Dissertations / Theses on the topic 'Nanohorns de carbono'

2013/2014
La nanotecnologia è chiamata a rivoluzionare molti settori della nostra vita. Tra tutti i campi in cui è convolta, la ricerca delle energie rinnovabili, la possibilità di ottenere acqua pulita in tutte le parti del mondo, il miglioramento della salute e l’aumento dell’aspettativa di vita e lo sviluppo di sistemi informatici, sono gli obiettivi che si distinguono. Le nanostrutture di carbonio sono materiali promettenti che possono aiutare a raggiungere questi obiettivi: includono fullereni, grafene, nanotubi e nanohorns di carbonio. Tutti hanno proprietà interessanti e offrono nuovi vantaggi per le applicazioni in chimica dei materiali e nella medicina. Il nostro gruppo di ricerca ha sviluppato interessanti metodi per modificare queste nanostrutture per poterli applicare nei campi sopra menzionate. In questo contesto, lo scopo generale di questa tesi è il disegno di sistemi multifunzionali basati su nanostrutture di carbonio destinati ai sensori e alle applicazioni biologiche. Nel capitolo 1, viene fatta una breve panoramica dei nanotubi e i nanohorns di carbonio, spiegando la loro struttura, le loro proprietà e le loro applicazioni. Inoltre, vengono descritte le diverse strategie per la loro funzionalizzazione. Il riconoscimento molecolare gioca un ruolo importante in molti sistemi biologici. In flavoproteine, l'interazione specifica tra il cofattore flavina e l’apoenzima determina la reattività della proteina. Di conseguenza, la modulazione dell'ambiente delle flavine può essere utilizzata come strumento per determinare il loro comportamento e anche per comprendere i processi molecolari negli enzimi. Con questi obiettivi in mente, nel capitolo 2 è descritta la sintesi di differenti derivati basati sul sistema nanotubi di carbonio-triazina per l’uso come ricevitori di riboflavina. In primo luogo, la sintesi e la caratterizzazione di diverse 1,3,5-triazine sono riportate. In una seconda fase, viene descritta la funzionalizzazione di nanotubi di carbonio a parete singola e a parete multipla con le differenti triazine e anche con catene di p-tolil, impiegando le radiazioni microonde. Dopo, si riporta la caratterizzazione completa di questi derivati con varie tecniche. L’auto-assemblaggio degli ibridi è stato analizzato con microscopia elettronica a trasmissione, osservando come i funzionalizzati con 1,3,5-triazine formano buone dispersioni in acqua, mentre loro si auto-assemblano in solventi non polari a causa del riconoscimento di legami d’idrogeno complementari. Tuttavia, derivati funzionalizzati con p-tolil formano migliori dispersioni in solventi organici ed invece si auto-assemblano in acqua. Viene poi studiata la capacità dei nanotubi di carbonio funzionalizzati a parete multipla di riconoscere la riboflavina con la spettroscopia di fluorescenza e ultravioletta visibile, analizzando la grandezza delle interazioni non-covalenti. Si vede come la funzionalizzazione covalente dei nanotubi di carbonio diminuisce la loro capacità di formare interazioni  mentre le interazioni di legame d’idrogeno giocano un ruolo fondamentale nel processo di riconoscimento tra i membri del sistema. Inoltre, si è demostrata l’influenza dei tipi di triazine nel comportamento della riboflavina. In questo modo, è dimostrata la modulazione del riconoscimento molecolare della riboflavina attraverso i diversi nanotubi. Così, recettori artificiali in processi di catalisi possono essere specificamente disegnati per ottenere il controllo delle interazioni tra i nanotubi di carbonio funzionalizzati e la riboflavina, modificando il suo comportamento. Inoltre, le dimensioni e le eccellenti proprietà di nanotubi permettono di utilizzarli come strumento nella progettazione di sensori per la rivelazione di singole molecole. Nel capitolo 3 si riporta la modifica di nanohorn di carbonio per l'impiego come farmaci selettivi nella terapia del cancro è rapportata. Prima, si mostra la sintesi e la caratterizzazione di diversi ibridi di nanohorn: Antibody-CNH, Drug-CNH, Antibody-Drug-CNH e Double Functionalized-CNH. In particolare vengono usati cisplatino, come profarmaco, ed un anticorpo specifico per le cellule che mostrano l’antigene PSMA (Prostate-specific membrane antigen). Di seguito, vengono presentati diversi esperimenti biologici sviluppati in collaborazione con il professor Marco Colombatti dell’Università degli Studi di Verona (Italia). L’ibrido Antibody-Drug-CNH possiede una migliore capacità di uccidere selettivamente le cellule che presentano l'antigene PSMA, rispetto ad altri derivati di nanohorns. Il nuovo sistema progettato offre un grande potenziale dato dalla possibilità di modificare il tipo e il grado di funzionalizzazione. Questo permette di variare la quantità di farmaco o di anticorpo nelle nanostrutture con lo scopo di migliorare l’efficienza dei nuovi derivati. Inoltre, questo metodo può incorporare altri farmaci o anticorpi al sistema, aprendo la porta al trattamento di altre malattie. Il capitolo 4 descrive l'applicazione di diverse nanostrutture di carbonio nella terapia genica. Prima, si mostra la funzionalizzazione di nanohorns di carbonio con gruppi amminici, impiegando diversi metodi che utilizzano le radiazioni a microonde (cicloaddizione 1,3-dipolare e addizione radicalica). In seguito, viene presentato il lavoro svolto in "the Nanomedicine Lab" (Università di Manchester), sotto la supervisione del Prof. Kostas Kostarelos. L'efficacia dei nanohorns di carbonio funzionalizzati per formare complessi con siRNA è comparata con quella dei nanotubi di carbonio forniti dal gruppo del professor Kostarelos. Si è visto come i nanohorn di carbonio formino complessi con siRNA a differenza dei nanotubi. I complessi siRNA/nanohorn si caratterizzano utilizzando varie tecniche e viene analizzata la loro capacità di rilasciare il siRNA. Sebbene nanohorn di carbonio funzionalizzati con l’addizione radicalica mostrano una forte interazione con il materiale genetico, i derivati funzionalizzati con la cicloaddizione 1,3-dipolare lo rilasciano più facilmente. I risultati suggeriscono che, per conseguire il miglior carrier, la complessazione totale del siRNA con le nanostrutture dovrebbe essere evitato. Tuttavia, gli ibridi devono essere analizzati in vitro per garantire la migliore scelta. Questo studio contribuisce alla comprensione dell’uso di nanohorn di carbonio come vettori per terapia genica; ma, un maggior numero di derivati deve essere analizzato per un confronto completo con i nanotubi di carbonio.
La nanotecnología se presenta como una nueva ciencia que podrá revolucionar multiples aspectos de nuestras vidas. Entre los numerosos campos en los que la nanotecnología está centrada, la búsqueda de energías renovables, la posibilidad de obtener agua limpia en cualquier parte del mundo, la mejora de la salud y la longevidad de las personas así como el avance de los sistemas informáticos, son los objetivos que más destacan. Las nanoestructuras de carbon son nanomateriales prometedores que pueden ayudar a lograr esas metas. Estos materiales incluyen fullerenos, grafeno, nanohorns y nanotubos de carbono, entre otros. Todos ellos presentan propiedades interesantes y ofrecen nuevas ventajas para aplicaciones en química de materiales y medicina. Nuestro grupo de investigación ha desarrollado metodologías interesantes para la modificación de esas nanoestructuras con el objeto de que puedan ser útiles en las aplicaciones citadas anteriormente. En ese contexto, el objetivo general de esta tesis es el diseño de sistemas multifuncionales basados en nanoestructuras de carbono para ser usados en sensores y en aplicaciones biológicas. En el capítulo 1 se detallan la estructura y las propiedades de los nanohorns y los nanotubos de carbono junto a sus aplicaciones. Además, se muestra un resumen de las diferentes metodologías usadas para su funcionalización. El reconocimiento molecular juega un papel importante en numerosos sistemas biológicos. En flavoproteinas, la interacción específica entre el cofactor flavina y la apoenzima determina la reactividad total de la proteina. De este modo, la modulación del entorno de la flavina puede usarse como herramienta para determinar su comportamiento y, además, para entender los procesos moleculares en las enzimas. Con esos objetivos en mente, en el capítulo 2 se describe la síntesis de diferentes derivados basados en el sistema nanotubo de carbono-triazina para usarlos como receptores múltiples de riboflavina. En primer lugar, se sintentizan y caracterizan distintas 1,3,5-triazinas. En un segundo paso, se funcionalizan nanotubos de carbono tanto de pared simple como de pared multiple con las diferentes triazinas así como con cadenas de p-tolilo usando radiación microondas, y esos derivados se caracterizan completamente mediante diversas técnicas. El autoensamblaje de los híbridos se analiza mediante microscopía de transmisión electrónica observando como los derivados de 1,3,5-triazinas forman buenas dispersiones en agua y se autoensamblan en disolventes no polares debido al reconocimiento mediante enlaces de hidrógeno complementarios. Sin embargo, los derivados de p-tolilo forman mejores dispersiones en disolventes orgánicos y se agregan en agua. Finalmente, la habilidad de los nanotubos de carbono de pared múltiple funcionalizados para reconocer la riboflavina se estudia mediante fluorescencia y espectrocopía ultravioleta visible, analizando el alcance de las interacciones no covalentes. La funcionalización covalente de nanotubos de carbono disminuye su habilidad para formar interacciones  mientras que las interacciones mediante enlaces de hidrógeno juegan un papel fundamental en el proceso de reconocimiento entre los componentes del sistema. También se estudia la infuencia de las diferentes triazinas en el comportamiento de los complejos. De esta manera, se demuestra la modulación del reconocimiento de la riboflavina por medio de los diversos híbridos de nanotubos de carbono. Así, los receptores artificiales en procesos de catálisis pueden ser específicamente diseñados para lograr control de la interacción entre los nanotubos de carbono funcionalizados y la riboflavina, modificando así su comportamiento. En el capítulo 3 se describe la modificación de nanohorns de carbon para ser usados como fármacos selectivos en la terapia contra el cancer. En primer lugar se muestra la síntesis y caracterización de diferentes híbridos de nanohorns: Antibody-CNH, Drug-CNH, Antibody-Drug-CNH and Double Functionalized-CNH. En particular se usan cisplatino en forma de prodroga y un anticuerpo específico (D2B) para células de próstata que muestran el antígeno PSMA. Finalmente se presentan diferentes experimentos biológicos desarrollados en colaboración con el profesor Marco Colombatti, de la Universidad de Verona (Italia). Se demuestra la mejor habilidad del híbrido Antibody-Drug-CNH para matar selectivamente células que muestran el antígeno PSMA en comparación con los otros derivados de nanohorns. El nuevo sistema diseñado ofrece gran potencial debido la la posibilidad de modificar tanto el tipo como el grado de funcionalización. Esto permite variar la cantidad de fármaco o anticuerpo en la nanoestructura con el objetivo de conseguir una mejor eficacia del derivado. Además, con este método se pueden incorporar otros fármacos o anticuerpos al sistema, lo que abre la puerta al tratamiento de otras enfermedades. El capítulo 4 describe la aplicación de distintas nanoestructuras de carbono en terapia génica. Primero se muestra la funcionalización de nanohorns de carbono con grupos amino mediante diferentes metodologías usando radiación microondas (cicloadición 1,3-dipolar y adición radicálica). Después, se presenta el trabajo desarrollado en “the Nanomedicine Lab” (Universidad de Manchester) bajo la supervision del profesor Kostas Kostarelos. Se compara la eficacia de los nanohorns de carbono funcionalizados para formar complejos con siRNA con la de una serie de nanotubos de carbono aportados por el grupo del profesor Kostarelos. En nuestros experimentos, los nanohorns de carbon forman complejos mejor que los nanotubos. Los complejos siRNA/nanohorns se caracterizan mediante diversas técnicas y se analiza su capacidad de liberar el siRNA. Aunque los nanohorns de carbono funcionalizados mediante adición radicálica muestran una interacción más fuerte con el material genético, los derivados funcionalizados mediante cicloadición 1,3-dipolar lo liberan de manera más fácil. Los resultados sugieren que la complejación total entre el siRNA y la nanoestructura debe ser evitada para lograr más fácilmente el posterior desplazamiento de este dentro de la célula. Sin embargo, para garantizar la elección del híbrido más eficaz, los complejos deben ser analizados in vitro. Por tanto, este estudio contribuye al entendimiento de los nanohorns de carbono como vectores en terapia génica. No obstante, un mayor número de derivados deben ser analizados para lograr una comparación completa con los nanotubos de carbono.
Nanotechnology is claimed to revolutionize every aspect of our life. Among the large number of fields in which nanotechnology is involved; finding renewable clean energy, obtaining clean water for all, improving health and longevity and enhancing computing power are the most noteworthy. Carbon nanostructures are promising nanomaterials that can help to achieve these objectives. Fullerenes, graphene, nanohorns and nanotubes are including within these materials. All of them exhibit interesting properties and offer new opportunities for applications in material chemistry and medicine. Our research group has developed interesting methodologies for modifying these nanostructures in order to be used in the aforementioned applications. In this context, the objective of this thesis is the design of multifunctional systems based on carbon nanomaterials to be applied in sensors and in biological applications. Chapter 1 explains the structure, properties and applications of carbon nanohorns and carbon nanotubes, together with their applications. In addition, it provides an overview of the different methodologies to functionalize them. Molecular recognition plays an important role in numerous biological systems. In flavoproteins, the specific interaction between the flavin cofactor and the apoenzyme determines the reactivity of the entire protein. Therefore, the modulation of the environment of flavins can be used as a tool to set their behaviour and to understand the molecular processes in enzymes. With these aims, chapter 2 describes the synthesis of different carbon nanotubes-triazine derivatives to be used as multi-receptors of riboflavin. Firstly, different triazines are synthesized and characterized. In a second step, both single-walled and multi-walled carbon nanotubes are functionalized with different 1,3,5-triazine and p-tolyl chains using radical addition under microwave irradiation and these derivatives are characterized by different techniques. The self-assembly of these hybrids is analysed by transmission electron microscopy, observing how the 1,3,5-triazines derivatives form good dispersions in water and self-assemble in non-polar solvents due to the DAD-ADA hydrogen bonding recognition, while the p-tolyl derivatives show better dispersability in organic solvents and aggregate in polar solvents. Finally, the ability of the functionalized multi-walled carbon nanotubes to recognize riboflavin is studied by fluorescence and UV spectroscopy, analysing the scope of the different non-covalent interactions. It is shown that the functionalization of nanotubes by covalent approach decreases the ability of them to form  stacking and also that the hydrogen bond interactions play an important role in the recognition processes between the components. The influence of the different triazines in the complexes is also shown. Thus, the modulation of the molecular recognition of riboflavin by the diverse nanotubes hybrids is demonstrated. Therefore, our study clarifies the understanding of non-covalent interactions in biological systems. In this way, artificial receptors in catalystic processes could be designed through a specific control of the interaction between functionalized carbon nanotubes and riboflavin. Additionally, the size and the excellent properties of carbon nanotubes will permit to use them as the building blocks in the design of sensors for single-molecule detection. In chapter 3, the modification of carbon nanohorns to be applied as new selective drugs in cancer therapy is shown. Firstly, the synthesis and characterization of different conjugates by the functionalization of carbon nanohorns with orthogonal chains is reported: Antibody-CNH, Drug-CNH, Antibody-Drug-CNH and Double Functionalized-CNH. In particular, cisplatin in a prodrug form and a specific D2B antibody for PSMA+ prostate cancer cells are attached. In collaboration with the group of Professor Marco Colombatti, different biological experiments are reported. The better ability of Antibody-Drug-CNH to selectively kill PSMA+ cancer cells in comparison with the other synthesized CNHs hybrids is demonstrated. This new system offers great potentiality due to the possibility of modifying the type and degree of functionalization. This allows the variation of the quantity of drug or antibody attached to the nanostructure in order to play with the killing efficacy. Similarly, the method is useful to attach different drugs or antibodies opening the way to the treatment of other diseases. Chapter 4 describes the application of different carbon nanostructures in gene delivery. Firstly, the functionalization of carbon nanohorns with amino moieties by different methodologies (1,3-dipolar cycloaddition and radical addition) under microwave irradiation and their characterization is shown. Then, the work developed at the Nanomedicine Lab (University of Manchester) under the supervision of Professor Kostas Kostarelos is reported. The efficacy of the functionalized carbon nanohorns to form complexes with siRNA is compared with the one of functionalized carbon nanotubes provides by Prof. Kostarelos’s group. In our experiments, carbon nanohorns form complexes better than nanotubes. The nanohors complexes are characterized by different techniques and their capability to release siRNA is analysed. Although the carbon nanohorns functionalized by radical addition showed the strongest complexation of siRNA, the derivatives functionalized by 1,3-dipolar cycloaddition showed its easiest release. The results suggest that, in order to obtain the best candidate, a complete complexation of siRNA with the carrier should be avoided. However, the analysis of the cellular uptake should be evaluated in the future to assess the greatest candidate. These outcomes contribute to the understanding of the role of carbon nanohorns as gene delivery vectors. Nevertheless, additional derivatives should be tested for a fully comparison with carbon nanotubes.
XXVII Ciclo
1986

