Academic literature on the topic 'Nanorod d'oro'

Cette thèse comporte trois parties principales : la première concerne la synthèse et la fonctionnalisation des nanoparticules (NPs) d’or de forme sphérique et cylindrique. Les NPs d’or sont obtenues par réduction d’un sel métallique. En faisant varier certains paramètres de synthèse tels que la concentration en sels et/ou la concentration en réducteur, on peut facilement ajuster la taille de NPs sphériques. Bien qu’il existe diverses méthodes permettant de préparer des NPs cylindriques, il subsiste un problème de reproductibilité basée sur la pureté des produits de synthèse. Les différentes analyses de CTAB nous ont permis de proposer des solutions à ce problème. La fonctionnalisation de la surface des NPs d’or permet d’apporter à ces dernières de nouvelles propriétés tout en conservant leurs propriétés intrinsèques. Le but de cette fonctionnalisation est de modifier la surface des NPs en fonction des applications visées. Nous présentons ainsi différentes études de fonctionnalisation par des polyélectrolytes (PEI et PSS), des couches oxydes de SiO2, et de TiO2 et par le TDBC. La réponse optique des NPs d’or étant sensible à l’indice de réfraction du milieu environnant, il est possible de suivre et de quantifier cette fonctionnalisation par spectroscopie d’absorption. Dans une seconde partie, nous avons développé une voie de synthèse simple permettant de préparer le cœur coquille Au@TDBC sans ajout supplémentaire de sels ou de bases et à température ambiante. Etant donné qu’il est possible de moduler la taille des particules, l’optimisation du couplage fort entre les transitions électroniques du TDBC et les modes plasmon de résonances des Nps d’Au a été obtenu correspondant à une énergie de Rabi de 220 meV valeur qui n’a pas encore été obtenue avec un tel système. Dans une troisième partie, nous avons développé une nouvelle approche basée sur la méthode de Stöber pour fonctionnaliser les NPs avec des couches d’oxyde de SiO2 et de TiO2. L’utilisation des systèmes Au@TiO2 est une perspective intéressante en photocatalyse car le contact entre le métal et le semi-conducteur devrait entrainer une nette augmentation de l’efficacité photocatalytique. En effet, le métal agit comme un réservoir de photoélectrons améliorant le transfert de charges interfaciales tout en retardant la recombinaison des paires électrons-trous photo excités du semi-conducteur
This thesis has three main parts: the first part relates to the synthesis and the functionalization of spherical gold nanoparticles (NPs) and nanorods. Gold NPs are obtained by chemical reduction of gold salt. By varying some synthesis parameters such as gold salt concentration and or reducing agent concentration, we can easily adjust the size of gold NPs. Different methods can be used to prepare gold nanorods, but there is a problem of reproducibility. This problem is based on the purity of products used to prepare gold nanorods. Different analysis of CTAB allowed us to propose solutions to this problem. Functionalization brings to gold NPs new properties. The aim of the functionalization is to modify the surface of gold NPs based on the intended applications. We present various functionalization of Au NPs by polyelectrolytes (PEI and PSS), oxides (SiO2 and TiO2) and TDBC. The optical response of Au NPs is sensitive to the refractive indexe of the surrounding medium, it is then possible to monitor and quantify this functionalization by absorption spectroscopy. In the second part of this work, we have developed a simple synthetic route for preparing Au@TDBC core shell without additional salts or bases at room temperature. Since it is possible to vary the particle size, optimization of the strong coupling between the electronic transitions of TDBC and the resonance plasmon of Au Nps obtained correspond to Rabi energy of 220 meV value which has not yet been achieved with such a system. In the third part, we have developed a new approach based on the Stöber method to functionalize the NPs with an oxide layer of SiO2 and TiO2. The use of Au@TiO2 core shell system is an interesting perspective in photocatalysis because the contact between metal and semiconductor should cause a marked increase in the photocatalytic efficiency. Indeed, the metal acts as a reservoir of photoelectrons improving the interfacial charge transfer while retarding the recombination of electron-hole pair of the semiconductor

De par leurs nombreuses applications potentielles, de nombreux efforts de recherche ontété poursuivis dans le domaine de la synthèse de nanoparticules. Cependant le mécanisme àl'origine des formes anisotropes de nanoparticules d'or, pour une taille et une structure biendéfinies, reste encore un sujet controverse.L'objectif général de cette thèse est de comprendre l'origine de cette anisotropie, lors dela formation de nanoparticules d'or, en particulier sous la forme de nano-bâtonnets d'or, enphase liquide. Parmi les nombreux procédés de synthèse existants, la "synthèse de particulesanisotropes par croissance à partir de germes" a été retenu, car il permet un contrôle précis dela taille et de la structure des nanoparticules. Lors de la synthèse de nanoparticules, les germesjouent un rôle de précurseur et permettent ainsi de maitriser la structure cristalline desnanoparticules finales. Si le rôle crucial des germes a déjà pu être étudié par différentsgroupes de recherche, une étude systématique sur la genèse de l'anisotropie par rapport à lataille et la structure initale des germes restait à réaliser. Ce travail a ainsi pour objectif derépondrre aux deux questions :i. Comment contrôler la structure cristalline et de la taille des germes?ii. Quelles sont les influences de la taille des germes et de leur structure sur la cinétique dela croissance?
