Pour résoudre la limitation inhérente au procédé d’impression laser LIFT, une approche utilisant une double impulsion (DP-LIFT) a été développée au cours de cette thèse. Dans ce processus, une irradiation laser de durée de quelques dizaines de microsecondes crée un bain de métal en fusion et une seconde impulsion ultra-brève induit le mouvement du fluide, la formation d’un jet ou d’une goutte et le transfert du métal liquide. Cette thèse présente une étude expérimentale détaillée sur le processus DP-LIFT. L'influence des paramètres des deux irradiations laser a été étudiée en s’appyuant sur un ensemble de méthodes d'observation. Pour étudier l’influence de ces paramètres sur la dynamique de l’éjection, un modèle basé sur la conservation de l’énergie a été utilisé. De plus, nous avons démontré que, pour certaines configurations des diamètres respectifs des deux spots lasers, des nanojets focalisés étaient générés. Enfin, en conservant une épaisseur fixe du film métallique, des gouttelettes uniques, sans débris, d'un diamètre allant de 670 nm à 6,0 µm ont été imprimées avec une reproductibilité élevée. des matrices de piliers ont également été imprimées pour démontrer le potentiel de la méthode LIFT à double impulsion pour la fabrication de micro-structures 3D / To solve the inherent limitation of Laser-induced Forward Transfer (LIFT), a double pulse LIFT (DP-LIFT) approach has been developed in this thesis. In this process, a first long pulse laser irradiation creates a melted metal pool and a second ultrashort pulse induces the fluid motion and initiates the jetting transfer. This thesis provides a detailed experimental study on the DP-LIFT process. The influence of double pulse parameters on the jetting phenomena has been carefully studied by means of various observation methods. To predict the jetting behaviors, an energy balanced model has been used. Moreover, we demonstrated that for some configurations of the respective diameters of the two lasers, focused nanojets are generated from the melting pool. Finally, from a fixed thickness of the donor film, debris-free single droplets with diameters ranging from 670 nm to 6.0 µm have been printed with high reproducibility. 2.5 D pillars matrix are printed to demonstrate the potential of the double pulse LIFT method for the fabrication of 3D micro-structures.

With the semiconductor industry racing toward a historic transition, nano chips with less than 45 nm features demand I/Os in excess of 20,000 with multi-core processors aggregately providing highest bandwidth at lowest power. On the other hand, emerging mixed signal systems are driving the need for 3D packaging with embedded active components and ultra-short interconnections. Being able to provide several fold increase in the chip-to-package vertical interconnect density is essential for garnering the true benefits of nanotechnology that will utilize nano-scale devices. Electrical interconnections are multi-functional materials that must also be able to withstand complex, sustained and cyclic thermo-mechanical loads. Device- to- system board interconnections are typically accomplished today with either wire bonding or solders. Both of these are incremental and run into either electrical or mechanical barriers as they are extended to higher interconnections densities. Downscaling traditional solder bump interconnect will not satisfy the thermo-mechanical reliability requirements at very fine pitches. Other approaches such as compliant interconnects require lengthy connections and are limited in terms of electrical properties. A novel chip-package interconnection technology is developed to address the IC packaging requirements and to introduce innovative design and fabrication concepts that will further advance the performance of the chip, the package, and the system board. The nano-structured interconnect technology simultaneously packages all the ICs intact in wafer form with quantum jump in the number of interconnections with the lowest electrical parasitics. The intrinsic properties of nano materials also enable several orders of magnitude higher interconnect densities with the best mechanical properties for the highest reliability and yet provide higher current and heat transfer densities. This thesis investigates the electrical and mechanical performance of nano-structured interconnections through modeling and test vehicle fabrication. Test vehicles with nano-interconnections were fabricated using low cost electro-deposition techniques and assembled with various bonding interfaces. Interconnections were fabricated at 200 micron pitch to compare with the existing solder joints and at 50 micron pitch to demonstrate fabrication processes at fine pitches. Experimental and modeling results show that the proposed nano-interconnections could enhance the reliability and potentially meet all the system performance requirements for the emerging micro/nano-systems.

