Ever since their discovery, Carbon nanotubes (CNTs) have been renowned to be potential candidates for a variety of applications. Nevertheless, the difficulties accompanied with their dispersion and poor solubility in various solvents have hindered CNTs potential applications. As a result, studies have been developed to address the dispersion problem. The solution is in modifying the surfaces of the nanotubes covalently or non-covalently with a desired dispersant. Various materials have been employed for this purpose out of which polymers are the most common. Non-covalent functionalization of CNTs via polymer wrapping represents an attractive method to obtain a stable and homogenous CNTs dispersion. This method is able to change the surface properties of the nanotubes without destroying their intrinsic structure and preserving their properties. This thesis explores and studies the surface modification and solublization of pristine single and multiwalled carbon nanotubes via a simple solution mixing technique through non-covalent interactions of CNTs with various anionic and cationic conjugated polyelectrolytes (CPEs). The work includes studying the interaction of various poly(phenylene ethynylene) electrolytes with MWCNTs and an imidazolium functionalized poly(3-hexylthiophene) with SWCNTs. Our work here focuses on the noncovalent modifications of carbon nanotubes using novel CPEs in order to use these resulting CPE/CNT complexes in various applications. Upon modifying the CNTs with the CPEs, the resulting CPE/CNT complex has been proven to be easily dispersed in various organic and aqueous solution with excellent homogeneity and stability for several months. This complex was then used as a nanofiller and was dispersed in another polymer matrix (poly(methyl methacrylate), PMMA). The PMMA/CPE/CNT composite materials were cast or electrospun depending on their desired application. The presence of the CPE modified CNTs in the polymer matrix has been proven to enhance the composites thermal, mechanical and electrical properties compared to pristine CNTs. Various spectroscopic and microscopic techniques such as UV-vis, fluorescence, TEM, AFM and SEM were used to study and characterize the CPE/CNT complexes. Also, TGA, DSC and DMA were used to study the thermal and mechanical properties of the composite materials. Our current work represents a fundamental study on the non-covalent interactions between CNTs and CPEs on one hand and gives a real life example on the CPE/CNT application in composite materials and electronics.

Matrix Assisted Laser Desorption Ionization–Time of Flight (MALDI-TOF) mass spectroscopy is used in the characterization of synthetic polymers. MALDI allows for determination of: modal, most probable peak (M P), molecular number average (MN), molecular weight average (MW), polydispersity (PD), and polymer spread (PSP). We evaluate a new sample preparation method using Induction Based Fluidics (IBF) to kinetically launch and direct nanoliter volumes to a target without contact. IBF offers signal improvement via field enhanced crystallization. This is the first study to discuss filed enhanced crystallization in MALDI sample preparation. IBF can increase signal/noise (S/N) and signal intensity for polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(ethylene glycol) (PEG) across a mass range of 2,500 to 92,000 Da showing more accurate PSP. Increases in S/N range up to: 279% for PS, 140% for PMMA, and 660% for PEG. Signal intensities increased up to: 438% for PS, 115% for PMMA, and 166% for PEG. Cross-polarization microscopy indicates dramatic morphology differences between IBF and micropipette. Finally, we speculate as to why IBF nanoliter depositions afford higher S/N values in experiments conducted in different instrumental configurations even without optimization. Next we sought to investigate whether nanoliter volumes of concentrated polar liquids and organic monomers launched to targets using IBF can be verified through the real time charge measurements. We show that using a nanoliter IBF dispensing device and nanocoulomb meter, charge measurements made on nanoliter drops in real time are correlated with the droplets surface area following Gauss’s Law. We infer the "induction only" formation of the double layer showing the ability to determine nanoliter volumes, nearly instantaneously, in real time. Implications are presented from these IBF measurement observations on improving/monitoring MALDI quantitation and its quality control. Polymer-dye interactions were further investigated using PMMA composites made from a polar metalloporphyrin [5-(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)-10,20-diphenylporphyrinato]zinc(II) (Zn(II)Bpin-DPP) in