In order to find/design porous materials that could be used in practical applications involving adsorption, it is important to investigate the basic properties (i.e. isosteric heat, specific surface area, binding energy, pore size, pore volume, etc.) of each material. With this aim in mind we have looked at three different types of materials: single-walled carbon nanotubes (prepared by the HiPco and laser methods), single-walled nanohorns (dahlia-like and bud-like) and metal-organic frameworks (Cu-BTC and RPM-1). For these substrates we have measured volumetric adsorption isotherms using several gases such as neon, argon, tetrafluoromethane (CF4), xenon, and methane (not all gases for all substrates). Experimental adsorption isotherms were measured using methane, argon, xenon, and neon gases on unpurified single-walled carbon nanotubes prepared by the HiPco method. The main idea behind these experiments was to investigate, using different size gas molecules, the sites available for adsorption on this type of porous material. We found that surface area occupied by these adsorbates on the sample is the same, regardless of their size. This means that all the gases have access to the same group of adsorption sites. Since the biggest adsorbate in this experiment was Xe, and since it is unlikely that it could penetrate the interstitial channels in the nanotube bundles, we conclude that none of the gases, including the smallest one - Ne, are able to adsorb in the interstitial channels in bundles of single-walled carbon nanotubes. For the case of argon on laser produced single-walled carbon nanotubes we measured 21 adsorption isotherms using argon gas temperatures between 40 and 153 K that were used to determine the isosteric heat of adsorption for this system. Our experimental results were compared to the ones from computer simulations performed by J. K. Johnson (from the University of Pittsburgh) for the same gas on heterogeneous and homogenous bundles. It was observed that the isosteric heat data matches better with data computed for heterogeneous nanotube bundles. This indicates that at the lowest pressure and coverages argon might be adsorbing in the defect-induced interstitial channels. We studied Cu3(Benzene-1,3,5-tricarboxylate)2(H2O)3 (abbreviated as Cu-BTC) metal-organic framework with argon to determine the sites available for adsorption on this material. Volumetric adsorption isotherms were measured at temperatures between 66 and 143 K. We found two substeps in the isotherm data, indicating that there are two types of pores present in the material: tetrahedrally-shaped side pockets and the main channels. Our experimental results were compared with data from simulations conducted using the Grand Canonical Monte Carlo method. We determined that the theoretical results match reasonably well with ours if the coverage is scaled down by a factor of 1.6. We explored the potential of two different metal-organic framework materials (Cu-BTC and RPM-1) for gas separation application. We used argon and tetrafluoromethane (CF4) gases to check if this can be achieved through kinetic and steric mechanisms. We found that Cu-BTC has excellent potential in gas separation using a steric mechanism, since argon easily adsorbs into the small pores present in the sample, while CF4 is excluded from them. Adsorption properties of RPM-1 showed that it could be employed in gas separation using a kinetic mechanism - argon gas adsorbs and reaches equilibrium in the pores of the sample more than the order of magnitude faster than CF4. Closed-ended dahlia-like nanohorns were studied with neon and tetrafluoromethane gases. In the first layer of neon and tetrafluoromethane adsorbed on dahlia-like nanohorns we found two substeps. These results were compared with results of computer simulations performed by Prof. M. Calbi. We determined, after comparison with the simulation isotherms, that the lower pressure substeps correspond to adsorption of Ne and CF4 in the narrowest parts of interstitial channels of the aggregates. Surface area calculated from neon isotherms was found to be higher than the one obtained using CF4, meaning that the smaller Ne molecule has the access to the parts of the interstitial channels that are not accessible for the bigger CF4 molecule. Features that appeared in neon adsorption isotherms on bud-like nanohorn aggregates were quite different from the ones on dahlia-like aggregates. We measured neon adsorption isotherms on this type of sample at temperatures between 22 and 49 K. In the monolayer regime we observed one single substep whose origin we can not definitely identify, because the structure of the bud-like nanohorns is not well-known. The binding energy value that was calculated from the isotherm data was lower than the value for neon adsorbed in the grooves of nanotube bundles but higher than for neon on graphite.

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. / Carbon nanotubes and graphene are promising allotropes of carbon for a large range of applications. Due to their tendency to aggregate, modifications of the carbon surface are required in order to manipulate them. Covalent functionalization is one of the ways commonly used to reach this target even if this route is not controllable. The study presented in this thesis deals with the chemical reduction of carbon nanotubes and other forms of carbon such as nanohorns, graphene, nanocones and nanodisks. Two main results have been demonstrated here. First, adding electrons to these materials renders them soluble at high concentrations in various organic solvents. Second, these reduced materials can be functionalized covalently thanks to the charges excess. Donor-acceptor dyads have thus been prepared by grafting organic dyes such as porphyrin and perylene to the nanotubes. Furthermore the extent of functional groups can be controlled preserving the electronic properties of carbon nanotubes.

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.

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

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

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 "skin"-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 sensor'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

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