Le but de la Nano- Opto- Mécanique et Electronic à base de graphène est d'utiliser des membranes de graphène en suspension comme blocs de construction pour aborder le couplage entre l'optique, la mécanique et l'électronique dans ce nouveau matériau. Avec un module d'Young similaire à celui du diamant (1 TPA), le graphène est une membrane extrêmement rigide, légère et mince (epaaisseur de seulement un atome) qui peut supporter son propre poids sans effondrement ou la rupture lorsqu'il est suspendu. Ces membranes, intégrées dans des dispositifs mécaniques, peuvent être actionnés à partir de DC jusqu'à des fréquences de vibration mécaniques très élevées (GHz). En outre, le graphène est un gaz d'électrons 2D exposé pour lequel une porte électrostatique tunes considérablement la densité de porteurs de charge et ses propriétés optiques. Last but not least, il offre une architecture unique pour effectuer la fonctionnalisation physico-chimiques et obtenir des matériaux hybrides combinant les propriétés particulières des espèces chimisorbées avec ceux du graphène. / The aim of the Graphene Nano- Opto- Mechanics and Electronics is to use suspended graphene membranes as building blocks to address the coupling of optics, mechanics and electronics in this novel material. With a Young modulus similar to that of diamond (1 TPa), graphene is an extremely stiff, light and atomically thin membrane that can withstand its own weight without collapsing or breaking when suspended. Such membranes, integrated as mechanical devices, can be actuated from DC up to very high mechanical vibration frequencies (GHz). Moreover, graphene is an exposed 2D electron gas for which an electrostatic gate dramatically tunes the charge carrier density and its optical properties. Last but not least, it provides a unique architecture to perform physico-chemical functionalization and obtain hybrid materials combining the peculiar properties of adsorbed and chemisorbed species with the graphene ones.

Different types of plasmonic nanostructures are proposed and examined experimentally and theoretically, with a view towards sensing applications. First, a self-assembly approach was developed to create arrays of well-ordered glass-supported gold nanoparticles (AuNPs) with controllable particle size and inter-particle spacing. Then, a periodic array of gold nano-disks (AuNDs) supported by a Bragg reflector was proposed and examined in a search for Fano resonances in its optical response. Arrays of heptamer-arranged nanoholes (HNH) in a thin gold film were also proposed and explored theoretically and experimentally, revealing a very rich spectrum of resonances, several exhibiting a Fano lineshape. A commercial implementation of the vectorial finite element method (FEM) was used to model our plasmonic structures. Taking advantage of the periodic nature of the structures, a unit cell containing a single element was modelled. The transmittance, reflectance or absorbance spectra were computed, and the associated electromagnetic fields were obtained by solving the vector wave equations for the electromagnetic field vectors throughout the structures, subject to the applicable boundary conditions, and the applied source fields. The sensing performance of the structures, based on the bulk sensitivity, surface sensitivity and figure of merit (FOM) was calculated. First, a novel bottom-up fabrication approach was applied (by our collaborators) to form a periodic array of AuNPs with controllable size over large areas on SiO2 substrates. In this method, self-assembly of block copolymer micelles loaded with metal precursors was combined with a seeding growth route to create ordered AuNPs of desired size. It was shown that this new fabrication method offers a new approach to tune the AuNP size and edge-to-edge inter-particle spacing while preserving the AuNP ordering. The optical characteristics of the AuNP arrays, such as their size, interparticle spacing, localized surface