select weight %s (wt%s). Fluorescence spectroscopy has revealed that the porphyrin was well dispersed within the composite. Differential Scanning Calorimetry (DSC) showed that porphyrin acted as an antiplasticizer raising the glass transition (Tg) from 105 °C to 123 °C. Dielectric Analysis (DEA) was performed in the frequency range of 0.3 Hz to 100 kHz between -150 to 270 ⁰C. Permittivity (ε’), loss factor (ε’’) and dielectric response of beta (β), alpha beta (αβ), and conductivity relaxations were studied. Previous DEA data was limited to 190 ⁰C. This study brings analysis to 270 ⁰C which is start point for the first part of PMMA degradation. Thus forwarding DEA can be used to evaluate PMMA degradation. The electric modulus formalism is used to reveal the β and conductivity relaxations. The apparent activation energies (Ea) for the molecular relaxations are presented. AC (ζAC) and DC (ζDC) conductivity are also evaluated. Tan delta (δ), dissipation factor, evaluated between 1 Hz to 100 kHz was shown to increase with porphyrin loading although locally affected by free volume restriction. Havriliak-Negami (H-N) equation was fit using the complex electric modulus (M*) modified form and was performed on the conductivity region 160 to 190 ⁰C and degradation region 190 to 270 °C. Relaxations above the Tg were proven to be conductivity relaxations using four proofs. This is the first study to investigate PMMA degradation DEA with the complex electric modulus, M*, revealing a unique occurrence of increasing central relaxation times (s-1) and reducing electric loss modulus (M") frequency maxima (Hz) after the degradation temperature of 220 ⁰C was reached supporting current literature of the first of a two part degradation process that proceeds via end chain scission.

L'objectif de ces travaux était de mettre au point des vecteurs de diffusion efficaces du thymol pour lutter contre un acarien parasite des abeilles. Le choix s'est porté sur la formation de nano-objets par émulsification spontanée pouvant libérer efficacement du thymol grâce à leur grande surface spécifique. L'émulsification spontanée par « effet Ouzo » a été choisie en raison de (i) la simplicité du procédé nécessaire pour son application par les apiculteurs et de (ii) la possibilité de former une grande diversité de nano-objets. L'émulsification spontanée par effet Ouzo a tout d'abord été étudiée fondamentalement avec un polymère (nanoprécipitation), le polyméthacrylate de méthyle (PMMA), pour s'affranchir des phénomènes déstabilisants typiques des émulsions tels que le mûrissement d'Ostwald et la coalescence. Cette étude a permis de définir clairement les compositions du système PMMA/solvant/eau pour lesquelles la nanoprécipitation du PMMA induit la formation exclusive de nanoparticules de distribution de taille étroite (zone Ouzo) ou la formation de nanoparticules additionnées de macroparticules (zone non-Ouzo), séparées par la limite Ouzo. Deux mécanismes de formation des nanoparticules ont été déduits suivant la sursaturation du PMMA (nucléation et croissance ou nucléation et agrégation). L'influence des stabilisants a montré l'importance de l'adsorption des ions OH- sur la taille des nanoparticules et sur le déplacement de la limite Ouzo alors que seule la stabilité colloïdale est améliorée avec l'ajout de tensioactifs. Cette étude fondamentale a servi de base pour la formation des nanogouttelettes de thymol et des nanocapsules thymol-PVA réticulé et thymol-PMMA par effet Ouzo. Des nanoparticules thymol-PVP ont également été formées par complexation de la poly(N-vinyl-2-pyrrolidone) en milieu aqueux. Ces nano-objets de thymol ont été testés sur des ruches infestées pour déterminer leur efficacité d'éradication de l'acarien Varroa Destructor. / The objective of this work dealt with setting up efficient thymol diffusion vectors to fight against a bee mite, the Varroa Destructor. The formation of nano-objects by spontaneous emulsification was investigated because they provide large specific area to enhance thymol evaporation. Spontaneous emulsification by so-called Ouzo effect was chosen because of (i) the simplicity of the process necessary for the transfer to beekeepers and (ii) the great diversity of nano-objects morphologies which can be designed. Spontaneous emulsification by Ouzo effect was first studied fundamentally with a polymer (nanoprecipitation), the poly(methyl methacrylate) (PMMA), in order to avoid typical emulsion destabilizing phenomena such as Ostwald ripening and coalescence. This study enabled to clearly define the PMMA/solvent/water system compositions for which PMMA nanoprecipitation induces only formation of nanoparticles with a narrow size distribution (Ouzo domain) or formation of