25923. Hybrid particles were obtained from dioctadecyldimethylammonium bromide (DODAB) bilayer fragments (BF), consecutively added of carboximethylcellulose (CMC) and poly (diallyldimethylammonium) chloride (PDDA) solutions, and then, characterized by dynamic light-scattering for determination of size distributions, z-average diameter (Dz) and zeta-potential (ζ). Hybrid films were obtained by spin-coating of a chloroformic solution of poly (methylmethacrylate) (PMMA) and QAC on glass coverslips at [PMMA] = 10 mg/mL and [QACs] = 0.03 -4 mM where QACs were DODAB, cetyltrimethylammonium bromide (CTAB) or tetrapropylammonium bromide (TPAB). Films wettability and QACs diffusibility in the films immersed in water were evaluated by determinations of contact angle and surface tension at air-water interface, respectively. Antimicrobial activity was evaluated by plating and CFU counting both for particles and films. For the hybrid films, width of inhibition zone was also determined. DODAB BF/ CMC/ PDDA particles exhibited Dz and ζ dependent on the concentrations of the components. At 0.1 mM DODAB, 0.1 mg/mL CMC, and 0.1 mg/mL PDDA, small cationic particles were obtained (Dz = 100 nm; ζ = 30 mV). At 0.5 mM DODAB, 0.5 mg/mL CMC and 0.5 mg/mL PDDA, large cationic particles were obtained (Dz = 470 nm; ζ = 50 mV). At 107 CFU/mL, cell viability of 1 % for P. aeruginosa was obtained for PDDA in solution or covering particles at 1 or 2 µg/mL PDDA, respectively. Against S. aureus (107 CFU/mL) at 10 µg/mL PDDA, a similar result was obtained. The antimicrobial effect was dependent on the amount of positive charge on particles and independent on particle size. The hybrid films of PMMA/ QAC showed higher wettability than those of pure PMMA. PMMA/ DODAB and PMMA/ TPAB hybrid films, submerged in water, did not cause changes in surface tension at the air-water interface, indicating low diffusibility for both DODAB and TPAB in hybrid films. Films of PMMA/ CTAB, submerged in water, reduced the surface tension to about 60 mN/m, showing that CTAB could diffuse from the film to the air-water interface and change its surface tension. The antimicrobial effect of PMMA/ DODAB and PMMA/ CTAB hybrid films was clearly dependent on the QAC concentration used to prepare the films. Cell viability of 0% for P. aeruginosa and S. aureus (107 CFU/mL) occurred at 4 mM DODAB, or 2 and 0.2 mM CTAB, respectively. Films of PMMA/ TPAB showed no antimicrobial activity. With the emergence of microorganisms resistant to antibiotics, the novel hybrid antimicrobial nanomaterials may become important since they are inexpensive and easy to obtain.

Partículas e filmes híbridos de polímeros e compostos de amônio quaternário (CAQ) foram caracterizados quanto a propriedades físicas e atividade contra cepas de Pseudomonas aeruginosa ATCC 27853 e Staphylococcus aureus ATCC 25923. Partículas híbridas foram obtidas a partir de fragmentos de bicamada (BF) de brometo de dioctadecildimetilamônio (DODAB), adicionados consecutivamente de soluções de carboximetilcelulose (CMC) e cloreto de poli (dialildimetilamônio) (PDDA) e, a seguir, caracterizadas por espalhamento de luz dinâmico para determinação de distribuições de tamanho, diâmetro médio (Dz) e potencial-zeta (ζ). Filmes híbridos foram obtidos por revestimento rotacional de lamínulas de vidro a partir de uma solução clorofórmica de poli (metil metacrilato) (PMMA) e CAQ onde [PMMA] = 10 mg/mL e [CAQs] = 0,03 4 mM de DODAB, brometo de cetiltrimetilamônio (CTAB) ou brometo de tetrapropilamônio (TPAB). Molhabilidade dos filmes e difusibilidade dos CAQs nos filmes imersos em água foram avaliadas por determinação de ângulo de contato e de tensão superficial na interface ar-água, respectivamente. Atividade antimicrobiana foi avaliada por plaqueamento e contagem de viáveis, tanto para os filmes quanto para as partículas. Para os filmes, também foram determinados halos de inibição. Partículas de DODAB BF/ CMC/ PDDA exibiram Dz e ζ dependentes da concentração dos componentes. A 0,1 mM de DODAB, 0,1 mg/mL de CMC e 0,1 mg/mL de PDDA, foram obtidas partículas pequenas (Dz = 100 nm; ζ = 30 mV). Com 0,5 mM de DODAB, 0,5 mg/mL de CMC e 0,5 mg/mL de PDDA foram obtidas partículas grandes (Dz = 470 nm; ζ = 50 