plasmon resonance (LSPR) wavelength, and bulk sensitivity, were examined, numerically and experimentally. This proposed novel fabrication method is applicable for low-cost mass-production of large-area arrays of high-quality AuNPs on a substrate for sensing applications. Then, we proposed and examined the formation of Fano resonances in a plasmonic-dielectric system consisting of uncoupled gold nano-disk (AuND) arrays on a quarter-wave dielectric stack. The mechanism behind the creation of Fano resonances was explained based on the coherent interference between the reflection of the Bragg stack and the LSPPs of the AuNDs. Fano parameters were obtained by fitting the computational data to the Fano formula. The bulk sensitivities and figure of merit of the Fano resonances were calculated. This plasmonic structure supports Fano resonances with a linewidth around 9 nm which is much narrower than the individual AuND LSPP bandwidth ( 80 nm) and the Bragg stack bandwidth ( 100 nm). Supporting Fano resonances with such a narrow linewidth, the structure has a great potential to be used for sensing applications. Also, this metallic-dielectric nanostructure requires no near-field coupling between AuNDs to generate the Fano resonances. So, the AuNDs can be located far enough from each other to simplify the potential fabrication process. The optical properties of HNH arrays on an SiO2 substrate were investigated, numerically and experimentally. Helium focused ion beam (HeFIB) milling was applied (by Dr. Choloong Hahn) to fabricate well-ordered and well-defined arrays of HNHs. Transmittance spectra of the structures were obtained as the optical response, which exhibits several Fano resonances. Then, the mechanism behind the formation of the Fano resonances was explained, and the sensing performance of the structure was inspected by measuring the bulk sensitivities. This array of nanohole cluster is exciting because it supports propagating SPPs and LSPPs, and also Wood’s anomaly waves, which makes the optical response very rich in excitations and spectral features. Also, as a periodic array of sub-wavelength metallic nanoholes, the system produces extraordinary optical transmission - highly enhanced transmission through (otherwise) opaque metallic films at specific wavelengths, facilitating measurement acquisition in transmission.

[EN] The aim of this PhD thesis is the study, development and characterization of biodegradable and biocompatible polymeric-based nanomaterials, such as polylactic acid (PLA). Those nano materials are loaded with multiwalled carbon nanotubes (MWCNT's) and Halloysite nanotubes (HNT's) in order to determine the thermal, rheological and mechanical characteristics and their applications in different areas of additive manufacturing. The addition of nanofiller in the polymeric matrix stiffened the material. Thus, in order to modify its stiffness, a study was carried out on the addition of vegetable plasticizer maleonized linseed oil (MLO) in the nanocomposites, obtained by mixing, by means of a co-rotating twin-screw extruder. In the first stage, PLA is mixed with MWCNTs and HNTs, with contents 0.5wt.%, 0.75wt.% y 1wt. % by weight, which was obtained by melting in a co-rotating twin-screw extruder. Then, the nanomaterials were characterized, the viscosity of the nanocomposites produced by capillary rheometry was obtained and the fluidity index analysis was carried out. During the second stage and in order to improve the fluidity of the nanomaterials, an analysis was made on the influence maleonized linseed oil (MLO) has a lubricant on the thermal, rheological and morphological properties. In order to do so, the same techniques used during the first stage were used: DSC, Capillary Rheometry, MFI. Addionally, field emission electron microscopy (FESEM) was used to analyse the morphology of the composites, with cryogenized samples. Hereafter, morphological tests of the material were conducted by FESEM. Mechanical