microparticles besides nanoparticles (non-Ouzo domain), separated by the Ouzo boundary. Two nanoparticles formation mechanisms were deduced with respect to the supersaturation of PMMA (nucleation and growth or nucleation and aggregation). Stabilizers influence set off the importance of OH- ions adsorption on nanoparticles size and on Ouzo boundary shifting whereas only colloidal stability is improved through surfactant addition. This fundamental study laid down basis for thymol nanodroplets and for thymol-cross linked PVA and thymol-PMMA nanocapsules formation by Ouzo effect. Thymol-PVP nanoparticles were also prepared by poly(N-vinyl-2-pyrrolidone) complexation in aqueous medium. These thymol nano-objects were tested on infested beehives to determine their efficiency to eradicate the Varroa Destructor mite.

Polymer composites containing nanosized fillers have generated explosive interest since the early 1980's. Many recent studies have been conducted incorporating nano-fillers into polymer matrices to design and synthesize materials with tunable mechanical, thermal, and optical properties. Conventional filled polymers, where the reinforcement is on the order of microns, have been replaced by composites with discrete nanosized fillers. Gradually, theories that predicted that composite properties are independent of particle size in the micron range were challenged by nanocomposites. Rather, nanocomposite properties are greatly influenced by the surface area of the. All of this is complicated by the fact that nanoparticles are inclined to aggregate or migrate to interfaces. Much effort has been devoted to optimize dispersion of nanofillers in the polymer matrices, as polymer-nanoparticle interactions and adhesion greatly influence performance of the material. A well- dispersed composite system with various noncovalent interactions such as those that arise from hydrogen bonding, electrostatic attractions and π-π interactions between the filler and the matrix, can transfer stress and the interface will stop the development of cracks and impede stress concentrations. Overall, large reinforcement increases are noted at low nanoparticle loadings. Additionally, functional properties such as thermal, electrical conductivity and porosity can be tailored for specific applications. The design of high performance composites requires optimizing dispersion, nanoparticle-polymer noncovalent interactions and the chemistry of the materials. Therefore polymer composites with different types of nanofillers were investigated to prove various noncovalent interaction and to improve the mechanical, thermal and electrical properties in this study. Poly (methyl methacrylate) (PMMA) with BaTiO3 and Bi2O3 composites were fabricated by two different methods; sonication of fillers in PMMA and in situ polymerization. Samples were irradiated in air via a JL Shepherd Mark I cesium-137 source. The dose rate was 985 rads/min and the total dose was 2.0 Mrad. The polymer sonication (PSON) method has a greater effect than in situ polymerization on sample uniformity. With the PSON method there was a slight improvement in rad hardness in the barium titanate composites. This is the case with and without MWNTs and coupling agents. The storage modulus and loss modulus were measured via Dynamic Mechanical Analyzer (DMA) under the tension film mode using a heating rate of 5 °C min-1 from -150 °C to 200 °C and a scanning frequency range of 1-100 Hz. Scanning electron microscopy (SEM) provided images of the polymer-nanocomposites. An aliphatic isocyanate, polyether, polyol thermoplastic polyurethane, Tecoflex® SG-85A, was solution processed with the varying amounts of silica nanowire. A new grade polyurethane, Tecoflex®, was synthesized from the aliphatic 4,4-methylene dicyclohexyl diisocyanate (H12MDI) with polytetramethylene ether glycol. Despite Tecoflex®'s longevity and wide use, this polymer's dielectric behavior has not been widely studied. Therefore, the dielectric response of neat PU, Tecoflex®, and PU composites with silica nanowire from -150 to 150 °C is presented. The mechanism of nanowire growing with diameters ranging from 50 to 500 nm has been established to follow the vapour liquid solid (VLS) model via the PtSi phase acting as the catalyst. Our previous thermal stability study of PU nanowire composites have yielded increased heat stability to 330 °C. In comparison, neat PU only maintains thermal stability in temperatures that range to 250 °C. The onset of decomposition temperature was measured by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) provided images of the polymer-nanocomposites. A series of PMMA-dodecyloxy NB and PHEMA-dodecyloxy NB composites were synthesized in situ and characterized. The