Mesoporous silica nanoparticles (MSNs) have attracted great interest for last two decades due to their unique and advantageous structural properties, such as high surface area, pore volume, stable mesostructure, tunable pore size and controllable particle morphology. The robust silica framework provides sites for organic modifications, making MSNs ideal platforms for adsorbents and supported organocatalysts. In addition, the pores of MSNs provide cavities/ channels for incorporation of metal and metal oxide nanoparticle catalysts. These supported metal nanoparticle catalysts benefit from confined local environments to enhance their activity and selectivity for various reactions. Biomass is considered as a sustainable feedstock with potential to replace diminishing fossil fuels for the production of biofuels. Among several strategies, one of the promising methods of biofuel production from biomass is to reduce the oxygen content of the feedstock in order to improve the energy density. This can be achieved by creating C-C bonds between biomass derived intermediates to increase the molecular weight of the final hydrocarbon molecules. In this context, pore size and organic functionality of MSNs are varied to obtain the ideal catalyst for a C-C bond forming reaction: the aldol condensation. The mechanistic aspects of this reaction in supported heterogeneous catalysts are explored. The …

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In this thesis, we explore both total syntheses and methodologies of several aromatic heterocyclic molecules. Extensions of the Kraus indole synthesis toward 2-substituted and 2,3-disubstituted indoles, as well as biologically attractive indolo[2,1-a]isoquinolines are described. Recent renewable efforts directed to commodity maleic acid and the first reported furan-based ionic liquids are described. Our total synthesis of mRNA aptamer ligand PDC-Gly, and its dye coupled forms, plus aminoglycoside dye coupled ligands used in molecular imaging, are described.

The world is currently facing an energy and environmental crisis for which new technologies are needed. Development of cost-competitive materials for catalysis and hydrogen storage on-board motor vehicles is crucial to lead subsequent generations into a more sustainable and energy independent future. This thesis presents work toward the scalable synthesis of bimetallic heterostructures that can enable hydrogen to compete with carbonaceous fuels by meeting the necessary gravimetric and volumetric energy densities and by enhancing hydrogen sorption/desorption kinetics near ambient temperatures and pressures. Utilizing the well-known phenomenon of hydrogen spillover, these bimetallic heterostructures could work by lowering the activation energy for hydrogenation and dehydrogenation of metals. Herein, we report a novel method for the scalable synthesis of silica templated zero-valent nickel particles (Ni⊂SiO{sub 2}) that hold promise for the synthesis of nickel nanorods for use in bimetallic heterostructures for hydrogen storage. Our synthesis proceeds by chemical reduction of a nickel-hydrazine complex with sodium borohydride followed by calcination under hydrogen gas to yield silica encapsulated nickel particles. Transmission electron microscopy and powder X-ray diffraction were used to characterize the general morphology of the resultant nanocapsules as well as the crystalline phases of the incorporated Ni{sup 0} nanocrystals. The structures display strong magnetic …

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After a decade of preparations, the Qweak experiment at Jefferson Lab is making the first direct measurement of the weak charge of the proton, Q^p_W. This quantity is suppressed in the Standard Model making a good candidate for search for new physics beyond the SM at the TeV scale. Operationally, we measure a small (about -0.200 ppm) parity-violating asymmetry in elastic electron-proton scattering in integrating mode while flipping the helicity of the electrons 1000 times per second. Commissioning took place Fall 2010, and we finished taking data in early summer 2012. This dissertation is based on the data taken on an initial two weeks period (Wien0). It will provide an overview of the Qweak apparatus, description of the data acquisition and analysis software systems, and final analysis and results from the Wien0 data set. The result is a 16% measurement of the parity violating electron-proton scattering asymmetry, A = -0.2788 +/- 0.0348 (stat.) +/- 0.0290 (syst.) ppm at Q^2 = 0.0250 +/- 0.0006 (GeV)^2. From this a 21% measurement of the weak charge of the proton, Q_w^p(msr)= +0.0952 +/- 0.0155 (stat.) +/- 0.0131 (syst.) +/- 0.0015 (theory) is extracted. From this a 2% measurement of the weak mixing angle, sin^2theta_W(msr)= …

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This thesis outlines advancements in Raman scatter enhancement techniques by applying evanescent fields, standing-waves (waveguides) and surface enhancements to increase the generated mean square electric field, which is directly related to the intensity of Raman scattering. These techniques are accomplished by employing scanning angle Raman spectroscopy and surface enhanced Raman spectroscopy. A 1064 nm multichannel Raman spectrometer is discussed for chemical analysis of lignin. Extending dispersive multichannel Raman spectroscopy to 1064 nm reduces the fluorescence interference that can mask the weaker Raman scattering. Overall, these techniques help address the major obstacles in Raman spectroscopy for chemical analysis, which include the inherently weak Raman cross section and susceptibility to fluorescence interference.