tests were also performed on injected samples. Moreover, the printed samples were analysed using filament previously obtained by means of a FILABOT EX2 FILAMENT EXTRUDER extruder. More samples were also printed on a Tumaker NX Pro Pellets 3D printer, which were tested for tensile, flexural and resilence. Finally, developing this PhD thesis increases the technological possibilities of nanocomposites in 3D printing applications. This is due to the encouraging results of materials with high chances of being used both in the industrial and surgical fields. / [ES] El objetivo de la presente tesis de doctoral es el estudio, desarrollo y caracterización de nano materiales con base polimérica biodegradable y biocompatible como el ¿acido poli láctico (PLA), cargados con nano tubos de carbono de pared múltiple (MWCNT's) y nano tubos de Halloysita (HNT's), para determinar las características térmicas, reológicas y mecánicas y sus aplicaciones en diferentes áreas de la fabricación aditiva. La adición de nano carga en la matriz polimérica rigidizo el material, por tal motivo para modificar su rigidez, se llevó a cabo el estudio de la incorporación de plastificante vegetal aceite de linaza maleonizado (MLO) en los nano compuestos, los cuales se obtuvieron por mezclado por extrusora de doble husillo co-rotante. En la primera etapa se realiza la mezcla de PLA con MWCNTs y HNTs, con contenidos de 0.5wt.%, 0.75wt.% y 1wt.% en peso, el cual se obtuvo mediante fusión en una extrusora de doble tornillo co-rotativa. Se caracterizaron los nano materiales, se obtuvo la viscosidad de los nano compuestos obtenidos en reometría capilar y se ejecutó también el análisis del Índice de fluidez Durante la segunda etapa y con el fin de mejorar la fluidez de lo nano materiales, se analizó la influencia del aceite de linaza maleinizado (MLO) como lubricante en las propiedades térmicas, reológicas y morfológicas, para lo cual se ocuparon las mismas técnicas utilizadas en la primera etapa DSC, Reometría Capilar, MFI, y adicionalmente para analizar la morfología de los compuestos se utilizó microscopia electrónica de emisión de campo (FESEM), con muestras criogenizadas. Se realizaron pruebas morfológicas del material realizadas por FESEM, y también se realizaron pruebas mecánicas con probetas inyectadas. Además se analizaron las probetas impresas partiendo de filamento previamente obtenido por medio de un extrusor FILABOT EX2 FILAMENT EXTRUDER. También se realizó la impresión de probetas en una impresora 3D Tumaker NX Pro Pellets, los cuales se los realizo ensayos de tracción, flexión y resiliencia. Con el desarrollo de esta tesis de doctorado, se aumentan las posibilidades tecnológicas de los nanocompuestos en aplicaciones de impresión 3D. Siendo resultados alentadores de materiales con altas posibilidades de ser utilizados tanto en el ámbito industrial como en el ámbito quirúrgico. / [CAT] L’objectiu de la present tesi de doctoral ´es l’estudi, desenvolupament i caracterització de nano materials amb base polimèrica biodegradable i biocompatible com l’àcid polilàctic (PLA), carregats amb nano tubs de carboni de paret múltiple (MWCNT s) i nano tubs de halloysita ( HNT s), per a determinar les característiques t`ermiques, reològiques i mecàniques i les seves aplicacions en diferents àrees de la fabricació additiva. L’addicio de nano càrrega en la matriu polimèrica elevar la rigidesa del material, per tal motiu i per modificar la seva rigidesa, es va dur a terme l’estudi de la incorporació de plastificant vegetal oli de llinosa maleonizat (MLO) en els nano compostos, els quals es van obtenir per barrejat per extrusora de doble cargol co-rotant. En la primera etapa es realitza la barreja de PLA amb MWCNTs i HNTs, amb continguts de 0.5wt. %, 0.75wt. % I 1wt. % en pes, el qual es va obtenir mitjan¸cant fusió en una extrusora de doble cargol co-rotativa. Es van caracteritzar els nano materials, es va obtenir la viscositat dels nano compostos obtinguts en reometria