mV). Contra 107 UFC/mL, 1 - 2 µg/mL de PDDA, sozinho em solução ou em forma de partículas, matou 99 % das células de P. aeruginosa. O mesmo ocorreu contra S. aureus (107 UFC/mL) em 10 µg/mL de PDDA. A ação antimicrobiana mostrou-se dependente da quantidade de cargas positivas nas partículas e independente do tamanho da partícula. Filmes de PMMA/ CAQ apresentaram maior molhabilidade do que aqueles de PMMA puro. Filmes de PMMA/ DODAB e PMMA/ TPAB submersos em água não causaram alterações de tensão superficial na interface ar-água, indicando baixa difusibilidade destes CAQs a partir dos filmes. Filmes de PMMA/ CTAB submersos em água reduziram a tensão superficial até aproximadamente 60 mN/m, mostrando a difusibilidade do CTAB no filme e sua organização na interface ar-água. O efeito antimicrobiano dos filmes PMMA/ DODAB e PMMA/ CTAB foi dependente da concentração do CAQ utilizada no preparo do filme. Viabilidade celular de 0% contra 107 UFC/mL de ambas as bactérias ocorreu com 4 mM de DODAB ou, com 2 ou 0,2 mM de CTAB contra P. aeruginosa ou S. aureus, respectivamente. Filmes de PMMA/ TPAB não apresentaram atividade antimicrobiana. Com a emergência de micro-organismos resistentes aos antibióticos, os novos nanomateriais antimicrobianos híbridos de polímeros e compostos de amônio quaternário podem representar uma alternativa de fácil obtenção e baixo custo. / Hybrid particles and films from polymers and quaternary ammonium compounds (QAC) were characterized regarding its physical properties and antimicrobial activity against strains of Pseudomonas aeruginosa ATCC 27853 or Staphylococcus aureus ATCC 25923. Hybrid particles were obtained from dioctadecyldimethylammonium bromide (DODAB) bilayer fragments (BF), consecutively added of carboximethylcellulose (CMC) and poly (diallyldimethylammonium) chloride (PDDA) solutions, and then, characterized by dynamic light-scattering for determination of size distributions, z-average diameter (Dz) and zeta-potential (ζ). Hybrid films were obtained by spin-coating of a chloroformic solution of poly (methylmethacrylate) (PMMA) and QAC on glass coverslips at [PMMA] = 10 mg/mL and [QACs] = 0.03 -4 mM where QACs were DODAB, cetyltrimethylammonium bromide (CTAB) or tetrapropylammonium bromide (TPAB). Films wettability and QACs diffusibility in the films immersed in water were evaluated by determinations of contact angle and surface tension at air-water interface, respectively. Antimicrobial activity was evaluated by plating and CFU counting both for particles and films. For the hybrid films, width of inhibition zone was also determined. DODAB BF/ CMC/ PDDA particles exhibited Dz and ζ dependent on the concentrations of the components. At 0.1 mM DODAB, 0.1 mg/mL CMC, and 0.1 mg/mL PDDA, small cationic particles were obtained (Dz = 100 nm; ζ = 30 mV). At 0.5 mM DODAB, 0.5 mg/mL CMC and 0.5 mg/mL PDDA, large cationic particles were obtained (Dz = 470 nm; ζ = 50 mV). At 107 CFU/mL, cell viability of 1 % for P. aeruginosa was obtained for PDDA in solution or covering particles at 1 or 2 µg/mL PDDA, respectively. Against S. aureus (107 CFU/mL) at 10 µg/mL PDDA, a similar result was obtained. The antimicrobial effect was dependent on the amount of positive charge on particles and independent on particle size. The hybrid films of PMMA/ QAC showed higher wettability than those of pure PMMA. PMMA/ DODAB and PMMA/ TPAB hybrid films, submerged in water, did not cause changes in surface tension at the air-water interface, indicating low diffusibility for both DODAB and TPAB in hybrid films. Films of PMMA/ CTAB, submerged in water, reduced the surface tension to about 60 mN/m, showing that CTAB could diffuse from the film to the air-water interface and change its surface tension. The antimicrobial effect of PMMA/ DODAB and PMMA/ CTAB hybrid films was clearly dependent on the QAC concentration used to prepare the films. Cell viability of 0% for P. aeruginosa and S. aureus (107 CFU/mL) occurred at 4 mM DODAB, or 2 and 0.2 mM CTAB, respectively. Films of PMMA/ TPAB showed no antimicrobial activity. With the emergence of microorganisms resistant to antibiotics, the novel hybrid antimicrobial nanomaterials may become important since they are inexpensive and easy to obtain.

