Mesoporous silicates are excellent materials for supported catalysis due to their ease of functionalization, tunable pore size and high surface areas. Mesoporous silicates have been utilized in a variety of applications such as drug delivery scaffolds and catalyst supports. Functionalization of the surface can be achieved by either grafting of alkoxy silanes or co-condensation of the organosilane with the inorganic silica source. My research in this area can be divided into two components. In the first, we address the significant issue of metal contamination after reactions that are catalyzed by transition metals. In the second, we examine the design of new catalysts based on organic/inorganic composites. Ruthenium catalyzed processes such as olefin metathesis or asymmetric hydrogenation, are often underutilized due to the difficulty of removing the ruthenium by-products. Attempts to remove ruthenium involve treating the solution with a scavenging reagent followed by silica chromatography. Often these scavenging agents are expensive phosphines or toxic agents like lead tetra-acetate. SBA-15 functionalized with aminopropyl triethoxysilane displays a high affinity for ruthenium. Furthermore, it can be utilized to remove ruthenium by-products from olefin metathesis or hydrogenation reactions without the need for silica chromatography. We have also prepared sulfur-functionalized mesoporous silicates that have a high affinity for palladium. The materials after loading prove to be active catalysts for a variety of palladium catalyzed processes such as Suzuki-Miyaura and Sonogashira couplings. The catalysts are recyclable with moderate loss of activity and structure, depending on the method of incorporation of the thiol. We have characterized the as-synthesized and used catalysts by nitrogen sorption, TEM, X-ray photoelectron spectroscopy (XPS) and a variety of homogeneity tests were performed on the catalysts. Periodic mesoporous organosilicates (PMOs) are a well known class of inorganic-organic hybrid materials. The majority of PMOs prepared utilize simple organic bridges such as ethyl, phenyl or biphenyl. The use of a chiral organic bridging group, such as BINAP, allows the synthesis of chiral PMOs with possible applications in catalysis and separation science. The synthesis of a triethoxysilyl functionalized BINAP as well as its incorporation into PMO materials with 4,4’-bistriethoxysilyl biphenyl or tetraethylorthosilicate as co-silica sources are described. / Thesis (Ph.D, Chemistry) -- Queen's University, 2009-04-20 10:49:13.443

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CP violation is an important condition to explain the preponderance of baryons in our universe, yet the available CP violation in the Standard Model (SM) via the so-called Cabibbo-Kobayashi-Maskawa mechanism seems to not provide enough CP violation. Thus searching for new sources of CP violation is one of the central tasks of modern physics. In this thesis, we focus on a new possible source of CP violation which generates triple-product correlations in momenta which can appear in neutron and nuclear radiative β decay. We show that at low energies such a CP violating correlation may arise from the exotic coupling of nucleon, photon and neutrino that was proposed by Harvey, Hill, and Hill (HHH). One specialty of such an exotic HHH coupling is that it does not generate the well-known CP-violating terms such as ``D-term'', ``R-term'', and neutron electric dipole moment, in which particle's spins play critical role. We show that such a new HHH-induced CP violating effect is proportional to the imaginary part of c5gv, where gv is the vector coupling constant in neutron and nuclear β decay, and c5 is the phenomenological coupling constant that appears in chiral perturbation theory at O(M-2) with M referring to the nucleon or nuclear mass. We consider a possible non-Abelian hidden sector model, which is beyond the SM and may yield a nontrivial Im(c5). The available bounds on both Im(c5) and Im(gv) are considered, and a better limit on Im(c5) can come from a direct measurement in radiative beta decay. We calculate the competitive effect that arises from the general parameterization of the weak interaction that was proposed by Lee and Yang in 1956. We also show that in the proposed measurements, the CP-violating effect can be mimicked by the SM via final-state interactions (FSI). For a better determination of the bound of Im(c5), we consider the FSI-induced mimicking effect in full detail in O(α) as well as in leading recoil order. To face ongoing precision measurements of neutron radiative β decay of up to 1% relative error, we sharpen our calculations of the CP conserving pieces of neutron radiative β decay by considering the largest contributions in O(α2): the final-state Coulomb corrections as well as the contributions from two-photon radiation.