capil·lar i es va executar també l’anàlisi de l’´Index de fluïdesa Durant la segona etapa i per tal de millorar la fluïdesa del nano material, es va analitzar la influència de l’oli de llinosa maleinizat (MLO) com a lubricant en les propietats tèrmiques, reològiques i morfològiques. Per això, es van fer sevir les mateixes tècniques utilitzades en la primera etapa DSC, Reometria Capilar, MFI, i addicionalment per analitzar la morfologia dels compostos es va utilitzar microscòpia electrònica d’emissió de camp (FESEM), amb mostres criogenitzades. Es van realitzar proves morfològiques del material realitzades per FESEM, i també es van realitzar proves mecàniques amb provetes injectades. A més es van analitzar les provetes impreses partint de filament prèviament obtingut per mitjà d’un extrusor FILABOT EX2 filament extruder. També es va realitzar la impressió de provetes en una impressora 3D Tumaker NX Pro Pellets, els quals se’ls va realitzar assajos de tracció, flexió i resiliència. Amb el desenvolupament d’aquesta tesi doctoral, s’augmenten les possibilitats tecnològiques dels nanocompostos en aplicacions d’impressi´o 3D. Sent resultats encoratjadors de materials amb altes possibilitats de ser utilitzats tant en l’àmbit industrial com en l’àmbit quirúrgic. / Cobos Maldonado, CM. (2021). Caracterización de nano compuestos a base de nanotubos de carbono y fibras para aplicaciones en tecnologías aditivas (impresión 3D) [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/176061 / TESIS

In this study nano-patterning was carried out using two different nano-optic devices namely- the NSOM and Fresnel zone plate. In the first study, NSOM was used to generate nano-patterns on selected semiconducting (Si and Ge) and metallic (Cr, Cu and Ag) targets under different laser pulse durations, laser energies and number of laser pulses. Based on the experimental results, femtosecond laser pulses, provided lower pattern generation thresholds on targets but higher damage thresholds to the NSOM probes at the wavelength (~400-410 nm) studied, compared with nanosecond laser pulses. Three different mechanisms were identified as the dominant processes for pattern generation under different conditions, namely nano-scale laser ablation, nano-scale thermal oxidation and nano-scale melting/recrystallization of the targets. Furthermore, the resulting nano-patterns also showed a significant dependence on the optical properties (i.e., absorption coefficient and surface reflectivity) of the target material. By comparing the obtained experimental results, it was concluded that the optical energy transport from the NSOM probe to the target dominates the pattern generation when femtosecond laser is applied to the NSOM system. When nanosecond laser is applied, both the thermal and optical energy transported from the NSOM probe to the targets attribute to the obtained morphology of nano-patterns on different targets under the experimental conditions studied. In the second study, a traditional Fresnel zone plate with a focus length of 3 micrometres was fabricated with a novel lift-off process in e-beam lithography. The fabrication process involved, using a HSQ/PMMA bi-layer in a negative tone lift-off process with a layer of conducting polyaniline for charge dissipation. HSQ was used as the high resolution negative resist for e-beam patterning and the PMMA under-layer was used to enable a HSQ lift-off process. The fabricated Fresnel zone plate was used to generate nano-patterns on a UV sensitive photoresist using nanosecond laser light with lamda~409nm. The smallest pattern sizes generated was close to the diffraction limit. Nano-pattern sizes generated on the photoresist were comparable with a numerically calculated intensity distribution at the focus spot of the designed Fresnel zone plate obtained from Scalar Diffraction Theory.