La presente tesis doctoral titulada ¿Supramolecular and heterosupramolecular chemistry in controlled release and molecular recognition processes¿ está centrada en los dos aspectos principales de la química supramolecular que han experimentado un gran auge en los últimos años: el reconocimiento molecular y los procesos de liberación controlada. En particular la primera parte de la tesis se focaliza en el diseño y síntesis de moléculas orgánicas que pueden ser empleados cómo sensores para especies aniónicas y neutras. El paradigma seleccionado para los procesos de reconocimiento molecular fue la aproximación del dosimetro químico. Esta aproximación presenta ventajas con respecto a los otros dos métodos de determinación de aniones (desplazamiento y unidad coordinanteunidad indicadora), cómo, por ejemplo, la posibilidad de determinar los analitos en disolución acuosa. Así se sintetizaron dos sensores selectivos, uno para el anión fluoruro (F-) y el otro para glutatión (GSH). El sensor selectivo para la determinación de F- está basado en un colorante azoico funcionalizado, en su ¿OH fenólico, cómo silileter. Esta molécula presenta una banda de absroción muy intensa centrada a 350 nm que, después de la adición de F- , sufre un efecto hipocrómico significativo y un desplazamiento batocromico ligero (de ca. 10 nm), mientras aparece una nueva banda a 470 nm, determinando un cambio de incoloro a amarillorojo. Para obtener un sensor selectivo para GSH se sintetizó una sonda químico basado en una sal de 2,6-difenilpirilio. Sucesivamente se preparó una disolución de este compuesto en agua/CTAB, que se caracterizaba por un intenso color azul. En este caso, la adición de GSH produce una disminución significativa de la banda del visible, acompañada por la consecuente decoloración. Además la adicón de GSH induce la aparición de Resumen vi una intensa banda de emisión centrada a 485 nm (después de la irradiación a 350 nm). La segunda parte de esta tesis doctoral se basa en el diseño y síntesis de nuevos sistemas híbridos orgánicos-inorgánicos para procesos de liberación controlada en ambiente celular. Estos materiales híbridos se componen en general, de dos unidades: una matriz inorgánica mesoporosa de base silícea, capaz de almacenar moléculas orgánicas (colorantes, farmacos...) y un compuesto orgánico anclado covalentemente a la superficie externa del soporte inorgánico mesoporoso, que actúa cómo puerta molecular. La aplicación de un estímulo externo puede modificar la conformación de la puerta molecular permitiendo o bien impidiendo la difusión de la carga almacenada en los mesoporos hacía el exterior (disolución o citoplasma). El primer sistema sintetizado y estudiado se compone de una matriz inorgánica mesoporosa (MCM-41), cargada con el colorante Ru(bipy)3 2+ y funcionalizada en la superficie con un oligoetilen glicol mediante un grupo ester. La adición de la enzima esterasa determinaba la hidrólisis del grupo ester y la consecuente reducción del tamaño de la puerta molecular, acompañada por la liberación del colorante previamente cargado. Otro sistema de liberación preparado consiste en el uso de la misma matriz MCM-41 nanoscópica y el mismo colorante Ru(bipy)3 2+, pero se funcionalizó la superficie con una puerta molecular fotolabil. La irradiación en el maximo de absorción de la puerta molecular inducía la fotodegradación de la misma y la consecuente liberación del colorante. Un tercer ejemplo de sistema de liberación consiste en una puerta molecular caracterizada por la presencia de dos grupos funcionales hidrolizables con enzimas diferentes: grupos urea y amida. vii El material final, caracterizado por la presencia del mismo esqueleto inorgánico, y cargado con Ru(bipy)3 2+, era capaz de liberar selectivamente cantidades distintas de colorante, dependiendo del enzima empleado. Así se podían conseguir dos tipos de perfiles de liberación: uno muy rápido y poco intenso y otro más lento pero mucho mas intenso. Finalmente se sintetizó un material híbrido siempre basado en la misma matriz de MCM- 41, cargado con rodamina-B y funcionalizado en la superficie con galactooligosacáridos. Con este material se podía conseguir una liberación controlada del colorante selectivamente en células senescentes, debido a que estas sobreexpresan el enzima ß-galactosidasa que es capaz de hidrolizar los galactooligosacáridos. / Agostini, A. (2013). Supramolecular and heterosupramolecar chemistry in controlled release and molecular recognition processes [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/29397 / TESIS