2006/2007
“Funzionalizzazione ed applicazione di carbon nanohorns e di carbon onions” Dalla scoperta della microscopia a scansione a sonda (SPM) nel 1980 a quella del fullerene, molti sono stati i premi Nobel nel campo delle Nanotecnologie. Diverse compagnie, attualmente, hanno investito fondi in questo settore. Ma cosa sono le Nanotecnologie? La parola e’utilizzata per descrivere diversi tipi di ricerca dove le dimensioni caratteristiche sono dell’ordine dei nanometri. I principali approcci impiegati nell’assemblaggio del materiale sono: “top-down” (dal più grande al più piccolo) e “bottom-up” (dal più piccolo al più grande). Il primo consiste nel ridurre le dimensioni della struttura fino alla nanoscala. Il secondo, proposto per la prima volta nel 1959 da Richard Feyman nel congresso dell’American Physical Society, consiste nel partire da strutture nanometriche per realizzare dei sistemi più grandi attraverso assembly o selfassembly. Attualmente, i principali strumenti, per caratterizzare e manipolare nano strutture, sono SEM (Microscopia a Scansione Elettronica) TEM (Microscopia a Trasmissione Elettronica), AFM (Atomic Force Microscopy) e STM (Microscopia a corrente di Tunnelling). Nanotubi, fullerene e recentemente carbon nanohorns (CNHs) e carbon onions (multishell fullerene, CNOs) sono considerati buoni candidati per applicazioni in differenti settori delle nanotecnologie. CNOs e CNHs sono due nuove forme allotropiche di carbonio, scoperte rispettivamente da Ugarte nel 1992 e da Iijima nel 1999, che hanno attratto l’attenzione di molti ricercatori. Negli ultimi tre anni, diversi studi sono stati riportati sui CNHs mentre i CNOs sono ancora largamente inesplorati. I pristine carbon nanohorns (p-CNHs) e CNOs (p-CNOs) non sono solubili nei comuni solventi organici ma, per studiare le loro potenziali applicazioni nel campo delle scienze dei materiali, è necessario migliorarne la solubilità. Il primo aspetto, preso in considerazione in questa tesi di dottorato, riguarda la funzionalizzazione e la caratterizzazione dei CNHs. A tale proposito, è stato sintetizzato un amminoacido impiegato nella reazione di ciclo addizione 1,3-dipolare. Reazioni di amidazione e di addizione nucleofila, inoltre, hanno portato alla sintesi dei due primi sistemi in cui CNHs fungono da elettron accettori e la porfirina da elettron donatori al fine di studiare il trasferimento elettronico tra la porfirina ed CNHs. Successivamente, sia i CNOs di 5 nm (N-CNOs) che di 20 nm di diametro (A-CNOs) sono stati presi in considerazione e paragonati. Dato che gli N-CNOs risultano più reattivi, sono stati utilizzati nella sintesi di nuovi sistemi in cui CNOs fungono da elettron accettori ed il ferrocene da elettron attrattore. Per la prima volta, sono state eseguite delle misure di fotofisica e di elettrochimica del derivato ottenuto. La tesi è divisa in 4 capitoli. Il primo riguarda una descrizione panoramica delle diverse forme allotropiche del carbonio, in paricolare nanotubi e fullereni. Tecniche come arco elettrico, ablazione con laser di grafite e la deposizione mediante vapore chimico sono descritte brevemente. Quindi tre diversi approcci per funzionalizzare le nanoparticelle di carbonio sono riportati in dettaglio. Nel secondo capitolo sono stati introdotti i CNHs, le loro proprietà ed applicazioni ed un confronto tra i nanotubi e CNHs. Infine tre differenti studi sono stati affrontati: · Funzonalizzazione mediante cicloaddizione 1,3-dipolare per migliorare la solubilità dei CNHs; · Funzionalizzazione dei CNHs attraverso addizione nucleofila e reazione con la porfirina; · Funzionalizzazione dei CNHs mediante amidazione e reazione con la porfirina. Il trasferimento elettronico tra porfirina e CNHs è stato discusso. Nel terzo capitolo sono stati introdotti e confrontate le proprietà dei diversi tipi di CNOs. Successivamente e’ stato descritto uno studio relativo alla: · Funzionalizzazione mediante cicloaddizione 1,3 dipolare e reazione con l’acido carbossilico del ferrocene. L’nterazione elettronica tra il ferrocene ed i CNOs è stata studiata. Tutti i dettagli sperimentali sono descritti nel quarto capitolo.
“Functionalization and application of carbon nanohorns and carbon onions” Since the discovery of scanning probe microscope (SPM) in 1980 to that of fullerene, several Nobel Prizes have been awarded in Nanotechnology. Many companies are also currently working in this field such as IBM and Samsung. Government and corporations worldwide have invested over $ 4 billion into nanotechnology in the last year alone. What is exactly Nanotechnology? The word “Nanotechnology” is used to describe different types of research where the characteristic dimensions are in a nanometer range. Two main approaches are used to assemble materials at the nanoscale: “top-down” (from larger to smaller) and “bottom-up” (from smaller to larger). The first one consists in reducing the dimension of the structures until nano levels. The second one was proposed for the first time in 1959 by Richard Feyman in the annual congress of American Physical Society. It consists in using nanometric structure, such as a molecule, and to create a mechanism larger through a process of assembly or self-assembly. To characterize and manipulate nanostructures, sophisticated techniques are required. Presently the main instruments are SEM (Scanning Electron Microscopy), TEM (Transmission Electron Microscopy), AFM (Atomic Force Microscopy), STM (Scanning Tunnelling Microscopy). Carbon nanoparticles such as carbon nanotubes (CNTs), fullerenes and recently carbon nanohorns and carbon onions, are considered good candidates in different nanotechnological applications. Carbon onions (multishell fullerene, CNOs) and carbon nanohorns (CNHs) are new allotropes of carbon. Discovered respectively by Ugarte in 1992 and by Iijima in 1999, these carbon nanoparticles start to attract the attention of many researchers. In the last three years, several studies have been reported about CNHs while CNOs are still largely unexplored. Pristine carbon nanohorns (p-CNHs) and CNOs are not soluble in common solvents. In order to study their potential applications in the field of material science, improving their solubility was necessary. First I focused my attention on the functionalization and characterization of CNHs. An aminoacid was synthesized and used in 1,3-dipolar cycloaddition reaction. This functionalization leads to an increase of the solubility of CNHs in various organic solvents. Using other reactions, such as amidation or nucleophilic additions, two assemblies, in which CNHs are electron acceptors and porphyrins the electron donors, were synthesized and the electron transfer between the porphyrins and the CNH core was studied. Then, CNOs either of 5 nm or 20 nm of diameter were synthesized, respectively by annealing of nanodiamonds and by arc discharge. These two samples of CNOs present different properties and reactivity. As CNOs produced by annealing of nanodiamonds are more reactive, they were used to synthesize a new assembly, in which CNOs are the electron acceptors and ferrocene the electron donors. For the first time, electrochemical and photophysical measurements of CNOs were performed. The thesis is divided in four chapters. The first one provides an overview of carbon allotropes, in particular CNTs and fullerenes. Different techniques as arc discharge, laser ablation and chemical vapour deposition are briefly described. Finally three general approaches to functionalize carbon nanoparticles are reported in detail. In the second chapter CNHs are introduced. The properties and the applications are shown. A comparison between CNTs and CNHs is also given. Then three different studies are presented: · Functionalization by 1,3-dipolar cycloaddition to improve the solubility of CNHs; · Functionalization by nucleophilic addition and coupling with porphyrin; · Functionalization by amidation and coupling with porphyrin. The electron transfer between the porphyrin and CNH core is discussed. In the third chapter CNOs are introduced. Two different type of CNOs are described and compared in order to choose the more reactive nanoparticles. Then a study is reported: · Functionalization by 1,3 dipolar cycloaddition and coupling with ferrocene carboxylic acid. The interaction between the ferrocene moiety and the CNOs is discussed. All the experimental details are given in the fourth chapter.
XX Ciclo
1976

