Nanotechnology has made it possible to create materials with unique properties. This development offers new opportunities and overcomes challenges for many thermal transport applications. Yet, it requires a more fundamental scientific understanding of nanoscale transport. This thesis emphasizes how simulation, mathematical, and numerical methods can lead to more grounded studies of nanoscale thermal transport for biological and physical applications. For instance, magnetic fluid hyperthermia (MFH), an emerging cancer treatment, is a noninvasive method to selectively destroy a tumor by heating a ferrofluid-impregnated malignant tissue with minimal damage to the surrounding healthy tissue. We model the problem by considering an idealized spherical tumor that is surrounded by healthy tissue. The dispersed magnetic nanoparticles in the tumor are excited by an AC magnetic field to generate heat. The temperature distribution during MFH is investigated through a bioheat transfer relation which indicates that the P\'eclet, Joule, and Fourier numbers are the more influential parameters that determine the heating during such a thermotherapy. Thus, we show that a fundamental parametric investigation of the heating of soft materials can provide pathways for optimal MFH design. Since ferrofluid materials themselves play a key role in heating, we examine six materials that are being considered as candidates for MFH use. These are simulated to investigate the heating of ferrofluid-loaded tumors. We show that iron-platinum, magnetite, and maghemite are viable MFH candidates since they are able to provide the desired heating of a tumor which will destroy it while keeping the surrounding healthy tissues at a relatively safe temperature. Recent advances in the synthesis and nanofabrication of electron devices have lead to diminishing feature sizes. This has in turn increased the power dissipation per unit area that is required to cool the devices, leading to a serious thermal management challenge. The phonon thermal conductivity is an important material property because of its role in thermal energy transport in semiconductors. A higher thermal conductivity material is capable of removing more heat since higher frequency phonons are able to travel through it. In this thesis, the effects of surface stress on the lattice thermal conductivity are presented for a silicon nanowire. Based on a continuum approach, a phonon dispersion relation is derived for a nanowire that is under surface stress and the phonon relaxation time is employed to subsequently determine its thermal conductivity. The surface stress is found to significantly influence the phonon dispersion and thus the Debye temperature. Consequently, the phonon thermal conductivity decreases with increasing surface stress. Different magnitudes of surface stress could arise from various material coatings and through different nanofabrication processes, effects of which are generally unclear and not considered. Our results show how such variations in surface stress can be gainfully used in phonon engineering and to manipulate the thermal conductivity of a nanomaterial. The thermal transport during thermoelectric cooling is also an important property since thermoelectric devices are compact, reliable, easy to control, use no refrigerants and require lower maintenance than do more traditional refrigeration devices. We focus on the Thomson effect that occurs when there is a current flow in the presence of a temperature gradient in the material, and investigate its influence on an intrinsic silicon nanowire cooler. The temperature dependence of the Thomson effect has a significant influence on the cooling temperature. We also consider thermal nonequilibrium between electrons and phonons over the carrier cooling length in the nanowire. The results show that a strong energy exchange between electrons and phonons lowers the cooling performance, suggesting useful strategies for thermoelectric device design. / Ph. D.

