The structural and electronic properties of covalently and non-covalently functionalized graphene are investigated by means of first-principles density-functional-theory. The electronic characteristics of non-covalently functionalized graphene by a planar covalent organic framework (COF) are investigated. The aromatic central molecule of the COF acts as an electron donor while the linker of the COF acts as an electron acceptor. The concerted interaction of donor acceptor promotes the formation of planar COF networks on graphene. The distinctive electronic properties of covalently functionalized fluorinated epitaxial graphene are attributed to the polar covalent C–F bond. The partial ionic character of the C–F bond results in the hyperconjugation of C–F σ-bonds with an sp2 network of graphene. The implications of resonant-orbital-induced doping for the electronic and magnetic properties of fluorinated epitaxial graphene are discussed. Isolation of single-walled carbon nanotubes (SWNTs) with specific chirality and diameters is critical. Water-soluble poly [(m- phenyleneethynylene)- alt- (p- phenyleneethynylene)], 3, is found to exhibit high selectivity in dispersing SWNT (6,5). The polymer’s ability to sort out SWNT (6,5) appears to be related to the carbon–carbon triple bond, whose free rotation allows a unique assembly. We have also demonstrated the important role of dispersion forces on the structural and electronic stability of parallel displaced and Y-shaped benzene dimer conformations. Long-range dispersive forces play a significant role in determining the relative stability of benzene dimer. The effective dispersion of SWNT depends on the helical pitch length associated with the conformations of linkages as well as π-π stacking configurations. We have revisited the constructing schemes for a large family of stable hollow boron fullerenes with 80 + 8n (n = 0,2,3,...) atoms. In contrast to the hollow pentagon boron fullerenes the stable structures constitute 12 filled pentagons and 12 additional hollow hexagons. Based on results from density-functional calculations, an empirical rule for filled pentagons is proposed along with a revised electron counting scheme. We have also studied the relative stability of various boron fullerene structures and structural and electronic properties of B80 bucky ball and boron nanotubes. Our results reveal that the energy order of fullerenes strongly depends on the exchange-correlation functional employed in the calculation. A systematic study elucidates the importance of incorporating dispersion forces to account for the intricate interplay of two and three centered bonding in boron nanostructures.

In 2012 the net world electricity generation was 21.56 trillion kilowatt hours. Photovoltaics only accounted for only 0.1 trillion kilowatt hours, less than 1 % of the total power. Recently there has been a push to convert more energy production to renewable sources. In recent years a great deal of interest has been shown for dye sensitized solar cells. These devices use inexpensive materials and have reported efficiencies approaching 12% in the lab. Here methods have been studied to improve upon these, and other, devices. Different approaches for the addition of gold nanoparticles to TiO2 films were studied. These additions acted as plasmonic and light scattering enhancements to reported dye sensitized devices. These nanoparticle enhancements generated a 10% efficiency in device performance for dye sensitized devices. Quantum dot (QD) sensitized solar cells were prepared by successive ionic layer adsorption and reaction (SILAR) synthesis of QDs in mesoporous films as well as the chemical attachment of colloidal quantum dots using 3-mercaptopropionic acid (3-MPA). Methods of synthesizing a copper sulfide (Cu2S) counter electrode were investigated to improve the device performance. By using a mesoporous film of indium tin oxide nanoparticles as a substrate for SILAR growth of Cu2S catalyst, an increase in device performance was seen over that of devices using platinum. These devices did suffer from construction drawbacks. This lead to the development of 3D nanostructures for use in Schottky photovoltaics. These high surface area devices were designed to overcome the recombination problems of thin film Schottky devices. The need to deposit a transparent top electrode limited the success of these devices, but did lead to the development of highly ordered metal nanotube arrays. To further explore these nanostructures depleted heterojunction devices were produced. Along with these devices a new approach to depositing lead sulfide quantum dots was developed. This electrophoretic deposition technique uses an applied electric field to deposit nanoparticles onto a substrate. This creates the possibility for a low waste method for depositing nanocrystals onto nanostructured substrates.