We have measured adsorption isotherms at ten different temperatures from 90.432 K to 163.812 K for CF4 on a sample of chemically-opened carbon nanohorns. The interior of the individual nanohorns is accessible to sorbates in these chemically opened nanohorns. Two substeps are visible in the adsorption data, one corresponding to groups of stronger binding sites (lower pressure substep) and another corresponding to weaker binding sites (higher pressure substep). The stronger binding sites are interstitial pores and intra nanohorns pores and the weaker binding sites are outer surfaces and interior sites away from the tips. We have found that the isosteric heat is a decreasing function of coverage. Results for the effective specific surface area (≈969 m^2/gm), kinetics of adsorption, and the isosteric heat of adsorption as a function of sorbate loading will be presented. Comparison to absorption results for other sorbates on open carbon nanohorns will be discussed.

La caractérisation et modélisation de « nanohorns » monofeuillets (SWNH) et de forêts de nanotubes par microscopie analytique sont présentées ainsi que leurs applications pour le traitement du cancer. Dans une première partie, nous introduirons les méthodes de microscopie et de spectroscopie utilisées dans nos expériences. Nous étudierons ensuite le processus de croissance de forêts de nanotubes de carbone monofeuillets (dans le contexte d’une collaboration avec l'AIST au Japon). Les SWNH, leur structure, propriétés de remplissage et de fonctionnarisation seront analysés et une nouvelle méthode sera présentée pour l'étude de la porosité de matériaux inorganique en EELS. Des calculs ab-initio seront aussi utilisés pour étudier l'effet des défauts dans les parois des SWNH sur les phénomènes d'oxydation et de remplissage des SWNH. Finalement, nous étudierons les possibles applications de SWNH dans le domaine pharmaceutique, et en particulier pour les traitements cancéreux
In this manuscript, we will expose the characterization and modelling of Single Wall Nanohorns (SWNH) and Nanotube Forests by analytical microscopy and the functionalization of SWNH for drug delivery applications. Firstly, we will introduce the microscopy and spectroscopy methods used for our experiments. We will then study the growth process of Single Wall Carbon Nanotubes (SWCNT) forests (within the framework of a collaboration with AIST, Japan). SWCH, their structure, modifications and filling properties will be analysed in details. An original method will be presented to study the porosity of inorganic material with EELS. Ab initio calculation will also be used to explore the effect of the defects present in the SWNH wall on the oxidation and filling process. We will study the potentialities of Single Wall Carbon nanohorns as Drug Delivery Systems and particularly as anticancer drug carriers

Adsorption isotherms can be used to determine surface area of a substrate and the heat released when adsorption occurs. Our measurements are done determining the equilibrium pressures corresponding to a given amount of gas adsorbed on a substrate at constant temperature. The adsorption studies were done on aggregates of open dahlia-like carbon nanohorns. The nanohorns were oxidized for 9 hours at 550 °C to open them up and render their interior space accessible for adsorption. Volumetric adsorption measurements of Ne were performed at twelve different temperatures between 19 K and 48 K. The isotherms showed two substeps. The first substep corresponds to adsorption on the high energy binding sites in the interior of the nanohorns, near the tip. The second substep corresponds to low energy binding sites both on the outside of the nanotubes and inside the nanotube away from the tip. The isosteric heat measurements obtained from the isotherm data also shows these two distinct substeps. The effective surface area of the open nanotubes was determined from the isotherms using the point-B method. The isosteric heat and surface area data for neon on open nanohorns were compared to two similar experiments of neon adsorbed on aggregates of closed nanohorns.

Cancer therapies are often limited by bulk and cellular barriers to transport. Nanoparticle or chemotherapeutic compound intracellular transport has implications in understanding therapeutic effect and toxicity. The scope of this thesis was to study the intracellular transport of carbon nanohorns and to improve the efficacy of various chemotherapeutic agents through increased intracellular transport. In the first study, fluorescent probes (quantum dots) were conjugated to carbon nanohorns to facilitate the optical visualization of the nanohorns. These hybrid particles were characterized with transmission electron microscopy, electron dispersive spectroscopy and UV-VIS/FL spectroscopy. Their cellular uptake kinetics, uptake efficiencies, and intracellular distribution were determined in three malignant cell lines (breast – MDA-MB-231, bladder – AY-27, and brain – U87-MG) using flow cytometry and confocal microscopy. Intracellular distribution did not vary greatly between cell lines; however, the uptake kinetics and efficiencies were highly dependent on cell morphology. In the second study, the efficacy of various chemotherapeutic agents (i.e., doxorubicin, cisplatin, and carboplatin) was evaluated in AY-27 rat bladder transitional cell carcinoma cells. In the future, severe hyperthermia and chemothermotherapy (chemotherapy + hyperthermia) will also be evaluated. Doxorubicin and cisplatin compounds were more toxic compared to carboplatin. Hyperthermia has previously shown to increase the cellular uptake of chemotherapeutic agents; therefore, chemothermotherapy is expected to have synergistic effects on cell death. This work can then be translated to carbon nanohorn-based laser heating to generate thermal energy in a local region for delivery of high concentrations of chemotherapeutic agents. Although these two concepts are small pieces of the overall scope of nanoparticle-based therapies, they are fundamental to the advancement of such therapies.
Master of Science

Les nanotubes de carbone ou le graphène sont des formes allotropiques du carbone prometteuses pour un large domaine d'applications, mais des modifications de leur surface carbonée sont nécessaires pour leur manipulation et mise en forme. La fonctionnalisation covalente est un des moyens utilisés avec succès dans ce cadre, même si les modifications induites ne sont pas contrôlables. Les travaux réalisés au cours de cette thèse concernent l'utilisation de la réduction chimique des nanotubes et autres nanoformes de carbone, nanocornes, graphène ou nanodisques, pour d'une part obtenir des solutions stables et concentrées dans une gamme de solvants dépendant du type de nanoforme et d'autre part fonctionnaliser de manière covalente les différents types de surface carbonée de ces objets. Dans le cas des nanotubes, des molécules acceptrices ou donneuses d'électrons ont ainsi été greffées permettant la formation d'ensembles donneur-accepteur. D'autre part, le nombre de fonctions chimique greffées a pu être contrôlé, préservant ainsi les propriétés électroniques des nanotubes.