A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe{sub 2}){sub 3} and KC(SiHMe{sub 2}){sub 3}TMEDA are synthesized by deprotonation of the hydrocarbon HC(SiHMe{sub 2}){sub 3} with potassium benzyl. KC(SiHMe{sub 2}){sub 3}TMEDA crystallizes as a dimer with two types of three-center-two-electron KH- Si interactions. Homoleptic Ln(III) tris(silylalkyl) complexes containing β-SiH groups M{C(SiHMe{sub 2}){sub 3}}{sub 3} (Ln = Y, Lu, La) are synthesized from salt elimination of the corresponding lanthanide halide and 3 equiv. of KC(SiHMe{sub 2}){sub 3}. The related reactions with Sc yield bis(silylalkyl) ate-complexes containing either LiCl or KCl. The divalent calcium and ytterbium compounds M{C(SiHMe{sub 2}){sub 3}}{sub 2}L (M = Ca, Yb; L = THF{sub 2} or TMEDA) are prepared from MI{sub 2} and 2 equiv of KC(SiHMe{sub 2}){sub 3}. The compounds M{C(SiHMe{sub 2}){sub 3}}{sub 2}L (M = Ca, Yb; L = THF{sub 2} or TMEDA) and La{C(SiHMe{sub 2}){sub 3}}{sub 3} react with 1 equiv of B(C{sub 6}F{sub 5}){sub 3} to give 1,3- disilacyclobutane {Me2Si-C(SiHMe2)2}2 and MC(SiHMe2)3HB(C6F5)3L, and La{C(SiHMe{sub 2}){sub 3}}{sub 2}HB(C{sub 6}F{sub 5}){sub 3}, respectively. The corresponding reactions of Ln{C(SiHMe{sub 2}){sub 3}}{sub 3} (Ln = Y, Lu) give the β-SiH abstraction product [{(Me{sub 2}HSi){sub 3}C}{sub 2}LnC(SiHMe{sub 2}){sub 2}SiMe{sub 2}][HB(C{sub 6}F{sub 5}){sub 3}] …

The beam normal single spin asymmetry generated in the scattering of transversely polarized electrons from unpolarized nucleons is an observable of the imaginary part of the two-photon exchange process. Moreover, it is a potential source of false asymmetry in parity violating electron scattering experiments. The Q{sub weak} experiment uses parity violating electron scattering to make a direct measurement of the weak charge of the proton. The targeted 4% measurement of the weak charge of the proton probes for parity violating new physics beyond the Standard Model. The beam normal single spin asymmetry at Q{sub weak} kinematics is at least three orders of magnitude larger than 5 ppb precision of the parity violating asymmetry. To better understand this parity conserving background, the Q{sub weak} Collaboration has performed elastic scattering measurements with fully transversely polarized electron beam on the proton and aluminum. This dissertation presents the analysis of the 3% measurement (1.3% statistical and 2.6% systematic) of beam normal single spin asymmetry in electronproton scattering at a Q2 of 0.025 (GeV/c)2. It is the most precise existing measurement of beam normal single spin asymmetry available at the time. A measurement of this precision helps to improve the theoretical models on beam normal …

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In contrast to the nuclear charge densities, which have been accurately measured with electron scattering, the knowledge of neutron densities still lack precision. Previous model-dependent hadron experiments suggest the difference between the neutron radius, R{sub n}, of a heavy nucleus and the proton radius, R{sub p}, to be in the order of several percent. To accurately obtain the difference, R{sub n}-R{sub p}, which is essentially a neutron skin, the Jefferson Lab Lead ({sup 208}Pb) Radius Experiment (PREX) measured the parity-violating electroweak asymmetry in the elastic scattering of polarized electrons from {sup 208}Pb at an energy of 1.06 GeV and a scattering angle of 5{degrees}#14;. Since Z{sup 0} boson couples mainly to neutrons, this asymmetry provides a clean measurement of R{sub n} with respect to R{sub p}. PREX was conducted at the Jefferson lab experimental Hall A, from March to June 2010. The experiment collected a final data sample of 2x#2;10{sup 7} helicity-window quadruplets. The measured parity-violating electroweak asymmetry A{sub PV} = 0.656 {+-}#6; 0.060 (stat) {+-}#6; 0.014 (syst) ppm corresponds to a difference between the radii of the neutron and proton distributions, R{sub n}-R{sub p} = 0.33{sup +0.16}{sub -0.18} fm and provides the #12;first electroweak observation of the neutron skin …