<p>Predmet izučavanja ove disertacije je ispitivanje mogućnosti&nbsp; primene stabilisanog nano Fe(0)&nbsp; i &bdquo;zelenom&ldquo; sintezom produkovanog nano&nbsp; Fe(0)&nbsp; u uklanjanju Cr(VI), Cd(II), Cu(II), Ni(II), Pb(II) i As(III)&nbsp; iz vode.&nbsp; Sinteza nano Fe(0) za stabilizaciju izvr&scaron;ena je konvencionalnom metodom&nbsp; redukcije gvožđa sa natrijum borhidridom&nbsp; u prisustvu materijala za stabilizaciju: kaolinita,&nbsp; bentonita i karboksimetil celuloze. Za &bdquo;zelenu&rdquo; sintezu nano Fe(0) kori&scaron;ćeno je li&scaron;će drveća: hrasta, duda i vi&scaron;nje.&nbsp; Karakterizacija&nbsp; dobijenih nanomaterijala izvr&scaron;ena je transmisionom i skenirajućom elektronskom mikroskopijom. Rezultati karakterizacije su pokazali da se tokom sinteze nano Fe(0) natrijum borhidridom i stabilizacije kaolinitom, bentonitom i karboksimetil celulozom, formiraju nano čestice Fe(0) veličine 20 do 90 nm, dok su veličine čestica nano Fe(0) sintetisanih &bdquo;zelenom&ldquo; metodom iznosile 10-30 nm i okarakterisane su kao nano čestice sfernog oblika, različitih veličina bez značajane aglomeracije.&nbsp; Primena nano&nbsp;Fe(0) na efikasnost&nbsp; uklanjanja metala iz vode ispitivana je pri različitim uslovima:&nbsp; uticaju doze nanomaterijala, početne koncentracije&nbsp; metala, pH vrednosti rastvora i kontaktnog vremena.&nbsp; Dobijeni rezultati prilikom ispitivanja uticaja&nbsp; doze nanomaterijala&nbsp; na efikasnosti uklanjanja odabranih metala iz vode primenom stabilisanih i &bdquo;zelenih&ldquo; nanomaterijala&nbsp; pokazali&nbsp; su&nbsp; da se povećanjem doze nanomaterijala&nbsp; povećava efikasnost uklanjanja.&nbsp; Prilikom primene stabilisanih nanomaterijala, koncentracije 14.00 gFe(0)/l,&nbsp; postignute&nbsp; su visoke efikasnosti uklanjanja, već pri dozama od&nbsp; 2 ml, dok je efikasnost uklanjanja primenom&nbsp; &bdquo;zelenih&ldquo; nanomaterijala koncentracije 1,395 gFe(0)/l bila niža. Prilikom ispitivanja uticaja pH vrednosti na uklanjanje metala iz vode primenom ispitivanih nanomaterijala, određeni &nbsp;su optimalni opsezi pH vrednosti pri kojima se postiže najveća adsorpcija metala&nbsp; na ispitivanim nanomaterijalima.&nbsp; Veza između metala&nbsp; i&nbsp; ispitivanih nanomaterijala obja&scaron;njena je modelovanjem Langmuir-ove i Freunlich-ove&nbsp; adsorpcione izoterme. Veće adsorpcione kapacitete prilikom adsorpcije svih ispitivanih metala pokazali su nanomaterijali produkovani &bdquo;zelenom&ldquo; sintezom u odnosu na stabilisane nanomaterijale, &scaron;to je povezano sa veličinom čestica, tj. manje nanočestice nanomaterijala produkovanih &bdquo;zelenom&rdquo; sintezom imaju veću&nbsp; specifičnu povr&scaron;inu i samim tim mogu&nbsp; ponuditi&nbsp; vi&scaron;e reaktivnih mesta, veću reaktivnost i bolju disperziju. Ispitivanje kinetike adsorcije&nbsp; Cr(VI), Cd(II), Cu(II), Ni(II), Pb(II) i As(III) na ispitivanim stabilisanim i &bdquo;zelenom&ldquo; sintezom produkovanim nanomaterijalima pokazalo je veoma brzu reakciju adsorpcije metala na ispitivanim&nbsp;nanomaterijalima i&nbsp; bolje slaganje eksperimentalno dobijenih podataka sa pseudo-drugim kinetičkim modelom.&nbsp; Rezultati dobijeni u ovom&nbsp; istraživanju omogućiće procenu&nbsp; primene nano Fe(0) za uklanjanje metala iz vode, posebno adsorpciju metala iz vode kao i odabir najefikasnijeg i najekonomičnijeg adsorbensa za uklanjanje različitih metala iz vode.</p> / <p>This work is concerned with exploring the possibility&nbsp; of&nbsp; application of&nbsp; stabilized nano Fe(0)&nbsp; and nano Fe (0) produced by &ldquo;green&rdquo; synthesis&nbsp; in the&nbsp; removal&nbsp; of Cr(VI), Cd(II), Cu(II), Ni(II), Pb(II)&nbsp; and&nbsp; As(III)&nbsp; from&nbsp; the&nbsp; water.&nbsp; Synthesis of nano Fe(0) for the stabilization is carried out according to conventional method of iron reduction with sodium borohydride in the presence of a material for stabilization: kaolinite, bentonite and carboxymethyl cellulose. Leaves of oak, mulberry and cherry trees used for&nbsp; &ldquo;green&rdquo;&nbsp; synthesis of nano Fe(0). Characterization of nanomaterials&nbsp; was performed by transmission and scanning electron microscopy.