Commonly viewed as the shortest cross sections of armchair carbon nanotubes (CNTs), cycloparaphenylenes (CPPs) represent a unique class of conjugated macrocycles with rigid backbones. In addition to their utility in seeding the growth of uniform CNTs, these strained nanohoops and their derivatives have unique optoelectronic and supramolecular properties for potential applications in materials science. Herein we present our efforts in designing novel nanohoop architectures and new types of strained macrocycles that serve as building blocks for functional materials. Chapter I briefly reviewed the under-represented reactivity studies of strained aromatic macrocycles. Chapter II describes our early efforts in probing the structure-property relationships of oligophenylene macrocycles focusing on the understanding of the influence of structural bending and cyclic conjugation on the optoelectronic properties. Chapter III reports the reactivity study of 1,4-anthracene-incorporated [12]CPP, a model substrate to examine the feasibility of using anthracene as the functional handle to crosslink nanohoops. Chapter IV presents the synthesis of a molecular propeller with three nanohoop blades and examines its unique hexagonal layered packing structure. In Chapter V, we disclose the synthesis of strained stilbene macrocycles suitable for ring-opening metathesis polymerization (ROMP) as well as the initial ROMP studies of this monomeric system. This dissertation contains previously published and unpublished coauthored materials.

�Background: Photothermal therapy is an actively researched cancer treatment alternative to chemotherapy and resection due to its potential as a minimally invasive treatment with fewer health complications than high energy radiation therapies. �The effectiveness of photothermal therapy may be enhanced with the use of photoabsorbtive nanoparticles by increasing heat generation and improving spatial selectivity. �While photothermal therapy is a spatially distributed treatment, traditional experimental analysis methods used to assess photothermal therapy have either lacked spatial assessment such as is the case with standard viability assays of cell monolayers, or they only provide macroscopic treatment information, such as the measurement of the diameters of implanted mice flank tumors post-treatment. �
Goals: �This work aims to accomplish two major goals. �The first is to determine the therapeutic impact of combining Single Walled Carbon Nanohorns (SWNHs) with photothermal therapy. �The second is to advance the measurement tools used to assess photothermal therapy by developing viability measurement methods which incorporate detailed quantitative spatial information
Methods: Photothermal therapy was tested with and without SWNHs in in vitro cell monolayers, in vitro tissue phantoms, and ex-vivo tissue. �Digital image analysis methods were developed which allowed for the use of viability assays and histological information to be identified and organized spatially. �These methods were then used to compare the impact of cellular microenvironment and heating method on Arrhenius parameters.
Results: The inclusion of SWNHs dramatically increased the temperatures reached in each experiment. �Digital image analysis methods were shown to quantify spatial viability with a high degree of accuracy and precision in 2D and 3D. �Experimental data indicated that there were areas of collateral damage (partially treated tissue) surrounding areas of completely treated tissue ranging which were between 46% and 78% of the completely treated volume. �In each case the heat transfer properties of the experimental system had a large impact on the area of treatment. �Variation in the temperature and viability response of photothermal therapy for specific laser and nanoparticle treatment parameters was quantified. �
����Conclusions: This research has brought an experimental cancer treatment procedure from experiments in cell monolayers to tests in ex-vivo tissue to analyze viability response. �The strengths of photothermal therapy such as its minimally invasive nature, and effectiveness at killing cells were experimentally demonstrated. � �This research has also developed the tools necessary to assess the spatial impact in vitro and lay the foundations for assessing spatial impact in vivo. �These tools may be used to assess other treatments beyond photothermal therapy, and serve as a basis for improving the analysis of biological systems both in vitro and in vivo.

Ph. D.

Five systems consisting of different sorbate-sorbent combinations were studied using experimental volumetric adsorption techniques. Multiple adsorption isotherms were measured at low temperatures and low pressures for all of the systems studied which included CO2 adsorption on single walled carbon nanotubes (CO2 – SWCNT), Ethane adsorption on closed carbon nanohorns (Ethane-cNH), Ar adsorption on open carbon nanohorns (Ar – oNH), CO2 adsorption on zeolitic imidazolate framework-8 (CO2 – ZIF-8), and O2 adsorption on ZIF-8 (O2 – ZIF-8). Each of these systems offers a unique study of the relationship between the physical properties of the adsorbate and substrate and the effects of these properties on the thermodynamics and kinetics of adsorption. In addition to being of fundamental interest, the thermodynamics and kinetics of adsorption are important to understand for practical considerations in research fields such as gas storage and gas separation via adsorption processes, among other applications. CO2 – SWCNT is a system with a small linear molecular adsorbate with a permanent quadrupole moment adsorbing on a substrate with quasi-1D grooves and convex outer adsorption sites. Ethane-cNH is a system with a linear alkane adsorbing on a substrate with conical pores and convex outer adsorption sites. Ar – oNH is a system with a spherical atom sorbing in a substrate with two different groups of conical adsorption sites and both convex and concave surface sites. CO2 – ZIF-8 and O2 – ZIF-8 are both systems with small linear molecules sorbing in a flexible microporous scaffold-like substrate. Adsorption isotherms were analyzed to identify features corresponding to adsorbate-adsorbate and adsorbate-substrate interactions. Namely, the presence of substeps in the semi-logarithmic data were identified and interpreted to correspond to groups of adsorption sites of similar binding energy which likely depend on the morphology and/or structural flexibility of the substrates. All of the systems, with the exception of CO2 - SWCNTs, yielded at least some isotherms with substeps at pressures below that corresponding to saturation. Effective specific surface areas for all adsorbent-substrate combinations were calculated using the BET and Point-B methods for the sake of comparison. These surface area measurements are very dependent on the porosity and morphology of the substrate as well as the size and shape of the adsorbate atoms/molecules and therefore the values vary greatly between the different systems. The isosteric heat of adsorption was calculated using isotherms over the full range of temperatures for each system. A variant of the Clausius-Clapeyron equation was used for this purpose and the results were analyzed based on adsorbate-adsorbate and adsorbate-substrate interactions. Plateaus in the isosteric heat data for Ethane – cNH and Ar – oNH were related to the morphology of the substrates and properties of the adsorbate species. For CO2 – SWCNTs, the isosteric heat at all but the lowest coverages is below the latent heat of deposition. This is due to the quadrupole moment of CO2. For both of the studies of adsorption on ZIF-8, the isosteric heat contains peaks in the data which likely are the result of the flexibility of the ZIF-8 structure. The kinetics of adsorption (or, the rates at which the adsorption systems approach equilibrium) were analyzed as functions of isotherm temperature and coverage, vapor pressure, and fractional uptake point by point along individual isotherms using the linear driving force model. Certain trends in the kinetics of adsorption are consistent for all the systems studied and others vary depending on the specific adsorbate-substrate combination. As with the thermodynamic results, trends in the kinetics of adsorption are discussed in terms of the effects of adsorbate-adsorbate and adsorbate-substrate interactions.

Composites of carbon nanostructures (CNSs) and biocompatible polymers are promising materials for a series of advanced technological applications, ranging from biomedicine and bioelectronics to smart packaging and soft robotics. In this thesis, we present three types of organic functionalized CNSs, namely 4-methoxyphenyl functionalized multi-walled carbon nanotubes, carbon nanohorns and reduced graphene oxide, used as nanofillers for the preparation of homogeneous and well-dispersed composites of poly(l-lactic acid), a biocompatible and biodegradable FDA approved polymer. A thorough characterization of the composites is given in terms of calorimetric response, electrical and mechanical properties. Significant differences are observed among the different types of CNS nanofillers, underlying the key role played by the nanoscale shape, and distribution of the components in driving the macroscopic behavior of the composite material. Surface properties are probed through advanced atomic force microscopy techniques, on both flat substrates (films) and confined systems (nanofibers). All these composites are found to be fully biocompatible when tested as scaffolds for supporting the proliferation, and differentiations of human neuronal precursor cell line SH-SY5Y, and of human Circulating Multipotent stem Cells (hCMCs). Prototypes of Nerve Guide Conduits (NGCs) for in vivo tests were also designed, and obtained using the material based on functionalized Multi Walled Carbon Nanotubes (MWCNTs), and tested on mice, finding promising results. We also propose the functionalization of MWCNTs with “functional” organic groups (4-benzoic acids and styrene), and performed an additional derivatization on them respectively through an amidation reaction, and a “grafting from” polymerization. The so obtained CNSs are promising for the preparation of more complex composite materials. Finally, we analyzed the reaction pathway of the Tour functionalization of CNSs, and we hypothesized that the real reaction scheme could be a balance between two different pathways.
Le nanostrutture di carbonio (CNS) e i polimeri biocompatibili sono materiali molto promettenti in un grande numero di applicazioni tecnologicamente avanzate, che vanno dalla biomedicina e bioelettronica, allo smart packaging e alla robotica soft. In questa tesi presentiamo la funzionalizzazione organica tramite addizione della p-metossianilina di 3 diverse CNS: i nanotubi di carbonio a parete multipla, i nanoconi di carbonio e il grafene ossido risotto. Questi materiali sono impiegati come additivi per la preparazione di materiali compositi nanostrutturati a base di acido polilattico (PLLA). In questa tesi è riportata una completa caratterizzazione in termini di proprietà termiche, elettriche e meccaniche. Sono evidenti differenze significative tra le tre nanostrutture e sul loro effetto sulle proprietà dei compositi; ciò sottolinea il ruolo chiave giocato dalla morfologia e forma a livello nanometrico nell’interazione nanostruttura-polimero e quindi nella determinazione delle caratteristiche finali del composito. La superfice dei materiali è stata caratterizzata tramite AFM e CAFM sia nella forma di film piatti sia nella forma di nanofibre ottenute tramite eletrospinning. Sono state quindi testate le proprietà di biocompatibilità e induzione/controllo della differenziazione sia su cellule umane neuronali (SH-SY5Y), sia su cellule staminali umane (hCMCs). I materiali a base di nanotubi di carbonio a parete multipla (MWCNT) ottenuti sono stati utilizzati per la preparazione di prototipi di nerve guide conduits (NGC) per operazioni in-vivo su topi, ottenendo risultati molto promettenti. Presentiamo anche la funzionalizzazione dei MWCNT con 2 gruppi organici “funzionali” (l’acido p-benzoico e lo stirene) sui quali è stata effettuata una derivatizzazione aggiuntiva sfruttando rispettivamente una reazione di ammidazione e una reazione di polimerizzazione “grafting from”. Infine abbiamo analizzato lo schema di reazione della funzionalizzazione di Tour delle CNS a abbiamo ipotizzato che la reale via sintetica sia costituita da due differenti vie in equilibrio tra di loro.