dodecyl groups significantly alter the solubility of the nanoballs, imparting hydrophobicity to the surface of the nanoball. A comparison study was made between the PMMA-NB and PHEMA-NB nanocomposites. Structure property relations are discussed in terms of interactions between the polymer matrices and nanoball surfaces and interiors. These OC12 NB and the hydroxyl NB polymer composites are the first studies to date that probe relaxations and conductivity in discrete polyhedral metal-organic polymer composites. A novel ultra-flexible polycarbonate-polyurethane (PCPU) was synthesized with methylene bis(4-cyclohexylisocyanate), 1,4 butanediol as a chain extender and a polycarbonate polyol containing 1,6-hexanediol and 3-methyl-1,5-pentanediol. Through the techniques of water coagulation, the synthesis of self-healing PCPU with various concentrations of SWNT (Single-Walled Nanotubes) is possible. The resulting features of this synthesized rubber-like substance are to be evaluated to determine glass transition temperature. This novel type of polyurethane material targets growing markets for biocompatible polymers. Also, a secondary goal of this project is to obtain information useful to determining whether PCPU-carbon nanotube composites would be good candidates for use as a gel electrolyte in polymer batteries. All nanocomposites were characterized by differential scanning calorimetry (DSC) to determine glass transition temperatures. The dielectric permittivity (ε’) and loss factor (ε”) were also measured via Dielectric Analysis (DEA) in the frequency range 1Hz to 100 kHz and between the proper temperatures in all polymer composite. The electric modulus formalism was used to reveal structural relaxations including conductivity relaxation. The activation energies for the relaxations are presented.

Amine transaminases (ATA) catalyse the transfer of an amino group from one molecule and replaces a ketone or aldehyde with the amino group, the amino group on the amino-donor is replaced with a ketone or aldehyde. This enzyme, ATA from Chromobacterium violaceum, has previously been used to catalyse the reaction involving amphetamine, therefore, it might be possible to use this enzyme to convert amphetamine and the product absorbs in the UV spectrum and can therefore be measured spectrophotometrically. The aim of the project was to explore the possibility of using ATA in a portable biosensor for the detection of amphetamine. A literature study of commercially available portable biosensors was performed, activity of the free enzyme was tested against two substrates, methylbenzylamine (MBA) and amphetamine. Research on immobilization techniques, materials, and surface functionalization was done to chose suitable methods for immobilizing ATA. Two immobilization methods were suggested and one of the methods, ionic immobilization through His-tag towards Ni2+ on the surface, was tested for enzyme activity toward MBA. The enzyme activity of the free enzyme in solution towards MBA was comparable to previously reported enzyme activity, however, no enzyme activity towards amphetamine was observed. No activity was observed for the immobilized enzyme, but it might be due to the experimental design, more experiments need to be performed to draw conclusions. / Amintransaminaser (ATA) katalyserar överförandet av en amingrupp från en molekyl och ersätter en keton eller aldehyd med den amingruppen, amingruppen på amin-donatorn ersätts med en keton eller aldehyd. Det här enzymet, ATA från Chromobacterium violaceum (CvATA), har tidigare använts för att katalysera en reaktion som involverar amfetamin, därför skulle detta enzym kunna användas på amfetamin. Produkten av reaktionen absorberar i UV spektrumet och kan mätas med en spektrofotometer. Målet med projektet var att utforska möjligheten av att använda CvATA i en biosensor för att detektera amfetamin. En litteraturstudie på kommersiellt tillgängliga bärbara biosensorer genomfördes, aktiviteten av det fria enzymet testades mot två substrat, metylbenzylamin (MBA) och amfetamin. Information samlades om immobiliseringstekniker, material, och ytfunktionalisering gjordes för att välja ut lämpliga metoder för immobilisering av CvATA. Två immobiliseringsmetoder föreslogs och en av metoderna, immobilisering via enzymets His6-tagg och Ni2+ joner på ytan, testades för enzymaktivitet mot MBA. Enzymaktiviteten av det fria enzymet i lösning mot MBA var i samma storleksordning som tidigare rapporterad enzymaktivitet, men ingen enzymaktivitet mot amfetamin kunde observeras. Ingen aktivitet kunde observeras för det immobiliserade enzymet, men det kan vara på grund av designen på experimentet, fler experiment behöver göras för att kunna dra några fler slutsatser.