&nbsp; The&nbsp; characterization&nbsp; results&nbsp; have shown that during the synthesis and stabilization of nano Fe (0) process formed nanoparticles with size from 20 to 90 nm, while the nano Fe (0) particles synthesized by &quot;green&quot; method were within the&nbsp; size of&nbsp; 10-30 nm and characterized as spherical nanoparticles with&nbsp; various sizes without significant agglomeration.&nbsp; Application of nano Fe (0) on the&nbsp; removal&nbsp; efficiency of&nbsp; metals from water was studied under different conditions: the influence of&nbsp; nanomaterials&nbsp; dose, the initial metal concentrations, pH value of the solution&nbsp; and the contact time. The results obtained during the examination of the impact of nanomaterial&nbsp; dose&nbsp; on the&nbsp; removal&nbsp; efficiency&nbsp; of selected metals from water&nbsp; have shown that increasing&nbsp; of nanomaterial&nbsp; dose increases removal efficiency. High removal efficiency is achieved when used&nbsp; 2 ml of stabilized nanomaterials, concentration of 14.00 gFe(0)/L, while when &quot;green&quot; nanomaterials,&nbsp; concentration&nbsp; of&nbsp; 1,395&nbsp; gFe(0)/L,&nbsp; were&nbsp; used&nbsp; the removal efficiency&nbsp; was&nbsp; lower.&nbsp; The optimal ranges of pH values&nbsp; at which&nbsp; the tested&nbsp; nanomaterials&nbsp; reach the maximum adsorption of metals&nbsp; were obtained, during the examination of&nbsp; the influence of pH value on removal of metals from water by using the tested nanomaterials&nbsp; The&nbsp; relation&nbsp; between&nbsp; the metals&nbsp; and tested&nbsp;&nbsp; nanomaterials is explained by modeling&nbsp; of&nbsp; Langmuir&#39;s and Freunlich&#39;s adsorption isotherm.&nbsp; Nanomaterials&nbsp; produced&nbsp; by&nbsp; &quot;green&quot; synthesis&nbsp; showed higher&nbsp; adsorption capacity&nbsp; than&nbsp; stabilized&nbsp; nanomaterials, which is related&nbsp; with particle size, i.e. the&nbsp; nanoparticles&nbsp; produced by&nbsp; &quot;green&quot; synthesis&nbsp; have&nbsp; less particles, higher specific surface area and therefore can offer more reactive sites, greater reactivity and better dispersion. Kinetics&nbsp; tests&nbsp; showed a very fast adsorption of metal&nbsp; on&nbsp; the tested nanomaterials and better agreement with the experimental data to&nbsp; second&nbsp; pseudo-kinetic model.&nbsp; The results obtained in this study will enable the assessment of the application of nano&nbsp; Fe (0) for the removal of metals from water, especially for the adsorption of metals from water as well as the selection of the most&nbsp; efficient and most economical of the adsorbent for the removal of various metals from water.</p>

Nano-DESI Mass spectrometry imaging of eicosanoids in mouse kidney tissue using selected ion monitoring. Nano-DESI mass spectrometry imaging (MSI) is a technique for label-free spatial and molecular characterization of surfaces and biological samples. Eicosanoids are lipid mediators derived from eicosapolyenoic acid- products of arachidonic acid oxidation. Eicosanoids have been of interest to the medical field for many years. Major focus on this lipid class came from the development of nonsteroidal anti-inflammatory drugs (NSAIDs), some of these including aspirin, naproxen, ibuprofen, and acetaminophen work by blocking either the formation or the effects of eicosanoids. These lipids also play important roles in various body functions (cardiovascular, renal, gastrointestinal, neuronal) and as mediators of inflammation, asthma, fever, pain, hypertension, and stroke. Typically, eicosanoids occur in subnanomolar concentrations, despite their high level of bioactivity, which makes them significantly more difficult to analyze via direct mass spectrometry. Here, selected ion monitoring (SIM) is used to increase the signal-to-noise of the identified eicosanoids compared to a broadband full scan mode.