Between the ongoing research on various type of nanomaterials to tune the particle sizeand crystal design in nanoscale for their potential applications, anisotropic gold nanoparticleshas attracted the most intention not only because of their divine color but also their enhancedcatalytic activities, optical properties and electrical conductivities. Event though, many effortshave been already made in the field of synthesis of anisotropic gold nanoparticles, withdefined sizes and structures, growth mechanism of many unique anisotropic shapes is still acontroversial subject.Overall objective of this thesis is to understand the origin of anisotropy during theformation of anisotropic gold nanoparticles, especially gold nanorods, in liquid phase. For ourenvisaged aim, between numerous synthetic methods developed for production ofnanoparticles, seed mediated approach is chosen for the fabrication of final anisotropic goldnanoparticles from small seeds which is grown into final nanoparticle later on. During thesynthesis of nanoparticles, those seeds play critical role as precursors to control the yield ofand the crystal structure of final anisotropic nanoparticle. Here we offer a systematical studyon the origin of anisotropy with respect to “seed size” and “crystal morphology”. Since thesesmall particles are the genesis of anisotropic metal nanoparticle synthesis, in this thesis weanswer following questions to explain the origin of anisotropy;i. How to control the crystal structure and the size of the seeds?ii. What are the influences of controlled seed size and structure on the kinetics ofnanoparticle growth?

Une combinaison entre l’assemblage de monocouches au sommet de nano-cristaux d’or et la microscopie à sonde locale permet d’explorer l’interaction entre les molécules actives et son milieu, mais aussi démontrer expérimentalement une diode moléculaire peut travailler à haute fréquence. La fabrication des nanocristaux d’or par lithographie électronique rapide nous a permis leur caractérisation par des techniques nécessitant des surfaces millimétrique, mais également par des techniques en champ proche. La détection electrochimique d’un petit nombre de molécules par nanocrystal prévoit d’intéressantes recherches futures sur l’attache et la détection de molécules uniques sur la nano-particule d’or. D’un côté, cette étude confirme une théorie récente: les effets coopératifs entre les molécules ont un effet d’asymétrie sur « la courbe d’histogramme de conductance ». D’un autre côté, des théories d’électrochimie ont été utilisées pour investiguer les effets d’interaction entre molécules avec groupe redox et l’écart-type de l’énergie moléculaire. Cette étude nous a permis d’extraire des gammes d’énergie de couplage entre molécules, un premier pas vers une estimation quantitative expérimentale de ce paramètre clé pour les applications en électronique organique. A l’aide d’un AFM couplé à un système de mesure en hyperfréquences, nous mesurons les propriétés électroniques à l’échelle nanométrique. Nous prouvons une diode moléculaire à 18 GHz avec un ratio de redressement de 12 dB (facteur 4) à cette fréquence. Des petites capacitances, dans la gamme de l’aF ont en particulier permis d’observer ce comportement à hautes fréquences
An attractive combination of self-assembled monolayers on top of “Au” single crystal Nanoparticles (AuNp) and Scanning Probe Microscopies permits to explore the interaction between active molecules in the junction, as well as with the media. At the same time, we demonstrate the experimental proof of a molecular rectifying diode working at gigahertz frequency. Device fabrication by fast e-beam lithography allows their characterization by techniques that may need millimeter scale surfaces as well as by near field Scanning Probe Microscopies. Detection of a little number of molecules per AuNP promises interesting future research in the challenge of grafting and detecting single molecules per nanoparticle. On the one hand, this investigation confirms a recent theoretical prediction that cooperative effects between molecules may have an effect on the asymmetry of the conductance histogram line shape. On the other hand, established electrochemical theories are exploited to investigate similar factors such as interaction between redox molecules and the modification of the energy level of molecular orbitals. This study permits extracting a range of coupling energies between molecules that may be a first step towards the quantitative experimental estimation of this key parameter in molecular electronics. Thanks to an AFM connected to Network analyzer, we characterize a molecular diode operating at high frequency to 18 GHz with a rectification ratio of 12 dB (factor 4) at this frequency. Small capacitances in the order of few aF permit to see this behavior at high frequencies