Two-dimensional (2D) nanoscale confinement effects on poly(ε-caprolactone) (PCL) crystallization were probed through crystallization studies of PCL-b-poly(tert-butyl acrylate) (PCL-b-PtBA) copolymers, PCL with bulky tri-tert-butyl ester endgroups (PCL triesters), PCL with triacid end groups (PCL triacids), and magnetic nanoparticles stabilized by PCL triacid (PCL MNPs) at the air/water (A/W) interface. Thermodynamic analyses of surface pressure-area per monomer (Π−A)) isotherms for the Langmuir films at the A/W interface showed that PCL-b-PtBA copolymers, PCL triheads and PCL MNPs all formed homogenous monolayers below the dynamic collapse pressure of PCL, Π_C ~11 mN•m⁻¹. For compression past the collapse point, the PCL monolayers underwent a phase transition to three-dimensional (3D) crystals and the nanoscale confinements impacted the PCL crystalline morphologies. Studies of PCL-b-PtBA copolymers revealed that the morphologies of the LB-films became smaller and transitioned to dendrites with defects, stripes and finally nano-scale cylindrical features as the block length of PtBA increased. For the case of PCL triester, irregularly shaped crystals formed at the A/W interface and this was attributed to the accumulation of bulky tert-butyl ester groups around the crystal growth fronts. In contrast, regular, nearly round-shaped lamellar crystals were obtained for PCL triacids. These morphological differences between PCL triacids and PCL triesters were molar mass dependent and attributed to differences in dipole density and the submersion of carboxylic acid groups in the subphase. Nonetheless, enhanced uniformity for PCL triacid crystals was not retained once the polymers were tethered to the spherical surface of a PCL MNP. Instead, the PCL MNPs exhibited small irregularly shaped crystals. This nano-scale confinement effect on the surface morphology at the A/W interface was also molar mass dependent. For the small molar mass PCL MNPs, two layers of collapsed nanoparticles were observed. In a later chapter, studies of polyethylene glycol (PEG) surfactant adsorption onto phospholipid bilayers through quartz crystal microbalance with dissipation monitoring (QCM-D) measurements revealed a strong dependence of the adsorption and desorption kinetics on hydrophobic tail group structure. PEG surfactants with a single linear alkyl tail inserted and saturated the bilayer surface quickly and the surfactants had relatively fast desorption rates. In contrast, PEG lipids, including dioleoyl PEG lipids and cholesterol PEGs, demonstrated slower adsorption and desorption kinetics. The interactions of Pluronics and Nonoxynol surfactants with phospholipid bilayers were also studied. Pluronics showed no apparent affinity for the phospholipid bilayer, while the Nonoxynol surfactants damaged the lipid bilayers as PEG chain length decreased. / Ph. D.

Μαγνητικά νανοσωματίδια οξειδίων του σιδήρου παρασκευάσθηκαν μέσω της αλκαλικής συμπύκνωσης και ελεγχόμενης καταβύθισης συμπλόκων ιόντων FeII, υπό την παρουσία τυχαίου συμπολυμερούς PAA-co-MA. Οι παράμετροι της σύνθεσης μεταβλήθηκαν με σκοπό την απομόνωση προϊόντων που να εμφανίζουν τις καλύτερες μαγνητικές ιδιότητες. Όλα τα προϊόντα εμφάνισαν υψηλή κολλοειδή σταθερότητα σε υδατικά μέσα χαμηλής ιοντικής ισχύος, ενώ ο σιδηρομαγνητικός τους χαρακτήρας έδειξε να ποικίλει από ασθενής μέχρι αρκετά ισχυρός, όπως προέκυψε μετά τον χαρακτηρισμό τους με μαγνητοφόρηση και μαγνητική υπερθερμία με εναλλασόμενο μαγνητικό πεδίο. Το μέσο μέγεθος των νανοκρυσταλλιτών ήταν διαφορετικό σε κάθε προϊόν κυμαινόμενο από περίπου 3 έως 14 nm, όπως προσδιορίστηκε μέσω XRD. Η ανάλυση με ΤΕΜ έδειξε ότι στο προϊόν που εμφανίζει τις καλύτερες μαγνητικές ιδιότητες σχηματίζονται πλειάδες νανοσωματιδίων πυκνής διάταξης, και στις οποίες αποδίδεται η βελτιωμένη απόκριση σε μαγνητικά πεδία. Τα άλλα προϊόντα εμφάνισαν μικρότερα μεγέθη κρυσταλλιτών και διαφορετικά δομικά χαρακτηριστικά. Τα κολλοειδή καταβυθίζονταν κατόπιν αύξησης της ιοντικής ισχύος του διαλύτη. Για τον λόγο αυτό αποφασίστηκε η μελέτη της αντίδρασης σύζευξης των εξωτερικών καρβοξυλικών ομάδων του πολυμερικού φλοιού με mPEG-NH2, δεδομένου ότι η PEG αυξάνει σημαντικά τη σταθερότητα των κολλοειδών. Παρά το γεγονός ότι χρησιμοποιήθηκαν κοινά αντιδραστήρια σύζευξης, μόνο υπό πολύ ειδικές συνθήκες η απόδοση της αντίδρασης ήταν ικανοποιητική, οπότε και προέκυψαν σταθερά κολλοειδή σε συνθήκες υψηλής ιοντικής ισχύος. Τέλος, τα προϊόντα αξιολογήθηκαν για την ικανότητά τους να επάγουν υπερθερμία και μελετήθηκε ο χρόνος χαλάρωσης Τ2, ο οποίος σχετίζεται άμεσα με την ενίσχυση της αντίθεσης στην απεικόνιση μέσω μαγνητικού συντονισμού. Τέλος, ένα από τα προϊόντα, μελετήθηκε in vitro και in νίνο, προκειμένου να αξιολογηθεί η βιοσυμβατότητα του. Τα συστήματα αυτά παρουσιάζουν πολύ ενδιαφέρουσες ιδιότητες ώστε να τροποποιηθούν και να μελετηθούν περεταίρω ως