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Description
Nuclear magnetic resonance (NMR) is an important phenomenon involving nuclear magnetic moments in magnetic field, which can provide much information about a wide range of materials, including their chemical composition, chemical environments and nuclear spin interactions. The NMR spectrometer has been extensively developed and used in many areas of research.

Nuclear magnetic resonance (NMR) is an important phenomenon involving nuclear magnetic moments in magnetic field, which can provide much information about a wide range of materials, including their chemical composition, chemical environments and nuclear spin interactions. The NMR spectrometer has been extensively developed and used in many areas of research. In this thesis, studies in two different areas using NMR are presented. First, a new kind of nanoparticle, Gd(DTPA) intercalated layered double hydroxide (LDH), has been successfully synthesized in the laboratory of Prof. Dey in SEMTE at ASU. In Chapter II, the NMR relaxation studies of two types of LDH (Mg, Al-LDH and Zn, Al-LDH) are presented and the results show that when they are intercalated with Gd(DTPA) they have a higher relaxivity than current commercial magnetic resonance imaging (MRI) contrast agents, such as DTPA in water solution. So this material may be useful as an MRI contrast agent. Several conditions were examined, such as nanoparticle size, pH and intercalation percentage, to determine the optimal relaxivity of this nanoparticle. Further NMR studies and simulations were conducted to provide an explanation for the high relaxivity. Second, fly ash is a kind of cementitious material, which has been of great interest because, when activated by an alkaline solution, it exhibits the capability for replacing ordinary Portland cement as a concrete binder. However, the reaction of activated fly ash is not fully understood. In chapter III, pore structure and NMR studies of activated fly ash using different activators, including NaOH and KOH (4M and 8M) and Na/K silicate, are presented. The pore structure, degree of order and proportion of different components in the reaction product were obtained, which reveal much about the reaction and makeup of the final product.
ContributorsPeng, Zihui (Author) / Marzke, Robert F (Thesis advisor) / Dey, Sandwip Kumar (Committee member) / Neithalath, Narayanan (Committee member) / Chamberlin, Ralph Vary (Committee member) / Mccartney, Martha Rogers (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Spider dragline silk is well known for its outstanding mechanical properties - a combination of strength and extensibility that makes it one of the toughest materials known. Two proteins, major ampullate spidroin 1 (MaSp1) and 2 (MaSp2), comprise dragline silk fibers. There has been considerable focus placed on understanding the

Spider dragline silk is well known for its outstanding mechanical properties - a combination of strength and extensibility that makes it one of the toughest materials known. Two proteins, major ampullate spidroin 1 (MaSp1) and 2 (MaSp2), comprise dragline silk fibers. There has been considerable focus placed on understanding the source of spider silk's unique mechanical properties by investigating the protein composition, molecular structure and dynamics. Chemical compositional heterogeneity of spider silk fiber is critical to understand as it provides important information for the interactions between MaSp1 and MaSp2. Here, the amino acid composition of dragline silk protein was precisely determined using a solution-state nuclear magnetic resonance (NMR) approach on hydrolyzed silk fibers. In a similar fashion, solution-state NMR was applied to probe the "13"C/"15"N incorporation in silk, which is essential to understand for designing particular solid-state NMR methods for silk structural characterization. Solid-state NMR was used to elucidate silk protein molecular dynamics and the supercontraction mechanism. A "2"H-"13"C heteronuclear correlation (HETCOR) solid-state NMR technique was developed to extract site-specific "2"H quadrupole patterns and spin-lattice relaxation rates for understanding backbone and side-chain dynamics. Using this technique, molecular dynamics were determined for a number of repetitive motifs in silk proteins - Ala residing nanocrystalline &beta-sheet; domains, 3"1"-helical regions, and, Gly-Pro-Gly-XX &beta-turn; motifs. The protein backbone and side-chain dynamics of silk fibers in both dry and wet states reveal the impact of water on motifs with different secondary structures. Spider venom is comprised of a diverse range of molecules including salts, small organics, acylpolyamines, peptides and proteins. Neurotoxins are an important family of peptides in spider venom and have been shown to target and modulate various ion channels. The neurotoxins are Cys-rich and share an inhibitor Cys knot (ICK) fold. Here, the molecular structure of one G. rosea tarantula neurotoxin, GsAF2, was determined by solution-state NMR. In addition, the interaction between neurotoxins and model lipid bilayers was probed with solid-state NMR and negative-staining (NS) transmission electron microscopy (TEM). It is shown that the neurotoxins influence lipid bilayer assembly and morphology with the formation of nanodiscs, worm-like micelles and small vesicles.
ContributorsShi, Xiangyan (Author) / Yarger, Jeffery L (Thesis advisor) / Holland, Gregory P (Thesis advisor) / Levitus, Marcia (Committee member) / Marzke, Robert F (Committee member) / Arizona State University (Publisher)
Created2014
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Description
In this work, a new method, "Nanobonding" [1,2] is conceived and researched to bond Si-based surfaces, via nucleation and growth of a 2 D silicon oxide SiOxHx interphase connecting the surfaces at the nanoscale across macroscopic domains. Nanobonding cross-bridges two smooth surfaces put into mechanical contact in an O2/H2O mixed