Dans ce travail de thèse, le microscope à force atomique (AFM) a été utilisé comme outil de manipulation de haute précision pour construire des nanostructures plasmoniques avec des géométries définies et un réglage précis de la distance interparticulaire et également comme technique de spectroscopie d'absorption. Différentes études concernant les phénomènes pertinents pour la manipulation des nanoparticules et émergeant à l'interface substrat-nanoparticules, ont été réalisées. Des expériences de frottement menées sur diverses surfaces d'oxydes ont révélé un nouveau mécanisme de frottement à l’échelle nanométrique, expliqué par un modèle de potentiel d'interaction de type Lennard-Jones modifié. Les propriétés de frottement et d'adhésion de CTAB adsorbé sur silice sont également présentées. Des nano-bâtonnets d'or fonctionnalisés par du CTAB ont été manipulés par AFM afin de construire des nanostructures plasmoniques. La dernière partie de la thèse présente les efforts expérimentaux et théoriques pour démontrer la faisabilité de l'utilisation d'un AFM comme une technique de spectroscopie optoélectronique à base de force
In this thesis work the atomic force microscope (AFM) was employed first as a high precision manipulation tool for building plasmonic nanostructures with defined geometries and precise tuning of interparticle distance and second as an absorption spectroscopy technique. Different studies regarding phenomena emerging at sample nanoparticle interface relevant for nanoparticle manipulation were performed. Friction experiments conducted on various oxide surfaces revealed a novel nanoscale stick slip friction mechanism, explained by a modified Lennard-Jones-like interaction potential model. Frictional and adhesion properties of CTAB adsorbed on silica are also reported. CTAB functionalized gold nanorods were used for building specific plasmonic particulate nanostructures. The final part of the thesis presents experimental and theoretical efforts to demonstrate the feasibility of using an AFM as a force-based optoelectronic spectroscopy technique

**English** Plasmonic particles such as gold nanorods (GNRs) are showing themselves as powerful contrast agents for important applications such as photoacoustic imaging and photothermal ablation of cancer. However, their unique photothermal conversion efficiency can turn into a practical disadvantage, and expose them to the risk of overheating and irreversible photodamage. The processes of prefusion and remodeling of GNRs under illumination with optical pulses of typical duration of the order of a few ns will be studied in depth. A retrospective classification of these approaches will be undertaken according to often implicit principles, such as: constraining the initial shape, speeding up their thermal coupling with the environment by lowering their thermal resistance at the interface, or redistributing the incoming energy among several particles. Advantages and disadvantages and contexts of practical interest in which one solution may be more appropriate than the other will be discussed. Stabilization of the optical properties of anisotropic plasmonic particles by thermal heating and laser irradiation is an important issue in many biomedical applications. The effect that small thiols have on the thermal photostability of gold nanorods will be addressed. The nanoparticles were treated with mixtures of poly-ethylene-glycol thiolate (PEG-SH) and methyl-benzene-thiol (MBT) with molar ratios ranging from 0 (for the case of pure PEG) to 20, and then incubated in an oven. under sub-boiling conditions. Small thiols have been found to greatly improve the thermal stability of GNRs. For example, after 1 hour at 90 °C the samples with pure PEG lost more than 70% of the optical absorbance in their initial peak position, while the particles covered with a dense layer of MBT remained almost