Luminescent semiconductor quantum dots (QDs) are extensively researched for use in biological applications. They have unique optical and physical properties that make them excellent candidates to replace conventional organic dyes for cellular labeling, multiplexing, nucleic acid detection, and as generalized probes. The primary focus of this dissertation was to utilize quantum dots for improvement in immunoassays. Specifically, atherosclerosis biomarkers were detected simultaneously in an effort to demonstrate advances in early detection diagnostics. Quantum dot-antibody bioconjugates were prepared by encapsulation into mesoporous silica and functionalized with thiol and amine groups to enable bioconjugation. Functionalization of the mesoporous silica quantum dot composites facilitated biocompatibility for use with biological buffers in immunoassays. These bioconjugates were used in a sandwich immunoassay to detect atherosclerosis biomarkers IL-15 and MCP-1. Sandwich assays employ capture antibodies immobilized onto a well plate to bind as much of the antigen as possible. The capture antibodies increased binding by at least 4 times the amount of antigen bound to the surface of a direct detection assay. The sandwich immunoassay was able to detect 1 pg/mL of IL-15 and 50 pg/mL of MCP-1 biomarkers. Human serum albumin nanoparticles (HSAPs) were synthesized via a desolvation and crosslinking method. Human serum albumin is a versatile protein being used in a variety of applications. Quantum dots were loaded into HSAPs as potential detection probes for immunoassays. Efficient loading was not achieved, and the assay was unable to improve current detection limits. Controlled release studies were explored using HSAPs loaded with superparamagnetic iron oxide nanoparticles and a fluorescent drug analog. Exposure to a magnetic field resulted in degradation of the HSAPs. The fluorophore was released and measured to examine how cancer drugs might be controlled through a magnetic field. Gold nanorods and an anticancer drug, Sorafenib, were also encapsulated into HSAPs for treatment of renal cell carcinoma in vivo. Laser irradiation treatment combined with Sorafenib resulted in 100% tumor necrosis and total elimination of any viable tumor present. HSAPs have demonstrated remarkable potential as drug delivery nanocarriers.

A library of graphene-based hybrid materials was synthesized as novel hybrid electrochemical electrodes for electrochemical energy conversion and storage devices and electrocatalytical sensing namely enzymeless glucose sensing. The materials used were supercapacitive graphene-family nanomaterials (multilayer graphene-MLG; graphene oxide-GO, chemically reduced GO-rGO and electrochemical reduced GOErGO) and pseudocapacitive nanostructured transition metal oxides including cobalt oxide polymorphs (CoO and Co3O4) and cobalt nanoparticles (CoNP). These were combined through physisorption, electrodeposition, and hydrothermal syntheses approaches. This project was carried out to enhance electrochemical performance and to develop electrocatalytic platforms by tailoring structural properties and desired interfaces. Particularly, electrodeposition and hydrothermal synthesis facilitate chemically-bridged (covalently- and electrostatically- anchored) interfaces and molecular anchoring of the constituents with tunable properties, allowing faster ion transport and increased accessible surface area for ion adsorption. The surface morphology, structure, crystallinity, and lattice vibrations of the hybrid materials were assessed using electron microscopy (scanning and transmission) combined with energy dispersive spectroscopy and selected-area electron diffraction, X-ray diffraction, and micro-Raman Spectroscopy. The electrochemical properties of these electrodes were evaluated in terms of supercapacitor cathodes and enzymeless glucose sensing platforms in various operating modes. They include cyclic voltammetry (CV), ac electrochemical impedance spectroscopy, charging-discharging, and scanning electrochemical microscopy (SECM). These hybrid samples showed heterogeneous transport behavior determining diffusion coefficient (4⨯10-8 – 6⨯10-6 m2/s) following an increasing order of CoO/MLG < Co3O4/MLG < Co3O4/rGOHT < CoO/ErGO < CoNP/MLG and delivering the maximum specific capacitance 450 F/g for CoO/ErGO and Co3O4/ rGOHT. In agreement with CV properties, these electrodes showed the highest values of low-frequency capacitance and lowest charge-discharge response (0.38 s – 4 s), which were determined from impedance spectroscopy. Additionally, through circuit simulation of experimental impedance data, RC circuit elements were derived. SECM served to investigate electrode/electrolyte interfaces occurring at the solid/liquid interface operating in feedback probe approach and imaging modes while monitoring and mapping the redox probe (re)activity behavior. As expected, the hybrids showed an improved electroactivity as compared to the cobalt oxides by themselves, highlighting the importance of the graphene support. These improvements are facilitated through molecular/chemical bridges obtained by electrodeposition as compared with the physical deposition.