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Polymerní nanokompozity na bázi polyhedrálních oligomerních silsesquioxanů (POSS) představují slibnou oblast výzkumu, která potenciálně může využít samouspořádávní při navrhování nových materiálů. Tato diplomová práce popisuje postup přípravy oktafenyl-POSS/PS, oktafenyl-POSS/PMMA a oktamethyl-POSS/PS systémů a charakterizaci jejich termomechanických vlastností v pevné fázi a reologických vlastností v roztoku. Získané výsledky jsou diskutovány s přihlédnutím k teoriím zabývajících se stavem disperze nanočástic.

Polymerní nanokompozity (PNCs) mají slibnou budoucnost jako lehké funkční materiály zpracovatelné aditivními výrobními technologiemi. Jejich rychlému rozšíření však brání silná závislost jejich užitných vlastností na prostorovém uspořádání nanočástic (NP). Schopnost řídit disperzi nanočástic je tak klíčovým předpokladem pro jejich uplatnění ve funkčních kompozitech. Tato práce zkoumá přípravu polymerních nanokompozitů v modelové sklotvorné polymerní matrici roztokovou metodou, technikou schopnou vytvářet prostorové uspořádání nanočástic řízené strukturními a kinetickými parametry přípravného procesu. Prezentované výsledky popisují rozdíly mezi změnami rheologického chování roztoku polystyrenu při oscilačním smyku s vysokou amplitudou (LAOS) vyvolanými nanočásticemi. Výsledky vedou k závěru, že vysoce-afinní OP-POSS nanočástice při nízkých koncentracích dobře interagují s PS a tvoří tuhé agregáty, zatímco nízko-afinní OM-POSS nanočástice za těchto podmínek neovlivňují deformační chování polymerních řetězců. Dále byla pozornost zaměřena na vliv použitého rozpouštědla na uspořádání nanočástic v SiO2/PMMA a SiO2/PS nanokompozitech, který je v literatuře prezentován jako parametr řídící prostorové uspořádání nanočástic v pevném stavu. Důraz byl kladen na kvalitativní rozdíly mezi „špatně dispergovanými“ shluky nanočástic, které byly na základě rheologie a strukturální analýzy (TEM, USAXS) identifikovány jako polymerními řetězci vázané nanočásticové klastry a dva typy agregátů, jeden termodynamického a druhý kinetického původu. Jednotlivé druhy agregátů se vyznačují odlišnými kinetikami vzniku a rozdílnými vlastnostmi jak mezi sebou, tak v porovnání s dispergovanými nanočásticemi. Pozorované typy disperze nanočástic byly kvantitativně posouzeny podle svých rheologických vlastností během roztokové přípravy, podle kterých byla vyhodnocena míra adsorpce polymeru na povrch nanočástic a atrakce ve vypuzeném objemu. Výsledky byly porovnány s teorií PRISM. Důležitost uspořádání nanočástic byla demonstrována na porovnání teplot skelných přechodů různých struktur při stejném chemickém složení.