Laser therapies can provide a minimally invasive treatment alternative to surgical resection of tumors. However, therapy effectiveness is limited due to nonspecific heating of target tissue, leading to healthy tissue injury and extended treatment durations. These therapies can be further compromised due to heat shock protein (HSP) induction in tumor regions where non-lethal temperature elevation occurs, thereby imparting enhanced tumor cell viability and resistance to subsequent therapy treatments. Introducing nanoparticles (NPs), such as multi-walled nanotubes (MWNTs) or carbon nanohorns (CNHs), into target tissue prior to laser irradiation increases heating selectivity permitting more precise thermal energy delivery to the tumor region and enhances thermal deposition thereby increasing tumor injury and reducing HSP expression induction. This research investigates the impact of MWNTs and CNHs in untreated and laser-irradiated monolayer cell culture, tissue phantoms, and/or tumor tissue from both thermal and biological standpoints. Cell viability remained high for all unheated NP-containing samples, demonstrating the non-toxic nature of both the nanoparticle and the alginate phantom. Up-regulation of HSP27, 70 and 90 was witnessed in samples that achieved sub-lethal temperature elevations. Tuning of laser parameters permitted dramatic temperature elevations, decreased cell viability, and limited HSP induction in NP-containing samples compared to those lacking NPs. Preliminary work showed MWNT internalization by cells, which presents imaging and multi-modal therapy options for NT use. The lethal combination of NPs and laser light and NP internalization reveals these particles as being viable options for enhancing the thermal deposition and specificity of hyperthermia treatments to eliminate cancer.
Master of Science

Thesis (Ph. D.)--Southern Illinois University Carbondale, 2009.
"Department of Physics." Keywords: Adsorption, Gas separation, Gas storage, Metal-organic frameworks, Single-walled carbon nanotubes, Nanoporous materials. Includes bibliographical references (p. 86-96). Also available online.

The hydraulic resistance characterization manuscript chronicles the early development of the hollow-core fiberoptic microneedle device (FMD). The study determined that for straight tubing with an inner bore of 150 ?m and a length greater than 50 mm long, Poiseuille's Law was shown to be accurate within 12% of experimental data for the pressure range of 69-517 kPa. Comparison between different needle design geometries indicated that tip diameters <55 ?m cause a significant increase in hydraulic resistance. Tubing length should be kept to a minimum and tip diameter should be kept above this threshold to reduce overall hydraulic resistance. The bladder treatment study describes the fabrication and testing of the FMD for treatment of invasive urothelial cell carcinomas (UCCs). Experiments investigating the fluid dispersal of single-walled carbon nanohorns (SWNHs) in the wall of inflated, healthy ex vivo bladders demonstrated that perfusion of 2 cm° on the bladder wall's surface can be achieved with a 5 minute infusion at 50 ?L/min. Irradiation of the SWNH perfused bladder wall tissue with a free space, 1064 nm laser at an irradiance of 0.95 W/cm° for 40 seconds yielded a 480% temperature increase relative to similar irradiation of a non-infused control. Co-delivery experiments demonstrated both SWNH and light delivery though a single hollow-core fiber to heat the bladder wall 33 °C with an irradiance of 400 W/cm°, demonstrating that the FMD can be used to achieve hyperthermia-based therapeutic effects via interstitial irradiation.
Master of Science

Inspired by the roles of hair cells in nature, this study aims to develop and characterize two new sets of novel flow sensors. One set of sensors developed and studied in this work are flow sensors fabricated using carbon nanomaterials. These sensors are made by embedding carbon nanotubes (CNT) and carbon nanohorns (CNH) into a polymeric substrate and then tested by flowing a conductive aqueous solution over the surface of the exposed CNT and CNH. In response, a flow-dependent voltage is generated. The surface coverage and the electrical relationship between the sensor and water is investigated and the voltage measurements of sensors with different levels of resistance were tested in varying fluid velocities. In response to these fluid velocities, the least resistive sensor showed small, but detectable changes in voltages, while higher resistance sensors showed less response. In addition, plasma treatment of the carbon nanomaterial/PDMS films were conducted in order to render the PDMS on the surface hydrophilic and in turn to pull more fluid towards the carbon material. This showed to improve the sensitivity of the flow sensors. This work also builds on previous research by investigating the flow dependent electrical response of a â skinâ -encapsulated artificial hair cell in an aqueous flow. An artificial cell membrane is housed in a flexible polyurethane substrate and serves as the transduction element for the artificial hair cell. Flow experiments are conducted by placing the bio-inspired sensor in a flow chamber and subjecting it to pulse-like flows. This study demonstrates that the encapsulated artificial hair cell flow sensor is capable of sensing changes in flow through a mechanoelectrical response and that its sensing capabilities may be altered by varying its surface morphology. Furthermore, the sensorâ s response and dynamics as a function of its surface morphology and structural properties are investigated through synchronized motion tracking of the hair with a laser vibrometer and current measurements across the artificial cell membrane.
Master of Science

Carbon nanomaterials have attracted significant attention in the past decades for their unique properties and potential applications in many areas. This dissertation addresses the preparation, functionalization and potential biomedical applications of various carbonaceous nanomaterials. Trimetallic nitride template endohedral metallofullerenes (TNT-EMFs, M₃N@C₈₀, M = Gd, Lu, etc.) are some of the most promising materials for biomedical applications. Water-soluble Gd₃N@C₈₀ was prepared by the functionalization with poly(ethylene glycol) (PEG) and hydroxyl groups (Gd₃N@C₈₀[DiPEG(OH)ₓ]). The length of the PEG chain was tuned by changing the molecular weight of the PEG from 350 to 5000. The 1H magnetic resonance relaxivities of the materials were studied at 0.35 T, 2.4 T and 9.4 T. Their relaxivities were found to increase as the molecular weight of the PEG decreased, which is attributed to the increasing aggregate size. The aggregate sizes were confirmed by dynamic light scattering. In vivo study suggested that Gd3N@C₈₀[DiPEG(OH)x] was a good candidate for magnetic resonance imaging (MRI) contrast agents. Another facile method was also developed to functinalize Gd₃N@C₈₀ with both carboxyl and hydroxyl groups by reaction with succinic acyl peroxide and sodium hydroxide thereafter. The product was determined to be Gd₃N@C₈₀(OH)~₂₆(CH₂CH₂COOM)~₁₆ (M = Na, H) by X-ray photoelectron spectrometry. The Gd₃N@C₈₀(OH)~₂₆(CH₂CH₂COOM)~₁₆ also exhibited high relaxivity, and aggregates in water. The research on both pegylated and carboxylated Gd₃N@C₈₀ suggests that aggregation and rotational correlation time plays an important role in relaxation, and the relaxivities and aggregation of the water-soluble metallofullerenes can be tuned by varying the molecular weight of the functionality. TNT-EMFs can be encapsulated inside single-walled carbon nanotubes (SWNTs) to form "peapod" structures by heating the mixture of TNT-EMFs and SWNTs in a vacuum. The peapods were characterized by Raman spectrometry and transmission electron microscopy (TEM). The peapods were then functionalized with hydroxyl groups by a high speed vibration milling (HSVM) method in the presence of KOH. The functionalized Gd-doped peapods exhibited high relaxivites and had an additional advantage of "double carbon wall" protection of the toxic Gd atoms from possible leaking. The HSVM method was modified by using succinic acyl peroxide. The modified HSVM method could functionalize multi-walled carbon nanotubes (MWNT) and single-walled carbon nanohorns (SWNHs) with carboxyl groups. In the presence of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC), carboxylate MWNTs and SWNHs could be conjugated with CdSe/ZnS quantum dots (QDs). TNT-EMFs were also encapsulated inside SWNHs to form SWNH peapods. SWNH peapods were functionalized by the modified HSVM method and then were conjugated with CdSe/ZnS QDs. The peapods were characterized by TEM. In vitro and in vivo studies indicated that SWNH peapods could serve as a multimodal diagnostic agent: MRI contrast agent (Gd₃N@C₈₀ encapsulated), radio-active therapeutic agent (Lu₃N@C₈₀ encapsulated) and optical imaging agent (QDs).
Ph. D.