unchanged. It is possible to attribute this effect to a modulation of the activation barrier for the superficial diffusion of the gold atoms. Furthermore, we addressed the translation of this effect on the photostability of irradiated gold nanorods under conditions of interest for photoacoustic imaging and it was found that small thiols delay the damage thresholds by up to a factor of 2. In this work of thesis also describes the effect of the thermal resistance at the gold-water interface (Kapitza resistance) on the photoacoustic conversion performance of gold nanorods. The results indicate possible strategies for optimizing plasmonic particles as contrast agents for imaging, or even as transducers for biosensors. An effective approach is also suggested to modulate the Kapitza resistance by including features not yet well studied such as roughness or the presence of adsorbates. Following this idea, a rough variant of gold nanorods was synthesized by galvanic deposition and replacement of a silver shell, where roughness provides photoacoustic signals approximately 70% higher and damage thresholds of 120%. Furthermore, the particles were coated with a protein crown, which brings about a decrease in photoacoustic signals as the thickness of the shell increases; this could inspire new solutions for biosensors based on a photoacoustic transduction mechanism. Both of these results are consistent with effective modulation of Kapitza resistance, which can decrease with roughening, due to an increase in specific surface area, and can increase with the introduction of a protein coating (which can act as insulation thermal). Hybrid materials consisting of core/shell Au/Ag nanorods have also been developed, included in porous biomimetic phantoms (scaffolds) of chitosan/polyvinyl alcohol (chitosan/PVA) for applications in tissue engineering and wound healing. The combination of Au and Ag in a single construct provides synergistic opportunities for optical activation of functions such as near-infrared laser tissue welding and remote interrogation for the acquisition of prognostically relevant parameters in monitoring wound healing. In particular, the bimetallic component ensures improved optical tunability, shelf life and photothermal stability, acts as a reservoir for germicidal silver cations. At the same time, the polymer blend is ideal for bonding to connective tissue following photothermal activation and for supporting manufacturing processes that provide high porosity, such as electro-spinning, thus setting all the conditions for cell repopulation and antimicrobial protection. In summary, in this work, the optimization of an important system such as GNRs for complementary applications in different biomedical fields has been addressed; their stability and photoacoustic conversion efficiency have been optimized for use as contrast agents optical, developing functional coatings with small organic molecules or with metal porous layers. Finally, the integration of Au/Ag bimetallic nanorods into hybrid scaffolds for tissue engineering was evaluated, exploiting both the photothermal conversion efficiency and the optical sensitivity to oxidative stress conditions, in order to activate processes and monitor parameters of interest in scope of wound healing. **Italiano** Le particelle plasmoniche come i nanorods d'oro (GNRs) si stanno mostrando potenti agenti di contrasto per applicazioni importanti come l'imaging fotoacustico e l'ablazione fototermica del cancro. Però, la loro efficienza unica di conversione fototermica può trasformarsi in uno svantaggio pratico, e esporli al rischio di surriscaldamento e fotodanneggiamento irreversibile. Verranno approfonditi i processi di prefusione e rimodellazione dei GNRs sotto illuminazione con impulsi ottici di durata tipica dell'ordine di pochi ns. Verrà intrapresa una classificazione retrospettiva di tali approcci secondo principi spesso impliciti, come: vincolare la forma iniziale, velocizzare il loro accoppiamento termico con l'ambiente abbassando la loro resistenza termica all'interfaccia, oppure ridistribuire l'energia in ingresso tra più particelle. Saranno discussi vantaggi e svantaggi e contesti di interesse pratico in cui una soluzione può essere più appropriata dell'altra. La stabilizzazione delle proprietà ottiche delle particelle plasmoniche anisotrope tramite