This dissertation combines laboratory and field experiments to investigate the mechanisms of atropisomer enrichment for chiral polychlorinated biphenyls (PCBs) and their metabolites in organisms. Stereoselective biotransformation and bioaccumulation were identified as two major reasons for the different environmental fate of PCB atropisomers. Other affecting factors, such as presence of nanoparticles and changes in feeding ecology of organisms, also affect the fate of chiral contaminants. In vitro incubations of rat cytochrome P-450 2B1 (CYP2B1) isozyme with chiral PCBs indicated that different biotransformation kinetics and competition among PCB congeners or between atropisomers were two main factors affecting atropisomer enrichment. Different interactions between chiral PCB congeners or atropisomers with rat CYP2B1 may occur at the molecular level. Non-racemic meta-hydroxylated-PCBs (5-OH-PCBs) were the major metabolites. CYP-mediated stereoselective formation of dihydroxylated PCBs from OH-PCBs was observed. Gold nanoparticles affected biotransformation activity of rat CYP2B1 and changed PCB atropisomeric composition, directly by electrostatic interaction, or indirectly by changes to the surrounding ionic strength. Thus, stereoselective metabolism of chiral PCBs and OH-PCBs by CYPs is a major mechanism for atropisomer enrichment of PCBs and their metabolites in the environment, with the degree of enrichment dependent, at least in part, on charged nanoparticles and stereoselective interference of atropisomers with each other at the enzyme level. The atropisomer compositions of chiral PCBs were measured in the marine biota of Cumberland Sound (Canada) and Svalbard (Norway). High trophic level organisms, including harp seal, beluga, and narwhal reported for the first time, had species-specific atropisomer signatures, likely due to a combination of in vivo biotransformation and trophic transfer. PCB chiral signatures in Greenland sharks supported the hypothesis that some of these PCB atropisomer compositions shifted over time and space, possibly due to a change in feeding ecology. To our knowledge, this is the first report to investigate temporal trends of PCB atropisomer signatures in Arctic biota.

Chiral perturbation theory is a useful tool in the study of low energy reactions involving light particles. However the inclusion of heavy particles in chiral perturbation theory results in large contributions from loop diagrams which violate the standard power counting scheme. We review two methods, referred to as heavy baryon chiral perturbation theory and infrared regularization, which remove the high energy effects of the heavy particles and which therefore do not violate the power counting scheme. We then use these two methods to calculate the amplitude for pion photoproduction to fourth order and prove that the two amplitudes are equivalent.

ABSTRACT SYNTHESIS OF 1,2,3,5-TETRASUBSTITUTED PYRROLE DERIVATIVES VIA 5-EXO-DIG TYPE CYCLIZATION AND STEREOSELECTIVE FUNCTIONALISATION OF FERROCENE DERIVATIVES Metin Kayalar M.S., Department of Chemistry Supervisor: Prof. Dr. Ayhan S. Demir January 2005, 102 pages A convenient and new method for the synthesis of 1,2,3,5-tetrasubstituted pyrrole derivatives starting from 1,3,-dicarbonyl compounds through acid catalyzed cyclization reaction is described. Alkylation of 1,3-dicarbonyl compound with propargyl bromide followed by one step cyclization with the introduction of primary amines in the presence of catalytic amount of triflouroacetic acid (TFA) affords the corresponding pyrrole derivatives in high yields. The investigations on the studies of developing a new method for catalytic and stereoselective functionalisation of ferrocene derivatives were summarized. Functionalisation studies were carried out in three main strategy the first one of which is carboxylation, second one is arylation and the last one is oxidative cross-coupling with &amp / #945 / , &amp / #946 / -unsaturated carbonyl compounds.

The asymmetric synthesis of cis-1,4-aminoalcohols with norbornene backbone was performed starting with simple and cheap anhydride 30. Quinine-mediated desymmetrization of anhydride 30 with methanol resulted in (2S,3R)-(-)-cis-hemiester 31 (98% e.e.). Chemoselective amination with HMPTA and NH4OH followed by LAH reduction afforded (2S,3R)-(+)-36 and (2S,3R)-(-)-37, respectively. The amidoester (2S,3R)-(-)-32 was transformed into chiral ligand (2S,3R)-(-)-35 with Grignard reaction followed by LAH reduction. The chiral ligands (2S,3R)-(-)-35, (2S,3R)-(+)-36 and (2S,3R)-(-)-37 were subjected to asymmetric diethylzinc addition reaction to examine their effectiveness as chiral catalyst. Among these, chiral ligand 36 exhibited the highest enantioselectivity (88% e.e.)