This PhD thesis presents investigations of hydrogen incorporation in Zintl phases and transition metal oxides. Hydrogenous Zintl phases can serve as important model systems for fundamental studies of hydrogen-metal interactions, while at the same time hydrogen-induced chemical structure and physical property changes provide exciting prospects for materials science. Hydrogen incorporation in transition metal oxides leads to oxyhydride systems in which O and H together form an anionic substructure. The H species in transition metal oxides may be highly mobile, making these materials interesting precursors toward other mixed anion systems.  Zintl phases consist of an active metal, M (alkali, alkaline earth or rare earth) and a more electronegative p-block metal or semimetal component, E (Al, Ga, Si, Ge, etc.). When Zintl phases react with hydrogen, they can either form polyanionic hydrides or interstitial hydrides, undergo full hydrogenations to complex hydrides, or oxidative decomposition to more E-rich Zintl phases. The Zintl phases investigated here comprised the CaSi2, Eu3Si4, ASi (A= K, Rb) and GdGa systems which were hydrogenated at various temperature, H2 pressure, and dwelling time conditions. For CaSi2, a regular phase transition from the conventional 6R to the rare 3R took place and no hydride formation was observed. In contrast, GdGa and Eu3Si4 were very susceptible to hydrogen uptake. Already at temperatures below 100 ºC the formation of hydrides GdGaH2-x and Eu3Si4H2+x was observed. The magnetic properties of the hydrides (antiferromagnetic) differ radically from that of the Zintl phase precursor (ferromagnetic). Upon hydrogenating ASi at temperatures around 100 oC, silanides ASiH3 formed which contain discrete complex ion units SiH3-. The much complicated β – α order-disorder phase transition in ASiH3 was evaluated with neutron powder diffraction (NPD), 2H NMR and heat capacity measurements.  A systematic study of the hydride reduction of BaTiO3 leading to perovskite oxyhydrides BaTiO3-xHx was done. A broad range of reducing agents including NaH, MgH2, CaH2, LiAlH4 and NaBH4 was employed and temperature and dwelling conditions for hydride reduction examined. Samples were characterized by X-ray powder diffraction (XRPD), thermal gravimetric analysis and 1H NMR. The concentration of H that can be incorporated in BaTiO3-xHx was found to be very low, which is in contrast with earlier reports. Instead hydride reduction leads to a high concentration of O vacancies in the reduced BaTiO3. The highly O-deficient, disordered, phases - BaTiO3-xHy□(x-y) with x up to 0.6 and y in a range 0.05 – 0.2 and (x-y) &gt; y – are cubic and may represent interesting materials with respect to electron and ion transport as well as catalysis. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 5: Manuscript.</p>

Ion selectivity of minerals has traditionally been utilized in industry as a catalyst, metal separation, and environmental reclamation/sequestration tool. There is an increased interest in understanding ion selectivity mechanisms of micro-porous minerals and mineral-like structures and how they can be applied in various industries: environmental and, potentially, pharmaceutical. This study seeks to understand the ion exchange mechanisms in micro-porous zirconosilicates using time-resolved Raman spectroscopy and X-ray diffraction. The thesis material was exchanged with H+, Na+, K+, and Cs+ in order to better understand structural changes as well as the influence of the H+-bonding during the exchange process. It is hypothesized that the host (H+) ion strongly influences the ion selectivity of the mineral by changing framework polyhedra and ring geometry, and the geometry of the interstitial the OH…H2O bond network to only allow cations of certain sizes through the channels. In addition, the H+ may repel cations with high charge densities from entering the extra-framework sites in the crystal structure by protonating the channel pathways.