L’ingénierie de nanomatériaux hybrides semi-conducteurs/plasmoniques représente une technologie durable en raison de l’efficacité parfaite du couplage pour améliorer, rénover et enrichir les propriétés des composants intégrés. Ce couplage a pour résultat la variation des propriétés fonctionnelles du système, grâce auquel les plasmons de surface générés par les métaux peuvent améliorer la séparation des charges, l’absorption de la lumière et la luminescence du semi-conducteur. Ce phénomène permet de fortes interactions avec d'autres éléments photoniques tels que les émetteurs quantiques. Ces fonctionnalités aux multiples facettes découlent de l'interaction synergique exciton-plasmon entre les unités liées. Ainsi, les nanomatériaux hybrides conviennent à diverses applications, notamment : conversion de l'énergie solaire, dispositifs optoélectroniques, diodes électroluminescentes (LED), photocatalyse, détection biomédicale, etc. Les nanostructures Au-ZnO suscitent un intérêt croissant dans ces applications où le couplage de ZnO à de nanoparticules d’or (GNPs) favorise la réponse du système dans le domaine du visible grâce à leur résonance plasmon de surface (SPR). En fonction de la taille de deux nanomatériaux, de la distance qui les sépare et leurs rapports massiques dans un échantillon, les propriétés des particules hybrides peuvent varier. Dans ce contexte, nous nous sommes concentrés sur la construction de nano-cristaux (NCs) de ZnO purs de dimensions contrôlables, puis incorporés dans des solutions de GNPs par une simple voie chimique. Ce travail est divisé en deux parties : la première consiste à effectuer une synthèse de nanocristaux de ZnO (NCs) purs présentant d'excellentes propriétés de photoluminescence dans l’UV. Ceci a été réalisé par une synthèse à basse température, aboutissant à des structures rugueuses et amorphes. La synthèse a été suivie d'un traitement post-thermique afin de cristalliser les nanoparticules obtenues. Une étude structurale et optique poussée a été établie à la suite de la synthèse (SEM, TEM, DRX, photoluminescence). Les activités photocatalytiques des ZnO NCs ont été étudiées en mesurant leur capacité à dégrader le bleu de méthylène (MB). De plus, la relation entre les structures en ZnO, la luminescence et les propriétés photocatalytiques a été explorée en détail. Dans la deuxième étape, les ZnO NCs obtenus ont été couplés ajoutés à des nanoparticules d'or de tailles et fractions volumiques variables. Le rôle effectif des GNPs concernant leur morphologie, leur contenu et leur effet SPR sur la photoémission des nanostructures de ZnO est souligné par le transfert de charge et / ou d'énergie entre les constituants du système hybride. De plus, l’activité photocatalytique du système hybride a été examinée. Comme débouché et perspective de ce travail de thèse, l'intégration des ZnO NC dans une couche nanoporeuse de polymère (PMMA) a été réalisée et caractérisée afin d'obtenir un substrat de large surface à base de ZnO. Les ZnO NCs assemblés dans du PMMA pourraient être des substrats prometteurs en tant que catalyseurs pour la croissance de nanofils de ZnO, de nanomatériaux métalliques et de matériaux hybrides. / Hybrid heterojunctions composed of semiconductors and metallic nanostructures have perceived as a sustainable technology, due to their perfect effectiveness in improving, renovating, and enriching the properties of the integrated components. The cooperative coupling results in the variation of the system’s functional properties, by which the metal-generated surface plasmon resonance can enhance the charge separation, light absorption, as well as luminescence of the semiconductor. This phenomenon enables strong interactions with other photonic elements such as quantum emitters. These multifaceted functionalities arise from the synergic exciton-plasmon interaction between the linked units. Thereby, hybrid systems become suitable for various applications including: solar energy conversion, optoelectronic