θεραπευτικά ή/και διαγνωστικά νανοϋλικά. / Μagnetic nanoparticles of iron oxides were synthesized through condensation and controlled precipitation of a FeII complex, in alkaline environment, in the presence of a random copolymer PAA-co-MA, as polymeric corona. The synthetic parameters were varied with the aim of isolating products exhibiting the best magnetic properties. All products displayed high colloidal stability in low ionic strength aqueous media, while their ferromagnetic properties varied from weak to quite strong, as deduced after the characterization with magnetophoresis and magnetic hyperthermia with alternating magnetic field. The average crystallite size, as determined through XRD, varied from 8 to 14 nm depending on the product. TEM analysis showed that the product displaying the best magnetic properties formed clusters of densely packed nanocrystallites, leading to interesting superstructural motifs. All the other products displayed smaller crystallite sizes and different structural characteristics. The colloids precipitated upon increase of the ionic strength of the solvent (H2O) with NaCl. Therefore, it was decided to study the conjugation of the outer carboxyl groups of the polymeric corona with mPEG-NH2, since PEG is known to increase significantly the stability of colloids. Despite the fact that common conjugation reagents were used, only under specific conditions the yied of the reaction was appropriately high in order the resultant colloids to be stable in a high ionic strength (isotonic) medium. Finally the products were evaluated for their performance in magnetic hyperthermia and for contrast enhancement in magnetic resonance imaging, by studying the T2 relaxation time. One of the products was furthermore studied by in vitro and in vivo systems, in order to evaluate its biocompatibility. These colloidal systems exhibit very interesting properties in order to be further modified and studied as therapeutic and / or diagnostic (theragnostic) nanomaterials.

This thesis consists of two parts. The first part deals with the magnetic properties of Fe3O4 nanocrystals and their possible application in water remediation. The second part is on the delamination of layered materials and the preparation of new layered hybrids from the delaminated sheets. In recent years, nanoscale magnetic particles have attracted considerable attention because of their potential applications in industry, medicine and environmental remediation. The most commonly studied magnetic nanoparticles are metals, bimetals and metal oxides. Of these, magnetite, Fe3O4, nanoparticles have been the most intensively investigated as they are, non-toxic, stable and easy to synthesize. Magnetic properties of nanoparticles such as the saturation magnetization, coercivity and blocking temperature are influenced both by size and shape. Below a critical size magnetic particles can become single domain and above a critical temperature (T B , the blocking temperature) thermal fluctuations can induce random flipping of magnetic moments resulting in loss of magnetic order. At temperatures above the blocking temperature the particles are superparamagnetic. Magnetic nanocrystals of similar dimensions but with different shapes show variation in magnetic properties especially in the value of the blocking temperature, because of differences in the surface anisotropy contribution. The properties of magnetic nanoparticles are briefly reviewed in Chapter 1. The objective of the present study was to synthesize Fe3O4 nanocrystals of different morphologies, to understand the difference in magnetic properties associated with shape and to explore the possibility of using Fe3O4 nanocrystals in water remediation. In the present study, oleate capped magnetite (Fe3O4) nanocrystals of spherical and cubic morphologies of comparable dimensions (∼10nm) have been synthesized by thermal decomposition of FeOOH in high-boiling octadecene solvent (Chapter 2). The nanocrystals were characterized by XRD, TEM and XPS spectroscopy. The nanoparticles of different morphologies exhibit very different blocking temperatures. Cubic nanocrystals have a higher blocking temperature (T B = 190 K) as compared to spheres (T B = 142 K). From the shift in the hysteresis loop it is demonstrated that the higher blocking temperature is a consequence of exchange bias or exchange anisotropy that manifests when a ferromagnetic material is in physical contact with an antiferromagnetic material. In nanoparticles, the presence of an exchange bias field leads to higher blocking temperatures T B because of the magnetic exchange coupling induced at the interface between the ferromagnet and antiferromagnet. It is shown that in these iron oxide nanocrystals the exchange bias field originates from trace amounts of the antiferromagnet wustite, FeO, present along with the ferrimagnetic Fe3O4 