The advent of highly sophisticated drugs designed to interfere with specific cellular functions has created the demand for “intelligent” carriers that can efficiently deliver therapeutic agents in response to a pathophysiogical condition. Nanoscale intelligent systems can maximize the efficacy of therapeutic treatments in numerous ways because they have the ability to rapidly detect and response to disease states directly at the site and sparing physiologically healthy cells and tissues, thereby improving a patient’s quality of life. Nanoparticle fabrication has primarily relied on emulsions, self-assembly and micelles based methods which inherently generate polydisperse spherical particles with little control over particle geometry. Despite significant progress in such drug delivery systems, critical limitations remain in synthesizing nanocarriers with highly controllable architecture (size, shape or aspect ratio) that can, at the same time, impart response-sensitive release mechanisms. These parameters are essential for controlling the in-vivo transport, bio-distribution, and drug release mechanisms. The objective of my dissertation is to employ the nanofabrication technique Step and Flash Imprint Lithography (S-FIL) to synthesize stimuli-responsive nanocarriers of precise architectures and composition. Applying S-FIL technology, fabrication of nanocarriers of a variety of shapes and sizes (down to 36nm length scale) that are also environmentally responsive by incorporating enzymatically-degradable peptides into the nanocarrier hydrogel matrix, to provide triggered release of encapsulated therapeutic agents in response to specific pathophysiological conditions, has been accomplished. Besides disease-responsive release, the two key properties of an effective nanocarrier are (a) efficient targeting to specific tissues and cells and (b) avoiding rapid clearance and remaining in circulation in the blood stream for a significant amount of time to increase particle uptake in target tissues. These two properties are expected to be dependent on the shape and size of the carriers. Using various shape and size S-FIL fabricated nanoparticles, the effects of particle geometry on intracellular uptake has also been evaluated. In this dissertation, I will present the extensive work that has been done in the fabrication and optimization of the S-FIL nanocarriers, evaluation of the nanocarrier’s in vitro properties, and evaluation of the effects of nanocarrier geometry on intracellular uptake. / text

The research described in this Dissertation is concerned generally with the exploration of the potential use of lanthanide elements in nanostructured materials for the purpose of modification of the magnetic and optical properties. This is explored through a focus on the development of lanthanide-containing iron oxide nanosystems. Our objectives of producing lanthanide containing nanostructured materials with potentially useful optical and magnetic applications has been achieved through the development of lanthanide-doped Fe3O4 and -Fe2O3 nanoparticles, as well as a unique core-shell magnetic-upconverting nanoparticle system.Necessary background information on nanomaterials, rationale for the study of lanthanide-containing iron oxide nanosystems and context for discussion of the results obtained in each project is provided in the Introduction Chapter. The syntheses of Fe3O4 nanoparticles doped with Eu(III) and Sm(III) are discussed, along with structural characterization and magnetic property investigation of products In Chapter 2. The following Chapter expands the study of lanthanide doping to -Fe2O3, a closely related yet distinct magnetic nanoparticle system. A completely different synthesis is attempted, and comparisons between the two systems are made.The development of novel synthetic methodologies used to create such products has yielded high-quality lanthanide-containing materials and are evidenced by TEM images displaying nearly monodisperse particles in each of our efforts. The modifications to the magnetic properties resulting from lanthanide doping include theobservation of ferromagnetism in the Fe3O4 system and increased magnetic saturation of -Fe2O3 nanoparticles, and are characterized by VSM and the visual observation of magnetic alignment of products. Our efforts towards developing a novel methodology capable of producing high quality Fe3O4 nanoparticles, and subsequent characterization of products, were published in the Journal of the American Chemical Society.Optically active, magnetic, core-shell nanoparticles are investigated in Chapter 4 for the potential uses in diagnosis and treatment of cancer. This multifunctional system uses Fe3O4 as a magnetic core, shelled by upconverting lanthanide-containing nanomaterials, and is rendered biocompatible through encapsulation of the core-shell structure by a silica shell. Added functionality is achieved through amine functionalization of the silica surface, with the goal of coupling the inorganic nanoparticle with drug targeting groups. TEM results indicate successful formation of the core-shell nanoparticles, and expected magnetic and optical properties are shown by visual observation and luminescence spectroscopy, respectively.