Significant cost and debilitation results from connective tissue injury and disease every year. Prolotherapy is an effective medical treatment used to increase joint stability. However, most associated studies are retrospective or case studies, rather than comprehensive laboratory investigation originating with the cellular response to exposure to the proliferant solutions. As a parallel consideration, nanoparticles are being investigated for use in drug delivery and heat shock treatment of cancerous tissue due to their unique structural and thermal properties. The phenomenal strength and stiffness of carbon nanoparticles have been used for commercial purposes in composite materials, but investigation of biomedical applications is still fairly nascent. In an attempt to develop a non-surgical approach to supporting and healing damaged ligaments and tendons resulting from injury or disease by combining prolotherapy and the use of nanoparticles, the author presents studies investigating the cellular response to proliferative therapy solution as well as tendon and ligament tissue's mechanical and cellular response to exposure to nanoparticles. In the prolotherapy solution cell studies, the results suggested that there is an optimal dosage of the proliferant for in vitro studies, different responses between cell types, and a dosage-dependent response in cell viability and collagen production to the solution P2G in preosteoblasts. In the nanoparticle studies, cell populations tolerated nanoparticles at the levels tested, tendon mechanical properties were increased (stiffness significantly so), and bright field and transmission electron microscopic histological images were taken of connective tissue and carbon nanohorn interactions.
Master of Science

Titanium oxide has been widely studied for its potential application in many scientific and technological fields. In particular, its photoelectrochemical properties are of great interest for possible applications in the conversion of solar energy into electricity, hydrogen production by water photosplitting and photocatalytic degradation of recalcitrant organic and inorganic pollutants (O'Regan and Grätzel 1991; Linsebigler, Lu et al. 1995; Mills and Le Hunte 1997; Grätzel 2001; Carp, Huisman et al. 2004; Mor, Varghese et al. 2006; Aprile, Corma et al. 2008; Varghese, Paulose et al. 2009). During the three years of the Ph.D. School in Molecular Sciences, the experimental work, performed at the Institute for Energetics and Interphases (IENI) of the Italian National Research Council (CNR) of Padua (Italy) (under supervision of Dr Monica Fabrizio), was focused on the study and optimization of vapor deposition techniques, physical vapor deposition (PVD) e chemical vapor deposition (CVD), of titanium oxide-based nanostructured materials for photocatalytic applications and their chemical-physical, morphological and functional characterizations. The PVD magnetron sputtering instrumentation (located at IENI-CNR laboratories) was adapted for ceramic thin film deposition, varying the geometrical and mechanical configuration. Therefore, the optimal synthesis conditions of photocatalytic titanium oxide thin films were identified by tuning the main process parameters: power supply (DC or RF), deposition time, substrate heating and motion, target-substrate distance, total pressure, inlet gas partial pressure. In order to improve the photocatalytic efficiency of titanium oxide thin films, several nitrogen doping attempts were carried out. Such kind of doping, indeed, was reported in literature as the most efficient way to reduce the titanium oxide band gap thus permitting the absorption of a larger solar spectrum fraction maintaining its photochemical stability (Asahi, Morikawa et al. 2001; Kitano, Funatsu et al. 2006; Asahi and Morikawa 2007). A large part of the experimental work was addressed towards the development and setting up of an apparatus for the photoinduced current measurement in titanium oxide electrodes under UV irradiation. The thin film deposition process studies performed on several planar substrates, such as soda-lime glass, ITO or fused quartz, the optimization of the process parameters and the knowledge of the titanium oxide-based system behavior permitted to figure out and develop new materials with improved photocatalytic efficiency. In particular, hybrid nanocomposites employing single wall carbon nanohorns (SWCNHs) as substrate for titanium oxide deposition were developed. In recent years, many published papers aimed to improve the titanium oxide photocatalytic behavior with mesoporous carbon-based hybrid nanocomposites (Orlanducci, Sessa et al. 2006; Liu and Zeng 2008; Wang, Ji et al. 2008; Yu, Quan et al. 2008). As a potential titanium oxide support, SWCNHs are very interesting nanostructures in virtue of their electronic properties, morphological features and high production yield (Kasuya, Yudasaka et al. 2002; Gattia, Vittori Antisari et al. 2007). Part of the great family of carbon nanotubes, they consist of a single layer of a graphene sheet wrapped into an irregular cone-shaped tubule with a variable diameter of generally few nanometers and a length of about ten nanometers (Iijima, Yudasaka et al. 1999; Murata, Kaneko et al. 2000). Depending on synthesis parameters, the SWCNHs assemble together in three types of spherical aggregates with diameters in the order of hundred nanometers (Yudasaka, Iijima et al. 2008). The photocatalytic efficiency improvement of titanium oxide in the hybrid material SWCNHs/TiO2 is due to the mesoporous morphology with high surface area (over than 300 m2g-1) of such carbon nanostructure aggregates and to the formation of the heterojunction with the oxide, which can reduce the electron-hole recombination process and therefore the overall efficiency of photocatalytic process (Cioffi, Campidelli et al. 2007; Petsalakis, Pagona et al. 2007). An important result obtained during the Ph.D. activity was the synthesis, through magnetron sputtering, of a novel nanostructured morphology of titanium oxide named “strelitzia-like titanium oxide” induced by the SWCNHs employed as substrates (Battiston, Bolzan et al. 2009). Therefore, the experimental activity was focused on the comprehension and optimization of nucleation and growth of this novel titanium oxide architecture. Moreover, in collaboration with the Institute of Inorganic Chemistry and Surfaces (ICIS) of the Italian National Research Council (CNR) of Padua (Italy), the TiO2 metal-organic chemical vapor deposition (MOCVD) was performed (Battiston, Bolzan et al. 2009) obtaining the SWCNH coating with different morphologic features with respect to the PVD synthesized morphologies. The characterization the hybrid nanocomposite obtained via MOCVD, that showed a homogeneous covering of SWCNH grains, suggested its employment as substrate for the magnetron sputtering deposition thus maximizing the strelitzia-like titanium oxide structure nucleation on all SWCNH aggregates. The broad nucleation of such novel nanostructures permitted to perform a deeper structural and functional characterization which finally showed that strelitzia-like nanocomposites have higher photocatalytic performances compared to the other kinds of titanium oxide samples investigated. The characterizations of thin films and hybrid nanocomposites were carried out in close cooperation with Padua University (Italy), IENI-CNR, ICIS-CNR, ITC-CNR (Construction Technologies Institute in Milan, Italy), Turin University (Italy) and Piezotech Japan Ltd (spin off of Research Institute for Nanoscience Kyoto, Japan), where a three month stage was performed with a fellowship of Italian Interuniversity Consortium on Materials Science and Technology. The structural, compositional, morphological and functional analyses were performed respectively by XRD, Raman spectroscopy, ICP-MS, SIMS, XPS, Cathodoluminescence, SEM, TEM, AFM, mechanical profiler, photocurrent measurements and photocatalytic degradation of phenol under UV irradiation.
L'ossido di titanio è considerato un eccellente materiale fotocatalizzatore grazie alla sua elevata efficienza, alla stabilità fotochimica, all’atossicità e al basso costo. Grazie a queste proprietà, i materiali nanostrutturati di ossido di titanio sono largamente studiati e impiegati in diversi settori tecnologici quali quelli della fotocatalisi, della degradazione fotocalitica di composti organici ed inorganici, della sensoristica e della conversione dell’energia solare in elettricità (O'Regan and Grätzel 1991; Linsebigler, Lu et al. 1995; Mills and Le Hunte 1997; Grätzel 2001; Carp, Huisman et al. 2004; Mor, Varghese et al. 2006; Aprile, Corma et al. 2008; Varghese, Paulose et al. 2009). Il lavoro svolto nell’arco dei tre anni di attività di ricerca effettuata, nell’ambito della Scuola di Dottorato in Scienze Molecolari, presso i laboratori dell’Istituto per l’Energetica e le Interfasi (IENI) del CNR di Padova (sotto supervisione della Dott.ssa Monica Fabrizio), è stato focalizzato sullo studio e ottimizzazione di tecniche di deposizione da fase vapore, physical vapor deposition (PVD) e chemical vapor deposition (CVD), e caratterizzazione chimico-fisica, morfologica e funzionale di materiali nanostrutturati a base di ossido di titanio per applicazioni fotocatalitiche. La strumentazione PVD magnetron sputtering, presente presso i laboratori IENI, è stata adattata per la deposizione di film di natura ceramica, intervenendo sulla configurazione geometrica e meccanica dell’apparato. In seguito, è stato possibile individuare le condizioni ottimali di sintesi per la deposizione di film sottili di ossido di titanio efficienti dal punto di vista fotocatalitico, studiando ed agendo sui principali parametri di processo: modalità DC o RF, tempo di deposizione, movimentazione e riscaldamento del substrato, distanza target-substrato, pressione totale, pressioni parziali dei gas introdotti in camera e potenza trasferita al plasma. Al fine di incrementare l’efficienza fotocatalitica dei film sottili, sono stati condotti diversi tentativi di sintesi introducendo azoto come drogante dell’ossido di titanio. Tale drogaggio è riportato in letteratura (Asahi, Morikawa et al. 2001; Kitano, Funatsu et al. 2006; Asahi and Morikawa 2007) come il metodo più idoneo per ridurre l’energy gap efficace del materiale, permettendo contemporaneamente l’assorbimento di una frazione più ampia dello spettro solare ed il mantenimento della stabilità fotochimica. Parte consistente del lavoro sperimentale è stata impiegata, inoltre, per intraprendere lo sviluppo e l’allestimento di un sistema per la misura della corrente fotoindotta, in seguito ad irraggiamento di luce UV-VIS, dell’ossido di titanio. Lo studio del processo di deposizione su vari tipi di substrati piani (vetro, ITO, silice pura), l’identificazione dei parametri di processo ottimali e la conoscenza acquisita del comportamento di tali sistemi ha permesso, infine, lo sviluppo e la progettazione di nuovi materiali più efficienti dal punto di vista fotocatalitico. In particolare, sono stati progettati e realizzati nanocompositi ibridi, impiegando Single Wall Carbon Nanohorn (SWCNH) come substrati per le deposizioni di ossido di titanio. Negli ultimi anni, infatti, sono stati pubblicati numerosi articoli sulla sintesi di materiali nanocompositi ibridi che impiegano materiali mesoporosi a base di carbonio, con lo scopo di incrementare le proprietà fotocatalitiche dell’ossido di titanio (Orlanducci, Sessa et al. 2006; Liu and Zeng 2008; Wang, Ji et al. 2008; Yu, Quan et al. 2008). Con questo scopo, i SWCNH rappresentano un buon candidato grazie alle loro proprietà elettroniche, caratteristiche morfologiche e all’alta resa di produzione (Kasuya, Yudasaka et al. 2002; Gattia, Vittori Antisari et al. 2007). Essi sono costituiti da aggregati, a simmetria sferica e delle dimensioni dell’ordine del centinaio di nanometri, di coni irregolari di grafene a parete singola di qualche nanometro di diametro e qualche decina di nanometri di lunghezza (Iijima, Yudasaka et al. 1999; Murata, Kaneko et al. 2000; Yudasaka, Iijima et al. 2008). L’incremento dell’efficienza fotocatalitica dell’ossido di titanio nel materiale ibrido SWCNH/TiO2 è giustificato dalla morfologia mesoporosa ad elevata area superficiale di questi aggregati (superiore a 300 m2 g-1) e dalla formazione dell’eterogiunzione con l’ossido, che può ridurre sensibilmente la ricombinazione elettrone-lacuna e incrementare, perciò, l’efficienza globale del processo fotocatalitico (Cioffi, Campidelli et al. 2007; Petsalakis, Pagona et al. 2007). Un importante risultato conseguito nello svolgimento dell’attività di dottorato riguarda l’ottenimento, grazie all’impiego del magnetron sputtering, di una nuova singolare morfologia nanostrutturata dell’ossido di titanio, chiamata “strelitzia-like titanium oxide”, indotta proprio dalla particolare morfologia dei SWCNH impiegati come substrati (Battiston, Bolzan et al. 2009). La successiva attività sperimentale è stata, quindi, indirizzata alla comprensione e all’ottimizzazione dei meccanismi di nucleazione e crescita di queste innovative strutture nanocomposite ibride SWCNH/TiO2. A questo proposito, in collaborazione con l’Istituto di Chimica Inorganica e delle Superfici (ICIS) del CNR di Padova, è stato eseguito un approfondito studio sull’influenza del metodo di deposizione utilizzato su nucleazione e crescita dell’ossido di titanio sui SWCNH, impiegando anche la tecnica metal-organic chemical vapor deposition (MOCVD) (Battiston, Bolzan et al. 2009), che ha permesso di ottenere morfologie del rivestimento molto differenti da quelle ottenute tramite magnetron sputtering. Lo studio e la caratterizzazione del nuovo materiale nanocomposito, ottenuto via MOCVD, ne ha suggerito l’impiego come substrato per la deposizione via magnetron sputtering permettendo, infine, di giungere all’ottimizzazione della nucleazione delle strelitzie di ossido di titanio, sfruttando ogni singolo aggregato di SWCNH. Tale risultato ha permesso, inoltre, di eseguire una approfondita caratterizzazione di tipo strutturale e funzionale della nuova morfologia dell’ossido di titanio che, infine, ha dimostrato possedere proprietà fotocatalitiche superiori rispetto a tutti i materiali a base di ossido di titanio con cui è stata comparata. Le caratterizzazioni dei film sottili e dei nanocompositi ibridi sono state eseguite in stretta collaborazione con diversi gruppi di ricerca appartenenti, oltre che all’Università di Padova e al CNR IENI, anche al CNR-ICIS, al CNR-ITC (Istituto per le Tecnologie delle Costruzioni), l’Università di Torino e Piezotech Japan Ltd, spinoff del Research Institute for Nanoscience con sede a Kyoto (Giappone), presso cui è stato svolto uno stage della durata di tre mesi nell’ambito della convenzione Italia-Giappone a cui prende parte il Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM). Le analisi effettuate sono state di tipo strutturale (XRD e Spettroscopia Raman), composizionale (ICP-MS, SIMS, XPS, Catodoluminescenza), morfologico (SEM, TEM, AFM e profilometro meccanico) e funzionale (misure di fotocorrente e degradazione fotocatalitica di composti organici).