phase. It is also shown that the higher FeO content in nanocrystals of cubic morphology is responsible for the larger exchange bias fields that in turn lead to a higher blocking temperature. Magnetic nanoparticles with moderate magnetization can be easily separated from dispersions by applying low intensity magnetic fields. Oleate capped spherical and cubic iron oxide nanocrystals have considerable magnetic moment and hence have the potential as host-carriers for magnetic separation in environmental remediation. These nanocrystals are, however, dispersible only in non-polar solvents like chloroform, toluene, etc. Environmental remediation requires that the nanocrystals be water dispersible. This was achieved by functionalizing the surface of the iron oxide nanocrystals by coordinating carboxymethyl-β-cyclodextrin (CMCD) cavities (Chapter 3). The hydroxyl groups located at the rim of the anchored cyclodextrin cavity renders the surface of the functionalized nanocrystal hydrophilic. The integrity of the anchored CMCD molecules are preserved on capping and their hydrophobic cavities available for host-guest chemistry. The CMCD capped iron oxide particles are water dispersible and separable in modest magnetic fields (<0.5 T). Small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards arsenic ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. To extend the application of the iron oxide nanocrystals so that they can both capture and destroy organic contaminants present in water, cyclodextrin functionalized water dispersible core-shell Fe3O4@TiO2 (CMCD-Fe3O4@TiO2) nanocrystals have been synthesized (Chapter 4). The application of these particles for the photocatalytic degradation of endocrine disrupting chemicals (EDC), bisphenol A and dibutyl phthalate, in water is demonstrated. EDC molecules that may be present in water are captured by the CMCD-Fe3O4@TiO2 nanoparticles by inclusion within the anchored cavities. Once included they are photocatalytically destroyed by the TiO2 shell on UV light illumination. The magnetism associated with the crystalline Fe3O4 core allows for the magnetic separation of the particles from the aqueous dispersion once photocatalytic degradation is complete. An attractive feature of these ‘capture and destroy’ nanomaterials is that they may be completely removed from the dispersion and reused with little or no loss of catalytic activity. The second part of the thesis deals with the intercalation of surfactants in inorganic layered solids and their subsequent delamination of the functionalized solid in non-polar solvents. The solids investigated were - the anionic layered double hydroxides (LDH), the 2:1 smectite clay, montmorillonite (MMT), layered metal thiophosphates (CdPS3) and graphite oxide (GO). Layered Double Hydroxides (LDH) are lamellar solids of the general chemical formula [M0(1−x)Mx(OH)2], where M0 is a divalent metal ion and M a trivalent ion. The structure of the Mg-Al layered double hydroxide (Mg-Al LDH) may be derived from that of brucite, Mg(OH)2, by isomorphous substitution of a part of the Mg2+ by trivalent Al3+ ions with electrical neutrality maintained by interlamellar exchangeable ions like nitrate or carbonate. The ion exchange intercalation of the anionic surfactant dodecyl sulfate (DDS) in an Mg-Al LDH and the subsequent delamination of the surfactant intercalated LDH in non-polar solvent is reviewed in Chapter 5. Delamination results in a clear dispersion of neutral nanosheets. The delaminated sheets are neutral as the surfactant chains remain anchored to the inorganic sheet. On solvent evaporation, the sheets re-stack to give back the original surfactant intercalated solid. This strategy for delamination of layered solids by intercalation of an appropriate surfactant followed by dispersing in a non-polar solvent has been extended to montmorillonite (MMT) and cadmium thiophosphates (CdPS3) by ion-exchange intercalation of the cationic surfactant dioctadecyldimethylammonium bromide (DODMA) followed by sonication in non-polar solvents e.g. toluene or chloroform as in the case of the LDH (Chapter 6). The nanosheets of the MMT and CdPS3 are electrically neutral as the surfactant chains remain anchored to the inorganic sheet even after exfoliation. Graphite oxide (GO) too can be delaminated by functionalizing the sheets by covalently linking oleylamine chains to the GO sheets via an amide bond. The oleylamine functionalized GO is easily delaminated in non-polar solvents to give electrically neutral GO nanosheets. It is shown in Chapter 7 that the 1:1 mixtures of dispersions of montmorillonite-DODMA with Mg-Al LDH-DDS nanosheets can self assemble, on solvent evaporation, to give a new layered solid with periodically alternating montmorillonite and LDH layers. In this method attractive forces between the neutral exfoliated nanosheets of cationic and anionic ensures self-assembly of a perfectly periodic alternating layered structure. The method has been extended to synthesize new layered solids in which surfactant tethered cationic and anionic inorganic sheets alternate. The hybrid solids synthesized are CdPS3—MgAl-LDH, CdPS3—CoAl-LDH, GO—MgAl-LDH, GO—CoAl-LDH. The procedure outlined in Chapter 7 allows for a simple, but versatile, method for generating new periodically ordered layered hybrid solids by self-assembly.