Various synthetic methods have been developed to produce metal nanostructures including copper and iron nanostructures. Modification of nanoparticle surface to enhance their characteristic properties through surface functionalization with organic ligands ranging from small molecules to polymeric materials including organic semiconducting polymers is a key interest in nanoscience. However, most of the synthetic methods developed in the past depend widely on non-aqueous solvents, toxic reducing agents, and high temperature and high-pressure conditions. Therefore, to produce metal nanostructures and their nanocomposites with a simpler and greener method is indeed necessary and desirable for their nano-scale applications. Hence the objective of this thesis work is to develop an environmentally friendly synthesis method to make welldefined copper and iron nanostructures on a large-scale. The size and shape-dependent optical properties, solid-state crystal packing, and morphologies of nanostructures have been evaluated with respect to various experimental parameters. Nanostructures of copper and iron were prepared by developing an aqueous phase chemical reduction method from copper(II) chloride and Fe(III) chloride hexahydrate upon reduction using a mild reducing agent, sodium borohydride, under an inert atmosphere at room temperature. Well-defined copper nanocubes with an average edge length of 100±35 nm and iron nanochains with an average chain length up to 1.70 μm were prepared. The effect of the molar ratios of each precursor to the reducing agent, reaction time, and addition rate of the reducing agent were also evaluated in order to develop an optimized synthesis method for synthesis of these nanostructures. UV-visible spectral traces and X-ray powder diffraction traces were obtained to confirm the successful preparation of both nanostructrues. The synthesis method developed here was further modified to make poly(3-hexylthiophene) coated iron nanocomposites by surface functionalization with poly(3-hexylthiophene) carboxylate anion. Since these nanostructrues and nanocomposites have the ability to disperse in both aqueous-based solvents and organic solvents, the synthesis method provides opportunities to apply these metal nanostructures on a variety of surfaces using solution based fabrication techniques such as spin coating and spray coating methods.

Whey is a byproduct of cheese making; whey proteins are globular proteins which can be modified and polymerized to add functional benefits, these benefits can be both nutritional and structural in foods. Modified proteins can be used in non-foods, being of particular interest in polymer films and coatings. Food packaging materials, including plastics, can linings, interior coatings of paper containers, and beverage cap sealing materials, are generally made of synthetic petroleum based compounds. These synthetic materials may pose a potential human health risk due to presence of certain chemicals such as Bisphenol A (BPA). They also add to environmental pollution, being difficult to degrade. Protein-based materials do not have the same issues as synthetics and so can be used as alternatives in many packaging types. As proteins are generally hydrophilic they must be modified structurally and their performance enhanced by the addition of waterproofing agents. Polymerization of whey proteins results in a network, adding both strength and flexibility. The most interesting of the food-safe waterproofing agents are the (large aspect ratio) nanoclays. Nanoclays are relatively inexpensive, widely available and have low environmental impact. The clay surface can be modified to make it organophilic and so compatible with organic polymers. The objective of this study is the use of polymerized whey protein (PWP), with reinforcing nanoclays, to produce flexible surface coatings which limit the transfer of contents while maintaining food safety. Four smectite and kaolin type clays, one treated and three natural were assessed for strengthening qualities and the potential waterproofing and plasticizing benefits of other additives were also analyzed. The nutritional benefits of whey proteins can also be used to enhance the protein content of various foodstuffs. Drinkable yogurt is a popular beverage in the US and other countries and is considered a functional food, especially when produced with probiotic bacteria. Carbonation was applied to a drinkable yogurt to enhance its benefits. This process helps reduce the oxygen levels in the foodstuff thus potentially being advantageous to the microaerophilic probiotic bacteria while simultaneously producing a product, somewhat similar to kefir, which has the potential to fill a niche in the functional foods market. Yogurt was combined with a syrup to reduce its viscosity, making it drinkable, and also to allow infusion of CO2. This dilution reduced the protein content of the drink and so whey protein concentrate was added to increase levels in the final product. High-methoxyl pectins were used to provide stability by reducing the tendency of the proteins to sediment out. The objectives of this study were to develop a manufacturing technology for drinkable carbonated symbiotic yogurts, and to evaluate their physicochemical properties. Two flavors of yogurt drink, pomegranate and vanilla, were formulated containing inulin as prebiotic, along with probiotic bacteria, producing symbiotic dairy beverages.