*1-Dimensional Advective-Diffusion Model in Porous Media Infusion of therapeutic agents into tissue is makes use of two mass transport modes: advective transport, and molecular diffusion. Bulk infusion into a 0.6% wt agarose phantom was modeled as an infinite, homogenous, and isotropic porous medium saturated with the same solvent used in the infused dye tracer. The source is assumed to be spherical and isotropic with constant flow rate and concentration. The Peclet numberdecreases with power function Pe = 15762t0.337 due to the decrease in mean dye-front pore velocity as V goes to Vfinal. Diffusive mass transport does not become significant during any relevent time period. *Arborizing Fiberoptic Microneedle Catheter We have developed an arborizing catheter that allows multiple slender fused-silica CED cannulae to be deployed within a target volume of the brain via a single needle tract, and tested it in a widely accepted tissue phantom. The arborizing catheter was constructed by bonding and encapsulating seven slender PEEK tubes in a radially symmetric bundle with a progressive helical angle along the length, then grinding a conicle tip where the helical angle is greatest. The catheter was tested by casting 0.6% wt agarose around the device with all needles deployed to a tip-to-tip distance of 4 mm. Phantom temperature was maintained at 26 ± 2°C. 5% wt Indigo Carmine dye was infused at a rate of 0.3 uL/min/needle for 4 hours. N=4 infusions showed a Vd/Vi of 139.774, with a standard deviation of 45.01. This is an order of magnitude greater than single-needle infusions under similar conditions [45]. The arborizer showed the additional benefit of arresting reflux propagating up the lengths of individual needles, which has historically been a weakness of single-needle CED catheter designs. *In Vivo Co-Delivery of Single Walled Carbon Nano-horns and Laser Light to Treat Human Transitional Cell Carcinoma of the Urinary Bladder in a Rodent Model Using a rodent model we explored a treatment method for Transitional Cell Carcinoma (TCC) in the urinary bladder in which Single Walled Carbon Nanohorn (SWNH) solution and 1064 nm laser light are delivered into tumorous tissue via a co-delivery Fiberoptic Microneedle Device (FMD). Preliminary treatment parameters were determined by injecting SWNH solutions with concentrations of 0 mg/mL, 0.17 mg/mL, or 0.255 mg/mL into ex vivo porcine skin and irradiating each for three minutes at laser powers of 500 mW, or 1000 mW. The combination with the greatest temperature increase without burning the tissue, 0.17 mg/mL at 1000 mW, was selected for the in vivo treatment. TCC tumors were induced in a rodent model by injecting a solution of 106 AY27 urothelial carcinoma cells into the lateral aspect of the left hind leg of young, female F344 rats. When tumors reached 5-10 mm3, rats were anesthitized and treated. SWNH solution was injected directly into the tumor and irradiated until the target temperature of 60degC was achieved. The rats were then recovered from anestesia and monitored for 7-14 days, at which point they were humanely sacrificed, and the tumors prepared for histological examination. Histological assessment of areas of FMD treatment correlated well with gross morphological appearance. Foci of tumor necrosis showed sharp (1-2 mm) delineation from areas of viable tumor (not treated) and normal tissue. We believe we have demonstrated the feasibility of using the FMD for treatment of urothelial carcinoma using an animal model of this disease, and are encouraged to continue development of this treatment and testing in larger animal models.
Master of Science

2011/2012
Nanotechnology underwent a very rapid development in the last decades, thanks to the invention of different techniques that allow reaching the nanoscale. The great interest in this area arises from the variety of possible applications in different fields, such as electronics, where the miniaturization of components is a key factor, but also medicine. The creation of smart systems able to carry out a specific task in the body in a controlled way, either in diagnosis or therapy or tissue engineering, is the ultimate goal of a newborn area of research, called nanomedicine. In fact, to reach such an outstanding objective, a nanometer‐sized material is needed and carbon nanotubes (CNTs) are among the most promising candidates. The aim of this thesis was to study this opportunity and, in particular, the possible application of carbon nanotubes for spinal network repairing. After a review of the main features of neuronal network systems and the most common techniques to study their functionality, possible applications of nanotechnology for nanomedicine purposes are considered, focusing the attention on CNTs as neuronal interface in nerve tissue engineering. The work can be divided into two big parts. In the first part the impact of carbon nanotubes on various neuronal systems was studied. Different form of carbonaceous materials (carbon nanotubes, nanohorns and graphene) were deposited in a homogeneous way on a glass surface playing with organic functionalization and different deposition techniques. Hippocampal neuronal cells were grown on their surface to better understand how morphology and conductivity of the material could influence the activity of the neuronal network evidencing how both these characteristics could affect the electrophysiological properties of neurons. Then, also spinal neurons were grown on carbon nanotubes network deposited on a glass substrate to evaluate, for the first time, the impact of carbon nanotubes on this kind of cells. The tight interaction between these two materials appeared to cause a faster maturation of the spinal neurons with respect II to the control grown on a glass substrate. The long-term impact on a complex tissue (spinal cord slice) grown on carbon nanotubes carpet was also studied. The intimate interaction between the two materials observed by TEM and SEM analysis caused an increase in dimensions and number of neuronal fibers that comes out from the body of a spinal cord slice. An increase in electrophysiological activity of all neuronal network of the slice was also reported. In the second part of the work different conductive biocompatible nanocomposite materials based on carbon nanotubes and “artificial” polymers (such as Nafion, PVA, PET, PEI, PDMS and PANI) were investigated. The idea is to test these materials as neuronal prosthesis to repair spinal cord damage. All the prepared scaffolds showed CNTs on the surface favoring CNTs-neurons interaction. To address this aim different techniques and different organic functionalizations of CNTs were utilized to control supramolecular interactions between the nanomaterial and polymers orienting the deposition of the CNTs and preventing their aggregation. After that, an innovative method to study the possible ability of this nanocomposite materials to transmit a neuronal signal between two portions of spinal cord was designed. Functionalization of gold surfaces with thiolated carbon nanotubes have been conducted in order to develop suitable devices for neuronal stimulation and consequent spinal cord lesions repairing. In particular thiol groups were introduced on the graphitic surface of carbon nanotubes by means of covalent functionalization. First of all, the interaction of CNTs with gold nanoparticles has been evaluated, then a gold surface has been coated by means of contact printing technique with a homogeneous film of CNTs. This hybrid material could be useful to produce innovative electrodes for neuronal stimulation
XXV Ciclo
1985

碩士
國立臺灣科技大學
化學工程系
102
Single wall carbon nanohorns (SWNHs) is classified as one allotrope of nanocarbons which possesses interstitial and internal pores because of its unique spherical structure. Abundant spaces and sites make it become an attractive material for various applications, but prior treatment is needed in order to produce a versatile SWNHs. Facile method to introduce abundant carboxyl groups as well as to increase total surface area of SWNHs was investigated by oxidizing it with mild [HNO3]. With optimum time of 40 min to 1 h oxidation, carboxyl group functionalized, large surface area and well-dispersed SWNHs in water can be produced while maintaining its pristine morphological structure. Moreover, SWNHs-ox that was produced can be easily purified from graphite impurities, yielding an impurities-free SWNHs-ox. Current research of versatile SWNHs-ox can be used as a support for platinum nanoparticles (PtNPs) by means of amine-terminated fourth generation poly(amidoamine) (PAMAM) dendrimer (G4-NH2). With the existence of G4-NH2, dendrimer-encapsulated platinum nanoparticles (Den(PtNPs)) around 4 nm in size were homogeneously decorated and firmly attached on the SWNHs-ox surface. PtNPs content up to around 40 wt% can be achieved in current research. Three electrode system using dielectrophoretic (DEP) chip was used to analyze the SWNHs-ox-Den(PtNPs) electrocatalytic activity. With the help of G4-NH2, the catalyst possessed high durability since the deposition was still retained on the working electrode even after CV scanning of 250 cycles. More PtNPs content introduced results in higher electrocatalytic activity of catalyst, but the distribution of Den(PtNPs) also played an important role to enhance its electrocatalytic activity. Nevertheless, compact nanocarbon (carbon nanotube, graphene) was preferred for electrocatalyst application.