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / This dissertation reports the colloidal synthesis of iron silicide, hafnium oxide core-gold shell and water soluble iron-gold alloy for the first time. As the first part of the experimentation, plasmonic and superparamagnetic nanoparticles of gold and iron are synthesized in the form of core-shell and alloy. The purpose of making these nanoparticles is that the core-shell and alloy nanoparticles exhibit enhanced properties and new functionality due to close proximity of two functionally different components. The synthesis of core-shell and alloy nanoparticles is of special interest for possible application towards magnetic hyperthermia, catalysis and drug delivery. The iron-gold core-shell nanoparticles prepared in the reverse micelles reflux in high boiling point solvent (diphenyl ether) in presence of oleic acid and oleyl amine results in the formation of monodisperse core-shell nanoparticles. The second part of the experimentation includes the preparation of water soluble iron-gold alloy nanoparticles. The alloy nanoparticles are prepared for the first time at relatively low temperature (110 oC). The use of hydrophilic ligand 3-mercapto-1-propane sulphonic acid ensures the aqueous solubility of the alloy nanoparticles. Next, hafnium oxide core-gold shell nanoparticles are prepared for the first time using high temperature reduction method. These nanoparticles are potentially important as a high κ material in semiconductor industry. Fourth, a new type of material called iron silicide is prepared in solution phase. The material has been prepared before but not in a colloidal solution. The Fe3Si obtained is superparamagnetic. Another phase β-FeSi2 is a low band gap (0.85 eV) semiconductor and is sustainable and environmentally friendly. At last, the iron monosilicide (FeSi) and β-FeSi2 are also prepared by heating iron-gold core-shell and alloy nanoparticles on silicon (111) substrate. The nucleation of gaseous silicon precursor on the melted nanoparticles results the formation of nanodomains of FeSi and β-FeSi2. A practical application of these nanoparticles is an important next step of this research. Further improvement in the synthesis of β-FeSi2 nanoparticles by colloidal synthetic approach and its application in solar cell is a future goal.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / The research work in this thesis aims at investigating the basic physic-chemical properties of magnetic and metal nanoparticles (NPs) for biomedical applications such as magnetic hyperthermia and controlled drug release. Magneto-plasmonic properties of magnetic NPs are important to evaluate potential applications of these materials. Magnetic property can be used to control, monitor and deliver the particles using a magnetic field while plasmonic property allows the tracking of the position of the particles, but aggregation of NPs could pose a problem. Here, the aggregation of NPs is investigated via the Faraday rotation of gold coated Fe[subscript]2O[subscript]3 NPs in alternating magnetic fields. In addition, the Faraday rotation of the particles is measured in pulsed magnetic fields, which can generate stronger magnetic fields than traditional inductive heaters used in the previous experiments. In the second project, the formation of protein-NPs complexes is investigated for hyperthermia treatment. The interactions between gold and iron-platinum NPs with octameric mycobacterial porin A from Mycobacterium smegmatis (MspA) and MspA[superscript])cys protein molecules are examined to assemble a stable, geometrically suitable and amphiphilic proteins-NPs complex. Magnetic NPs show promising heating effects in magnetic hyperthermia to eliminate cancer cells selectively in the presence of alternating magnetic field. As a part of investigation, the heating capacity of a variety of magnetic NPs and the effects of solvent viscosity are investigated to obtain insight into the heating mechanism of these particles. Finally, the controlled drug release of magnetic NPs loaded liposomes by pulsed magnetic field is investigated. The preliminary data indicate about 5-10% release of drug after the application of 2 Tesla magnetic pulses. The preliminary experiments will serve as the initial stage of investigation for more effective magnetic hyperthermia treatment with the help of short magnetic pulses.