In this work, a new method, "Nanobonding" [1,2] is conceived and researched to bond Si-based surfaces, via nucleation and growth of a 2 D silicon oxide SiOxHx interphase connecting the surfaces at the nanoscale across macroscopic domains. Nanobonding cross-bridges two smooth surfaces put into mechanical contact in an O2/H2O mixed ambient below T <200 °C via arrays of SiOxHx molecules connecting into a continuous macroscopic bonding interphase. Nano-scale surface planarization via wet chemical processing and new spin technology are compared via Tapping Mode Atomic Force Microscopy (TMAFM) , before and after nano-bonding. Nanobonding uses precursor phases, 2D nano-films of beta-cristobalite (beta-c) SiO2, nucleated on Si(100) via the Herbots-Atluri (H-A) method [1]. beta-c SiO2 on Si(100) is ordered and flat with atomic terraces over 20 nm wide, well above 2 nm found in native oxides. When contacted with SiO2 this ultra-smooth nanophase can nucleate and grow domains with cross-bridging molecular strands of hydroxylated SiOx, instead of point contacts. The high density of molecular bonds across extended terraces forms a strong bond between Si-based substrates, nano- bonding [2] the Si and silica. A new model of beta-cristobalite SiO2 with its <110> axis aligned along Si[100] direction is simulated via ab-initio methods in a nano-bonded stack with beta-c SiO2 in contact with amorphous SiO2 (a-SiO2), modelling cross-bridging molecular bonds between beta-c SiO2 on Si(100) and a-SiO2 as during nanobonding. Computed total energies are compared with those found for Si(100) and a-SiO2 and show that the presence of two lattice cells of !-c SiO2 on Si(100) and a-SiO2 lowers energy when compared to Si(100)/ a-SiO2 Shadow cone calculations on three models of beta-c SiO2 on Si(100) are compared with Ion Beam Analysis of H-A processed Si(100). Total surface energy measurements via 3 liquid contact angle analysis of Si(100) after H-A method processing are also compared. By combining nanobonding experiments, TMAFM results, surface energy data, and ab-initio calculations, an atomistic model is derived and nanobonding is optimized. [1] US Patent 6,613,677 (9/2/03), 7,851,365 (12/14/10), [2] Patent Filed: 4/30/09, 10/1/2011
ContributorsWhaley, Shawn D (Author) / Culbertson, Robert J. (Thesis advisor) / Herbots, Nicole (Committee member) / Rez, Peter (Committee member) / Marzke, Robert F (Committee member) / Lindsay, Stuart (Committee member) / Chamberlin, Ralph V (Committee member) / Arizona State University (Publisher)
Created2011
ContributorsBach, Johann Sebastian, 1685-1750 (Composer)