riscaldamento termico e irradiazione laser è una questione importante in molte applicazioni biomediche. Verrà affrontato l'effetto che piccoli tioli hanno sulla fotostabilità termica dei nanorods d'oro. Le nanoparticelle sono state trattate con miscele di poli-etilen-glicole tiolato (PEG-SH) e metil-benzen-tiolo (MBT) con rapporti molari compresi tra 0 (per il caso del PEG puro) e 20, e poi incubati in stufa in condizioni di sub-ebollizione. È stato scoperto che i piccoli tioli migliorano notevolmente la stabilità termica dei GNRs. Ad esempio, dopo 1 ora a 90 °C i campioni con PEG puro hanno perso più del 70% dell'assorbanza ottica nella loro posizione di picco iniziale, mentre le particelle ricoperte di un denso strato di MBT sono rimaste pressoché invariate. È possibile attribuire questo effetto ad una modulazione della barriera di attivazione per la diffusione superficiale degli atomi d'oro. Inoltre, abbiamo affrontato la traduzione di questo effetto sulla fotostabilità dei nanorods d'oro irradiati in condizioni di interesse per l'imaging fotoacustico ed è stato scoperto che i piccoli tioli ritardano le soglie di danneggiamento fino a un fattore di 2. In questo lavoro di tesi viene descritto inoltre l'effetto della resistenza termica all'interfaccia oro-acqua (resistenza di Kapitza) sulle prestazioni di conversione fotoacustica dei nanorods d'oro. I risultati indicano possibili strategie per l'ottimizzazione delle particelle plasmoniche come agenti di contrasto per l'imaging, o anche come trasduttori per i biosensori. Viene inoltre suggerito un approccio efficace per modulare la resistenza di Kapitza includendo caratteristiche ancora non ben studiate come rugosità o presenza di adsorbati. Seguendo questa idea è stata sintetizzata una variante rugosa di nanorods d'oro per deposizione e sostituzione galvanica di un guscio d'argento, dove la rugosità fornisce segnali fotoacustici più elevati di circa il 70% e soglie di danneggiamento del 120%. Inoltre, le particelle sono state rivestite con una corona proteica, la quale apporta una diminuzione dei segnali fotoacustici con l'aumentare dello spessore del guscio; questo potrebbe ispirare nuove soluzioni per biosensori basate su un meccanismo di trasduzione fotoacustica. Entrambi questi risultati sono coerenti con un'efficace modulazione della resistenza di Kapitza, che può diminuire con l'irruvidimento, a causa di un aumento della superficie specifica, e può aumentare con l'introduzione di un rivestimento proteico (il quale può fungere da isolamento termico). Sono stati anche sviluppati materiali ibridi costituiti da nanorods core/shell Au/Ag, inclusi in fantocci biomimetici (scaffold) porosi di chitosano/polivinilil alcol (chitosano/PVA) per applicazioni nell'ingegneria tissutale e nella guarigione delle ferite (wound healing). La combinazione di Au e Ag in un unico costrutto fornisce opportunità sinergiche per l'attivazione ottica di funzioni come la saldatura dei tessuti con laser nel vicino infrarosso e l’interrogazione remota per l’acquisizione di parametri di rilevanza prognostica nel monitoraggio della guarigione delle ferite. In particolare, la componente bimetallica assicura sintonizzabilità ottica, durata di conservazione e stabilità fototermica migliori, funge da serbatoio di cationi d'argento germicidi. Allo stesso tempo, la miscela polimerica è ideale per essere legata al tessuto connettivo a seguito di attivazione fototermica e per supportare i processi di fabbricazione che forniscono un’elevata porosità, come l'elettrofilatura, ponendo così tutte le premesse per il ripopolamento cellulare e la protezione antimicrobica. In sintesi, in questo lavoro, è stata affrontata l'ottimizzazione di un sistema importante come i GNRs per applicazioni complementari in diversi ambiti biomedici; ne è stata ottimizzata la stabilità e l'efficienza di conversione fotoacustica per essere utilizzati come agenti di contrasto ottico, sviluppandone rivestimenti funzionali con piccole molecole organiche oppure con strati porosi metallici. Infine è stata valutata l'integrazione di nanorods bimetallici di Au/Ag in scaffold ibridi per ingegneria tissutale, sfruttandone sia l'efficienza di conversione fototermica sia la sensibilità ottica alle condizioni di stress ossidativo, allo scopo di attivare processi e monitorare parametri di interesse nell'ambito del wound healing.