Master of Science / Department of Chemical Engineering / Keith Hohn / Acid catalysts have been shown to be very successful in the pretreatment of cellulosic biomass to improve glucose yield and improve overall yield of ethanol. This report presents the results of a techno-economic study that looks into the use of nanoscale magnetic solid acid catalysts for glucose production. Magnetic solid acid catalysts are an improvement over using diluted acid due to eliminating acid-waste generation and corrosion hazards. Their magnetic nature also allows them to be easily separated from reaction products by an external magnetic force. After the technology is analyzed, a series of unit operations is proposed to go from the laboratory scale to the industrial plant scale. The next step was to develop material and energy balances using HYSYS process simulation software. Capital and operating costs are estimated and all the information is combined into a discounted cash flow economic model. The economic portion of the report uses a probabilistic cost assessment. It is used to quantify the range of risks in the project from swings in feedstock costs, differences in yield from catalysts, and any other significant variables. Both capital costs (initial equipment & construction investment) and operating costs (feedstock supply, chemicals, and personnell) are included with ranges of error based on databases and expert opinion. This method of evaluating investment efficiency can be helpful for predicting the cost benefits of proposed future research. The yield and percent catalyst magnetically recovered is assumed based on laboratory research to simplify the model. A 2000 metric tons of biomass per day facility was analyzed. Using the magnetic solid acid catalyst technology, the capital costs are estimated to be $160 million and this technology saves around 10% of capital costs compared to ethanol plants that uses conventional acid hydrolysis. The yield of the magnetic solid acid catalysts should be around 75% to compete with existing ethanol technologies. The metric used for this report is the discount profitability index (DPI) which is the ratio of future cash flows divided by investment. A DPI “hurdle rate” of 1.3 is used, which is similar to industry economic metrics of projects that include new process plants. The calculated DPI for the project is 1.38 DPI which is higher than using conventional cellulose treatment technologies. The recommendation is continue to study this technology’s large scale applicability before attempting any plant pilot studies.

Iron oxide magnetic nanoparticle synthesis and their surface functionalization hold a crucial position in the design and fabrication of functional materials for a variety of biomedical applications. Non-uniform nanoparticles with poor crystallinity, prepared by conventional methods, have only limited value in biological areas. Large scale synthesis methods that are able to produce high quality, mono-dispersed iron oxide nanoparticles using low cost and environment friendly chemicals are highly desirable. Following synthesis, appropriate surface functionalization is necessary to direct the dispersibility of nanoparticles in aqueous solution in order to provide them with acceptable colloidal stability against the ion strength and many biomolecules that nanoparticles may encounter under physiological conditions. Poorly stabilized nanoparticles that easily aggregate and form large size agglomerates would be quickly cleared by the liver and other organs and are not suitable for clinical purposes. Additionally, many interesting functionalities such as fluorescence, targeting and anti-cancer properties can be immobilized onto the surface of iron oxide magnetic nanoparticles during the surface functionalization process so as to build multifunctional platforms for disease diagnosis and treatment. Polyol method can be an effective way to prepare magnetite nanoparticles that are suitable for biological applications. In a polyol system, selected surface functionalities were introduced to the nanoparticle surface via a hot injection technique. The morphology, uniformity, crystallinity and magnetic properties were examined to understand the effect of different ligand molecules on the final product. Their surface chemistry, colloidal properties and surface reactivity were also studied to evaluate their practicability in different applications. A high efficiency in-situ method for the preparation of magnetite nanoparticles attached to silica nanospheres was also developed in a polyol system. This approach eliminates several time-consuming processing steps that are in the conventional fabrication route and directly produces water-stable magnetite-silica hybrid materials with surface availability for subsequent modifications. In addition to polyalcohol, the potential of polyamine in the preparation of water-soluble magnetite nanoparticles with amine surface functionalities was also evaluated. And it is suggested that polyamine acts as solvent, stabilizing agent and reducing agent simultaneously during the synthesis. The characterization of polyamine coated nanoparticles, their surface functionalization, and subsequent application for bioseparation and drug delivery were reported.