devices, light-emitting diodes (LED), photocatalysis, biomedical sensing, etc. Au-ZnO nanostructures have received growing interest in these applications, where the deposition of gold nanoparticles (GNPs) promotes the system’s response towards the visible region of the light spectrum through their surface plasmon resonance (SPR). Based on a specific size and purity of ZnO nanostructures, as well as the GNPs, and a definite inter-distance between the nanoparticles, the properties of the ZnO nanostructures are varied, especially the photoemission and photocatalytic ones. In this context, we have focused on the construction of size-tunable ZnO nanocrystals (NCs), then incorporated into GNPs solutions using a simple chemical way. This work is divided into two parts: the first is to perform synthesis of pure ZnO NCs having excellent UV photoluminescence. This was achieved through a low-temperature aqueous synthesis, resulting in rough and amorphous structures. The synthesis was followed by a post-thermal treatment in order to crystallize the obtained particles. The synthesis was followed by structural and optical studies (SEM, TEM, XRD, photoluminescence). The photocatalytic activities of ZnO NCs were studied through tailoring their ability to degrade the methylene blue (MB) dye. In addition, the relationship between ZnO structures, luminescence, and photocatalytic properties was explored in details. In the second step, the obtained ZnO NCs were added to gold nanoparticles of various sizes and volume fractions. The effective role of GNPs concerning their size, amount, and their capping molecule on the photoemission of the ZnO nanostructures was emphasized through the charge and/or energy transfer between the constituents in the hybrid system. In the same way, the systems photocatalytic activities were examined after coupling ZnO to GNPs. Further advancement in the integration of the ZnO NCs into PMMA polymer layers was featured in order to obtain large area template of homogenous ZnO properties. The PMMA-assembled ZnO nanoparticles could be promising substrates as catalysts for growing ZnO nanowires, metallic nanoparticles and hybrid nanomaterials.

Des couches fonctionnelles hybrides organiques/inorganiques ont été générées à une interface solide/liquide à l’aide d’une nouvelle technique de fabrication ascendante (bottomup) dénommée Croissance de Couche à partir d’une Surface (Surface Grown Layers - SgL)grâce à une modulation très fine de l’interaction électrostatique entre nano-objets decharges opposés en fonction de la force ionique de la dispersion aqueuse. Différents nanoparticules/tubes à la fois cationiques et anioniques et très stables vis-à-vis d’un environnement fortement salin ont été développés. La complexation électrostatique entre ces nanomatériaux a été étudiée en solution et près d’une interface au travers du concept de “transition de dessalage”. Dans un deuxième temps la croissance de couches hybrides à partird’un substrat a été étudiée en comparant l’approche SgL et la méthode classique d’adsorption séquentielle couche par couche (Layer by layer - LbL). Des expériences préliminaires ont montré le potentiel de cette approche dans le développement de substrats fonctionnels. / In this manuscript, one-step bottom-up fabrication of “smart organic-inorganic hybridfunctional layers” at a liquid/solid interface were fabricated via a novel surfacefunctionalization pathway termed as “Surface Grown Hybrid Functional Layers” or SgLthrough fine tuning of electrostatic interaction between “highly stable” and oppositelycharged nanomaterials as a function of ionic strength of the dispersion. Cationic and anionicnanomaterials based on different hybrid nanoparticles/nanotubes that are very stable towardshigh saline environment have been formulated. The electrostatic complexation between theseoppositely charged nanomaterials has been studied in bulk and at an interface through theconcept of “desalting transition” pathway. In a second step, the growth of functional hybridlayers directly from a substrate via the novel SgL approach was then compared with theconventional Layer-by-Layer approach (LbL). Finally the preliminary experiments haveshown the potential applications of generated functional surfaces.