碩士
國立臺灣科技大學
化學工程系
102
Single walled carbon nanohorns (SWNHs) is a horn-shaped sheath aggregate of graphene sheets and is expected high potential of applications including drug delivery system. Then surface modification of SWNHs is an important research direction for the adequate application. In this study, the oxidation of SWNHs was performed by acid-treatment, where 2 h reaction was preferable, because it produces enough carboxyl groups and less defect of graphene sheet. Thus acid-treated SWNHs is more dispersible in water than commercial SWNHs. The strategy in this study is biological application of SWNHs as drug delivery system. SWNHs were conjugated with folic acid (FA) molecules for targeting specific cell with folate receptors. Moreover, SWNHs were protected by poly(amido amine) (PAMAM) dendrimer for increasing poor dispersibility of SWNHs-FA. The OH-terminated PAMAM dendrimer (DenOH) is preferably used to be chemically immobilized on SWNHs than NH2-terminated Dendrimer (DenNH2), since SWNHs-DenOH shows higher dispersibility in water than SWNHs-DenNH2. Five drugs (temozolomide, phthalocyanine, doxorubicin, camptothecin and protoporphyrin) were selected as anticancer drugs in this study, because these have different therapeutic advantages and behaviors for the tumors. The controlled loading of drug on SWNHs and SWNHs-DenOH-FA carriers was investigated. The loading capacity of drug on SWNHs-DenOH-FA was always higher than on SWNHs, since DenOH gives additional hydrogen interaction with drug, while the loading of drug on SWNHs can occur via π-π stacking, hydrogen bonding and traping inside interior space. Release profile shows strong pH dependence, and drugs on SWNHs-DenOH-FA were less released than on SWNHs, because the interaction with dendrimer keeps drugs on carrier and DenOH-FA gives steric hindrance for removal of drugs.

碩士
國立臺灣科技大學
化學工程系
106
Carbon nanohorns as the drug carrier were modified by attaching the carbon dots coated iron oxide nanoparticles (CNH/Fe3O4@C) in order to perform multiple therapies and to improve their performance. CNH/Fe3O4@C has been successfully synthesized as previously reported for combination therapy of hyperthermia and chemotherapy. Iron oxide nanoparticles that showed a good magnet response are responsible to hyperthermia. Meanwhile, the carbon dots due to its ability to produce singlet oxygen as previous report are responsible to photodynamic therapy (PDT). Towards chemotherapy study, CNH/Fe3O4@C enhanced the doxorubicin (DOX) loading, DOX release and also gemcitabine loading, gemcitabine release. The temperature dependency of DOX release and gemcitabine release was also measured and resulted higher drug release in higher temperature. Towards the PDT study, the singlet oxygen generated by CNH/Fe3O4@C was examined. Furthermore, the combination of drug release and light irradiation has been performed and showed a good outcome in drug release.

碩士
國立臺灣科技大學
化學工程系
104
Magnetic nanoparticles for hyperthermic treatment of cancers have gained significant attention in recent years. In particular, iron oxide nanoparticles are being actively investigated to achieve highly efficient destruction of carcinogenic cells through magnetic hyperthermia treatments. However, magnetic nanoparticles, Fe3O4, tend to aggregate to form the thermodynamically favored bulk metal, which results in the loss of magnetism and dispersibility of naked magnetic nanoparticles. The highly dispersible magnetic carbon nanostructures may exhibit favorable chemical reactivity and minimal cytotoxicity. This offers promising opportunities in biomedical applications. Therefore, in this research, Fe3O4 magnetite nanoparticles with diameter under 20 nm were synthesized by using co-precipitate method. Moreover, the surface of Fe3O4 magnetite nanoparticles was coated with carbon dots (Fe3O4@C) by hydrothermal process which led to the appearance of the hydrophilic functional group (-COOH and –NH2) on magnetite surface. Additionally, acid-treated SWNH/magnetite hybrid nanoparticles were prepared by different methods which were the amidation of Fe3O4@C with acid-treated SWNHs and the direct synthesis of Fe3O4 on acid-treated SWNHs via ionic interaction. TEM images of SWNHs/Fe3O4@C demonstrated that some SWNHs were attached by the aggregate of Fe3O4@C particles. However, TEM images of SWNHs/Fe3O4 showed that SWNHs were attached to clusters of magnetite particles which completely and homogeneously surrounded SWNHs. These results reveal a possibility to improve the magnetite dispersion by using functionalized carbon nanohorns.

碩士
逢甲大學
纖維與複合材料學系
107
In this study, we prepared aluminum/carbon nanohorn and aluminum/carbon nanotube composites by powder metallurgy method, and discussed also the dispersibility and shape of the material powders of aluminum/carbon nanohorn and aluminum/carbon nanotube composites. The raw material of the composite material was 6003 aluminum alloy powder as a substrate, and two carbon materials (carbon nanohorn, carbon nanotube) were additives. We also analyzed the effect of carbon material amount on the tensile and compressive properties of aluminum/carbon composites. Finally, we explored weather aluminum alloys and carbon materials would produce new alloy phases by XRD analysis. The experiment is divided into two parts: The first part discusses the effects of different processes on the powder’s dispersibility of aluminum/carbon nanohorn and aluminum/carbon nanotube composites. The first process is a wet ball milling method; the second process is a method of adding a wetting agent to pre-disperse the nano powders before performing wet ball milling. Both are using the same process parameters and different dispersion methods to explore the dispersion effect of the powders. The experimental results showed the surfaces of the powders were rough and smooth after the first processing or the second processing, and both dispersion methods were mixed well. The compression performance test of the two process composites, compared with the pure aluminum substrate, revealed that the hardness and Young's modulus were increased with the addition of the carbon nanotubes and the carbon nanohorns, although the failure work, the load and the displacement are decreased. This demonstrated that the effect of reinforcement is obtained, and the composite material also becomes brittle. The rigid reinforcing effect of adding the wetting agent (Process 2) was more obvious (the Young's modulus increased greatly), but the tensile performance test in this study is not as expected, due to the structure being too loose. The second part discusses the effects of different carbon material additions on the mechanical properties of aluminum/ carbon nanohorn and aluminum/carbon nanotube composites, and further explores which carbon material structure has the best reinforcing effect. The experimental results showed that the addition of either carbon nanotubes or carbon nanohorn could effectively improve the hardness and Young's modulus, and the highest Young's modulus was obtained when the addition amount is 1.5 wt%, and the reinforcing effect of carbon nanohorn was better than carbon nanotube. The destructive work, the falling load and the decreasing displacement were all decreased, and the hardness of the composites made of carbon nanotube and the carbon nanohorn were not identical. XRD analysis showed that the both composites could not formed a new alloy phase, the carbon material couldn’t be effectively embedded in the lattice of aluminum. Due to the limitations of forming conditions, the current results cannot be applied to the industry. For subsequent experiments in the future, the pressure and sintering temperature should be increased to achieve abundant compaction to improve mechanical properties, or to prepare the composite powders by using a wetting agent for pre-dispersion of nano powders, and then by hot extrusion. The composite material is prepared in a manner such that the reinforcing material can be directional and orintated in the extrusion process, thereby improving its properties to meet the needs of the industry.

For the past three decades, newly discovered carbon nanostructures such as fullerenes, graphene and carbon nanotubes (CNTs) have revolutionized the field of nanoscience, introducing many practical and potential applications pertaining to their exceptional structural, mechanical, thermal, and optoelectronic properties. Raman spectroscopy has been an instrumental technique for characterizing these materials due to its non-destructive nature and high sensitivity to the material responses. While Raman spectroscopy is broadly used for identifying specific material types and quality, it has also been increasingly useful as a tool for probing the electronic and excitonic properties, as well as their interplay with the vibrational properties in the aforementioned carbon nanomaterials. In this dissertation, we present our Raman-related research on carbon nanotubes and a new member of the nano-carbon family - carbon nanohoops (cycloparaphenylenes, or CPPs). We discuss our new findings on the resonance Raman spectroscopy (RRS) of various semiconducting CNTs, with the focus on the Raman excitation profiles (REPs) for the G-band. The asymmetric lineshapes observed in the G-band REPs for the second excitonic (E22) transition of these CNTs contradict a long-held approximation, the Franck-Condon principle, for the vibronic properties of the carbon nanotubes. In addition, the G-band REPs from the closely spaced E33 and E44 transitions are investigated, and we demonstrate that these excitonic levels exhibit significant quantum interference effects between each other. We also present the first comprehensive study of Raman spectroscopy of CPPs. Analogously to CNTs, we show that Raman spectroscopy can be used to identify CPPs of different sizes. A plethora of Raman modes are observed in these spectra, including modes that are comparable to those of CNTs, such as the G-band, as well as Raman peaks that are unique for CPPs. Calculated Raman spectra using density functional theory (DFT) are compared with the experimental results for the assignment of different modes. Furthermore, we refine our knowledge of the CPP Raman modes by concentrating on the even-numbered CPPs. By taking advantage of the symmetry arguments in the even [n]CPPs, we are able to utilize group theory and accurately identify the size dependences of different Raman-active modes.