La récupération et le recyclage des catalyseurs représentent un véritable challenge économique, sanitaire et environnemental. Depuis quelques années, l’utilisation des nanoparticules magnétiques comme support de catalyseurs a émergé comme une voie alternative pour leur recyclage. En effet, les catalyseurs supportés sur des nanoparticules magnétiques peuvent être facilement isolés et recyclés par décantation magnétique avec un simple aimant. Dans ce travail, nous décrivons la synthèse de métallodendrons porteurs de site catalytiques diphosphinopalladium et leur greffage sur des nanoparticules magnétiques cœur-écorce. L’intérêt majeur de ce travail a été de montrer la grande efficacité du recyclage des catalyseurs notamment en milieu aqueux. L’utilisation judicieuse des structures dendritiques a permis d’augmenter la fonctionnalisation de la surface des MNPs. Ceci nous a permis de préparer des catalyseurs supportés très performants dans des réactions de couplage de Suzuki et de Sonogashira / The recovery and recycling of catalysts represent a real challenge for economic, health and environmental reasons. Since few years, the use of magnetic nanoparticles as catalysts supports has emerged as an alternative for their recovery. Indeed, magnetic nanoparticles-supported catalysts could be easily isolated and recycled from the reaction medium by magnetization with a simple magnet. In this work, we report the synthesis of metallodendrons bearing pallado phosphine catalysts and their grafting onto core-shell magnetic nanoparticles. The main interest of this work was to demonstrate the efficiency of the recycling especially in aqueous media. Judicious use of dendritic structures has increased the surface functionalization of nanoparticles. Therefore, it was possible to prepare highly performant catalysts for Suzuki and Sonogashira cross-coupling reactions.

Ce travail de thèse s’inscrit dans un projet plus large qui vise à développer avec le laboratoire Ampère et l’Etablissement Français du Sang un microsystème capable de réaliser un phénotypage plaquettaire pour le diagnostic de la thrombopénie néonatale. Ce microsystème doit permettre d’isoler les plaquettes du sang total et de détecter les antigènes plaquettaires présents à leur surface. L’isolation des plaquettes se fera grâce à un module de magnétophorèse et un module de diélectrophorèse. La détection sera électrochimique. Le cœur de ce travail de thèse a donc consisté à développer des nanoparticules magnétiques pour le module de magnétophorèse. Ces nanoparticules doivent permettre la capture spécifique des plaquettes et servir de marqueur pour la détection électrochimique. Pour ce faire, des nanoparticules magnétiques ont donc été doublement fonctionnalisées en une seule étape avec un anticorps anti-CD32 dirigé contre l’antigène CD32 présent à la surface des plaquettes et avec une molécule électroactive. Après optimisation des différents paramètres de greffage, les propriétés électrochimiques de ces particules ont été caractérisées. Leurs propriétés de bioreconnaissance ont été testées sur l’antigène purifié puis sur plaquettes entières. Enfin la faisabilité de la manipulation des structures nanoparticules/plaquettes par magnétophorèse avec des micro-aimants a été démontrée. / Fetal/neonatal alloimmune thrombocytopenia (F/NAIT) represents a great threat to new-borns or fetus. It occurs when a woman becomes alloimmunized against fetal platelet antigens. With the aim to improve fetal and neonatal survival, in collaboration with Ampere Laboratory and Etablissement Français du Sang, we plan at developing a Point-of-Care (POC) platform for platelet phenotyping. The final POC microsystem will be able to perform magnetophoresis and dielectrophoresis for platelets isolation from whole blood, and their selective electrochemical detection allowing for their phenotyping. The development of nanoparticles (NPs) with magnetic, electrochemical and bio-selection properties is a key issue. Herein, we have focused on the elaboration of magnetic NPs bearing 1) anti-CD32 antibody for specific interaction with CD32 antigen, which is present at the surface of platelets and 2) ferrocene carboxylic acid, an electroactive molecule for detection. To achieve this, the coupling reactions of this electroactive molecule and this antibody were optimized and a one-pot reaction for double functionalization was developed. The bioactivity of the immobilized antibody was tested at the molecular and cellular level. The dual-functionalized NPs voltammetric signals were also investigated. Finally the feasibility of platelets capture and actuation by magnetophoresis with micro-magnet array were demonstrated.