Le fort engouement pour les nanostructures luminescentes provient de leurs comportements émissifs originaux et de leur potentiel comme briques élémentaires pour de futurs dispositifs photoniques et optoélectroniques. Dans cette thèse, nous nous sommes intéressés au contrôle de la couleur d’émission de nano-systèmes 1D organiques composés de deux types de luminophores. Dans une première partie, une famille peu connue de luminophores nanométriques a été étudiée: les clusters octaédriques de molybdène. Leur comportement photophysique et l’ensemble des fréquences des modes de vibration de l’entité Mo6Br14 ont été déterminés. Les spécificités de ces clusters ont été exploitées au sein de nanofils.Un premier type de nanofil coaxial synthétisé par méthode template a été conçu afin de séparer les deux types de luminophores. Les clusters (dans une matrice de PMMA) et le PPV ont été sélectionnés comme émetteurs rouge et vert respectivement, pour avoir une séparation spectrale. Le contrôle de la couleur sans transfert de charge ou d’énergie entre les deux luminophores a été validé par l’étude du comportement de photoluminescence stationnaire et résolue en temps, en accord avec un modèle phénoménologique. A l’opposé, des nanofils exploitant deux polymères conjugués fluorescents (PFO bleu, F8T2 vert) comme système donneur-accepteur ont été élaborés. Leur mélange ou leur séparation en géométrie cœur-gaine a permis d’explorer une nouvelle voie pour moduler les comportements excitoniques. Ces résultats montrent la versatilité des nanofils à base de polymère pour contrôler à l’échelle nanométrique les comportements d’émission de systèmes multi-luminophores. / Luminescent organic nanostructures are of great importance as building blocks in future miniaturized photonic and optoelectronic devices because these systems rely upon the ability to tune and get new optical characteristics. One-dimensional luminescent nanostructures are new and promising systems with complex morphologies now available. In this work, we particularly investigated the control and the tuning of the emitted color of two-luminophore based nanowires. In a first part, an unfamiliar family of luminophore has been investigated: the octahedral molybdenum clusters. The vibrational modes frequencies of Mo6Br14 cluster were fully determined, as well as their photophysical properties. The unique features of these clusters were exploited into nanowires.Then, using a template method, we designed coaxial nanowires allowing the spatial separation of the two luminophores. The transition metal clusters in a PMMA matrix and PPV were selected as red and green emitters, respectively, to achieve the spectral separation. Remarkably, it was found from time-resolved photoluminescence study and confirmed by a phenomenological model that any charge or energy transfer is involved in this system.Alternatively, coaxial and blend designs were used to investigate and possibly tune energy/charge transfers involved in the donor-acceptor behavior of two conjugated polymers: PFO (blue emitter) and F8T2 (green emitter). These results demonstrate the great versatility of polymer-based nanowires to finely control at the nanoscale the emission features of multi-luminophore materials.