Low-density cellular solids have demonstrated superior mechanical properties as well as multifunctional characteristics, which may provide a basis for the development of novel structured materials. In particular, cellular solids offer great design flexibility, owing to their topology, which can provide desired functionalities via targeted geometric design and proper selection of the constituent material. While stochastic configurations such as metallic foams have proven to be effective for both thermal insulation and mechanical-energy absorption, the topology of deterministic architectures is not constrained by physical processes. This allows for a variety of configurations to be tailored to simultaneously fulfill disparate tasks. An additional aspect of deterministic cellular structures is the possibility of assembling materials or structures by the spatial repetition of a unit cell. The resulting periodicity of such systems simplifies the characterization of physical properties, which can be established by analyzing the unit cell only, and will provide new opportunities in the fields of structural dynamics, where periodicity-induced impedance leads to the control of both constructive and destructive interference on propagating waves. The objective of this work is to investigate the application of the chiral cellular topology for the design of novel macrostructural, mesostructural and microstructural configurations. A truss-core airfoil, and a truss-core beam are employed as a basis to demonstrate both large-displacement capabilities within the elastic regime of the constituent material, as well as operational deflection shapes with localized dynamic deformations. Large deformation capabilities and unique operational deflection shapes are to be attributed to the unusual deformation mechanism of the chiral lattice. Mesostructural and microstructural configurations, on the other hand, are characterized by an unique mechanical behavior, complex geometry, as well as geometric design flexibility to control both static and dynamic phenomena. The propagation of elastic waves, moreover, is characterized by significant band-gap density as well as strong energy focusing dependent on frequency and wavenumber. These features suggest the chiral topology as a basis for the development of acoustic meta-materials.

In this thesis, we investigate sigma models and algebraic structures emerging from a Hamiltonian description of their dynamics, both in a classical and in a quantum setup. More specifically, we derive the phase space structures together with the Hamiltonians for the bosonic two-dimensional non-linear sigma model, and also for the N=1 and N=2 supersymmetric models. A convenient framework for describing these structures are Lie conformal algebras and Poisson vertex algebras. We review these concepts, and show that a Lie conformal algebra gives a weak Courant–Dorfman algebra. We further show that a Poisson vertex algebra generated by fields of conformal weight one and zero are in a one-to-one relationship with Courant–Dorfman algebras. Vertex algebras are shown to be appropriate for describing the quantum dynamics of supersymmetric sigma models. We give two definitions of a vertex algebra, and we show that these definitions are equivalent. The second definition is given in terms of a λ-bracket and a normal ordered product, which makes computations straightforward. We also review the manifestly supersymmetric N=1 SUSY vertex algebra. We also construct sheaves of N=1 and N=2 vertex algebras. We are specifically interested in the sheaf of N=1 vertex algebras referred to as the chiral de Rham complex. We argue that this sheaf can be interpreted as a formal quantization of the N=1 supersymmetric non-linear sigma model. We review different algebras of the chiral de Rham complex that one can associate to different manifolds. In particular, we investigate the case when the manifold is a six-dimensional Calabi–Yau manifold. The chiral de Rham complex then carries two commuting copies of the N=2 superconformal algebra with central charge c=9, as well as the Odake algebra, associated to the holomorphic volume form.

Gas chromatography (GC) has been utilized for the study of enantiomer resolution of the atropisomers of PCBs, o,p´-DDD and o,p´-DDT. Different substituents and concentrations of cyclodextrin, capillary dimensions and type of stationary phase films have been investigated to achieve the resolution of as many of the atropisomers on one column as possible. The results indicated that the butyl substitution of 6-hydroxyl and the methyl substitution of 2- and 3-hydroxyl were the most promising for the enantiomeric separation. Using Capillary Electrophoresis (CE), the trimers and monomers of PM-β-CDs were compared for enantiomeric resolution, as well as comparing the cationic PMMA-β-CD with the anionic HS-β-CD. In these studies the trimer did not show an improved resolution for mepivacaine, when compared to the equimolar concentration of the monomer. The cationic CD gave increased resolution values for ibuprofen when compared to the anionic CD. A scheme for reversing enantiomeric elution order of both the basic propranolol and acidic ibuprofen is also presented, with the aim of facilitating the detection of impurities in a high sample loading. The detection of 1% of each enantiomer of propranolol, and 1% of R(-)-ibuprofen, was demonstrated, with elution prior to the tailing peak of the corresponding enantiomer. Dimethylacrylamide-coated capillaries were used in this work, and the stability of this coating was demonstrated, giving a highly reduced electroosmotic flow for up to six months. Enantiomeric baseline separations of omeprazole and 5-hydroxyomeprazole have also been achieved with both CE and Open Tubular Capillary Electrochromatography (OT-CEC) methods. With CE-UV, both a non-aqueous method (using HDMS-β-CD) and an aqueous method (using HS-β-CD) were used for enantiomeric resolution of the two racemates. Resolution of omeprazole was also achieved using CE-Electrospray Ionization-Mass Spectrometry (ESI-MS). In OT-CEC, avidin was immobilized on the inside surface of a fused silica capillary and was employed as chiral selector for the enantiomeric baseline resolution of omeprazole and 5-hydroxyomeprazole.