High surface area gold electrodes are very good substrates for biosensors, catalysis and drug delivery. Their performance is characterized by good sensitivity, low detection limit and high signal. As a result, extensive research is being carried out in this field using different approaches of fabrication to generate high surface area porous electrodes of different morphology, pore size and structure. The morphology of the electrodes can be changed based on whether the approach involves a template or not, types of metal deposition, method and time of dealloying etc. The deposition of metal can be carried out using various approaches such as electroless deposition, electrochemical deposition, combination of electroless and electrochemical deposition, pulsed laser deposition, laser deposition etc. These electrodes can then be used in electrochemical measurements and their performance compared with an unmodified flat gold electrode. We used a template based approach, combined with electrochemical deposition, to fabricate macroporous, macro-nanoporous and nanoporous gold electrodes. To generate nanopores, in case of macro-nanoporous and nanoporous gold electrodes, we used gold-silver alloy electrochemical deposition method, followed by chemical dealloying. The morphology of electrodes was later observed under HITACHI Scanning Electron Microscope (SEM) and their elemental composition studied using HITACHI Energy Dispersion Spectroscopy (EDS). The electrodes were used in electrochemical measurements and their voltammetric data was compared. These measurements involved the determination of surface area, faradaic current using redox molecules with fast and slow electron transfer and charging current in KCl. Surface adsorption of dopamine was studied and detection of dopamine in the presence of ascorbic acid was carried out.

The synthesis of highly porous organic polymers with predefined porosity has attracted considerable attention due to their potential in a wide range of applications. Porous organic polymers (POPs) offer novel properties such as permanent porosity, adjustable chemical nature, and noteworthy thermal and chemical stability. These remarkable properties of the POPs make them promising candidates for use in gas separation and storage. The emission of carbon dioxide (CO2) from fossil fuel combustion is a major cause of global warming. Finding an efficient separation and/or storage material is essential for creating a cleaner environment. Therefore, the importance of the POPs in the field is undeniable. Along these pursuits, several porous polymers have been synthesized with different specifications. The first class of porous polymers are called Covalent Organic Frameworks (COFs). They possess highly ordered structures with very high surface areas and contain light elements. COFs based on B-O, C-N, and B-N bonds have been reported so far. In particular, COFs based on B-O bond formation are well investigated due to the kinetically labile nature of this bond which is essential for overcoming the crystallization problem of covalent networks. Along this line, triptycene-derived covalent organic framework (TDCOF-5) has been synthesized through a condensation reaction between 1, 4-benzenediboronic acid and hexahydroxytriptycene which leads to the formation of boronate ester linkage. TDCOF-5 has the highest H2 uptake under 1 atm at 77K (1.6%) among all known 2D and 3D COFs derived from B–O bond formation and moderate CO2 uptake (2.1 mmol g-1) with Qst values of 6.6 kJ mol-1 and 21.8 kJ mol-1, respectively. The second class of porous structures discussed herein is diazaborole linked polymers (DBLPs). They are constructed based on B-N bond formation and possess amorphous structures due to the lack of the reversible bond formation processes. At this scope, 2, 3, 6, 7, 14, 15-hexaaminotriptycene (HATT) hexahydrocloride was synthesized and reacted with different boronic acid derivatives to produce three different porous polymers under condensation reaction conditions. DBLP-3, -4 and -5 have very high surface areas; 730, 904, and 986 m2 g-1, and offer high CO2 uptake (158.5, 198, and 171.5 mg g-1) at 1 bar and 273 K, respectively. DBLPs have much higher CO2 uptake capacity when compared to almost all reported B-N and B-O containing porous polymers in the field. In addition to high CO2 capacity, DBLPs showed remarkable CO2/N2 and CO2/CH4 selectivity, when the Henry`s law of initial slope selectivity calculations were applied. In general, DBILPs exhibit high selectivities for CO2/N2 (35-51) and CO2/CH4 (5-6) at 298 K which are comparable to those of most porous polymers.