Nous avons étudié les comportements dynamiques d'auto-assemblage des tensioactifs cationiques non-chiral en présence du contre-anion chiral.Lorsque le nucléotide anionique chiral est ajouté à des vésicules cationiques, la transition morphologique se produit et transforme in situ des vésicules sphériques en hélices micrométriques.D'autres types de Gemini tensioactifs cationiques forment des rubans nanométriques hélicoïdaux, en présence de tartrate contre-anions. La forme et l'hélicité de ces rubans peuvent être contrôlés in situ par la variation de l'excès énantiomérique.En outre, les nanohélices organiques peuvent être transcrite en nanohélices 3D de silice via une polycondensation sol-gel.Ces nanohélices de silice fonctionnalisées avec des groupes aminés peuvent interagir fortement avec des nanoparticules d'or (GNPs; 1 ~ 20 nm). Le réseau 3D de -nanohélices GNPs/silice sont potentiellement utilisables pour des applications de capteurs basée sur les SERS comme ceux chimiques et biologiques ultra-sensibles en phase liquide. / We have studied the dynamic self-assembly behaviors of non-chiral cationic surfactants in thepresence of chiral counter-anion.When the chiral anionic nucleotides are added to cationic vesicles, morphology transitionoccurs and spherical vesicles transform in situ to micrometric helices.Other types of cationic surfactant, gemini surfactants form nanometric helical ribbons in thepresence of tartrate counter-anion. The shape and helicity of these self-assembled structurescan be controlled in situ by the variation of enantiomeric excess.In both cases, they form gels in water by creating extended networks of nanometric tomicrometric chiral fibers.Additionally, the organic nanohelices can be transcribed to 3D silica nanostructures via solgelpolycondensation. These silica nanohelices functionalized with amino group can interactstrongly with gold nanoparticles (1 ~ 20 nm). The 3D network of GNPs/silica-nanohelices canpotentially be used for SERS-based sensing applications such as ultra-sensitive chemical andbiological sensors in liquid phase.

Le remplissage des nanotubes de carbone (NTC) est considéré comme une approche relativement simple permettant de synthétiser des nanocristaux du fait de l'effet de confinement 1D imposé par la cavité centrale des NTC, qui peut être seulement de l'ordre du nanomètre ou moins, notamment dans le cas des NTC monoparoi et en particulier des NTC biparois (DWCNT) sur lesquels nous avons concentré nos efforts. De tels nanocristaux devraient avoir des propriétés physiques (électriques, magnétiques) différentes de celles de leurs équivalents à l'état massif du fait de la modification de la coordinence des atomes ou des ions les composant. Parmi les différentes méthodes existantes pour le remplissage des NTC, (in situ pendant la synthèse, a posteriori à partir de solutions), la méthode faisant intervenir des matériaux fondus est la plus populaire pour le remplissage par des matériaux inorganiques. Elle permet en effet d'atteindre des taux de remplissage raisonnablement élevés et demeure assez simple à mettre en œuvre. Cependant, elle fait preuve d'un certain nombre de limitations (techniques) qui posent problème dans le cas de matériaux à haut point de fusion (typiquement > 1000°C), dont la réactivité avec le carbone à haute température pourrait être gênante (carboréduction des oxydes par exemples), ou encore dont la faible mouillabilité vis-à-vis du carbone à l'état fondu est rédhibitoire (métaux par exemple). Il est possible de palier à cette difficulté en procédant par étapes successives et en remplissant d'abord les NTC avec un précurseur puis d'utiliser la cavité interne des NTC comme des nanoréacteurs afin de procéder dans un second temps à une transformation in situ. Dans ces travaux, nous avons étudié (1) le remplissage de DWCNT avec de l'iode ainsi qu'avec différents iodures métalliques en mettant en œuvre essentiellement la méthode des sels fondus. Nous avons étudié en détails l'influence des paramètres physico-chimiques du matériau de remplissage (réactivité chimique sous la forme en particulier du potentiel rédox du couple iodure métallique / métal, mais aussi viscosité, tension de surface, pression de vapeur saturante en milieu fondu) mais aussi du NTC (texture cylindrique ou "en arrêtes de poisson", diamètre, nombre de parois) sur le taux de remplissage. (2) Nous avons étudié en détail un certain nombre de structures inhabituelles de nanomatériaux confinés dans les DWCNT, en faisant appel à la modélisation structurale et à la simulation d'images de microscopie électronique sur la base de ces modèles pour guider notre analyse. (3) Nous avons enfin étudié différentes réactions in situ dans les DWCNT telles que la sulfuration, la réduction sous hydrogène ou encore la fluoration afin de synthétiser des nanocristaux originaux et de les caractériser en détails à l'aide d'outils tels que par exemple le MET Haute Résolution et la spectroscopie de perte d'énergie des électrons (EELS). / Filling carbon nanotubes (CNTs) has been considered as an easy approach to synthesize various nanocrystals since the inserted materials are forced to adopt a nearly one-dimensional morphology arising from their very high aspect ratio, especially in the case of single-walled CNTs (SWCNTs) or double-walled CNTs (DWCNTs). Nanocrystals/nanowires of transition metals, especially those with very narrow diameters, are predicted to exhibit peculiar magnetic property differing from the bulk metals. Filling CNTs provides a possible way for the synthesis of such metal nanocrystals/nanowires. There are several methods for filling CNTs including the in situ method, gas phase method, molten phase method, solution method, etc. Among them, molten phase has been very popular for filling various types of nanotubes due to the possibility to reach high filling rates, simplicity and versatility. However, for materials with high melting point such as metals, it is difficult to insert them into CNTs directly. To solve this problem, we also took advantage of the inner cavity of CNTs which not only templates the growth but also acts as a nanoreactor in order to perform chemical reactions. The insertion of materials with high melting point is typically achieved by first filling CNTs with a precursor, and then transforming the precursor into the desired 1D nanostructure by post-treatments. In this thesis, (i) filling DWCNTs with iodine and various halides via the molten phase method was performed and the influence of the relevant physical and chemical properties of the halides on the filling rate was investigated. The role of the redox potential as a main parameter driving the filling efficiency is pointed out, and explained; (ii) peculiar structures of the nanocrystals confined within DWCNTs were imaged by transmission electron microscopy (TEM) and corresponding modeling of the observed crystal nanostructures and related TEM images were proposed; (iii) different in situ transformations on the iodide-filled DWCNTs were attempted and the chemical composition of the encapsulated 1D nanocrystals before and after post-filling treatments was systematically identified by means of electron energy loss spectroscopy (EELS).

Ce travail de thèse a porté sur l’élaboration de nanomatériaux hybrides de type nano-câbles fonctionnels, composés de polymères covalents et de molécules auto-assemblées. L’approche «bottom-up» adoptée repose sur des processus uniquement physiques, à savoir la nucléation hétérogène, la cristallisation et la gélification thermo réversible. Deux systèmes hybrides ont été élaborés et étudiés: le premier est composé de molécules de tetra-2-éthylhexanoate de bicuivre (CuS8) auto-assemblées en filaments, lesquels sont encapsulés au sein des fibrilles de polystyrène isotactique (iPS). Nous avons montré au travers de différentes études (DSC, DNPA,SQUID, EXAFS et IR-TF) que leur encapsulation permet non seulement de les stabiliser mais également de modifier leur comportement antiferromagnétique. Le deuxième système a consisté à des fibrilles de poly(alkylthiophène)s (P3AT), emmaillotées au moyen de molécules diamides (BHPB-10) capables de s'assembler en nanotubes. En plus des études de la morphologie et de la structuration par TEM et UV-Vis,nous avons étudié les propriétés de conductivité du système hybride P3BT/BHPB-10 en C-AFM. Nous avons montré qu’il est effectivement possible de réaliser des nano-câbles semi-conducteur gainés. / This thesis deals with new hybrid nanomaterials of functional nanocable-like structures, consisting of covalent polymers and self-assembled molecules. The «bottom-up» approach adopted for the elaboration is based only on physical processes such as heterogeneous nucleation, crystallization and thermoreversible gelation. This original approach allowed us to easily prepare two functional nanocables: the first consisted of bicopper tetra-2-ethylhexanoate (CuS8) molecules self-assembled on filaments which are encapsulated within isotactic polystyrene (iPS) fibrils. We proved throughout different studies (DSC, SANS, SQUID, EXAFS and FT-IR) that the encapsulation allows one to get stable filaments, and particularly to modify their antiferromagnetic behavior as well. The second system constituted of poly(alkylthiophene)s fibrilles (P3AT), sheathed by diamides molecules (BHPB-10) self-assembled on nanotubes. Besides the morphological and the structuration studies (TEM and UV-Vis), we investigated the conductivity of the hybrid system P3BT/BHPB-10 by C-AFM. Results showed the possibility to obtain sheathed semi-conducting nano-cables.