Phosphotriesterase (PTE) is a zinc metalloenzyme that catalyzes the hydrolysis of organophosphorus compounds. Metal ion roles during binding and catalysis are probed by comparing the kinetic properties of Zn/Zn, Cd/Cd, and Zn/Cd PTE with a variety of phosphate trisesters. The metal in the α-site of the binuclear metal center modulates the pKa values determined from pH-rate profiles. These results suggest that the α-metal is responsible for activating the nucleophilic hydroxide. In an effort to determine the function of the β-metal, the kinetic parameters for diethyl p-chlorophenyl thiophosphate are compared with diethyl p-chlorophenyl phosphate. The thiophosphate substrate is hydrolyzed 20 to 100-times faster than the phosphate substrate for Zn/Zn, Cd/Cd, and Zn/Cd PTE. When Cd2+ occupies the β-site, the inverse thio effect increases which suggests polarization by the β-metal on the phosphoryl oxygen or sulfur bond. The catalytic roles of Asp 233, His 254, and Asp 301 are determined by comparing the kinetic parameters of a series of alanine and asparagine mutations with paraoxon and diethyl p-chlorophenyl phosphate. The increased rate of hydrolysis for diethyl p-chlorophenyl phosphate with the mutants is consistent with the existence of a proton relay system from Asp 301 to His 254 to Asp 233. A detailed mechanism for the hydrolysis of organophosphates by PTE has been proposed. PTE hydrolyzes a number of chiral organophosphorus esters. The pKa of the leaving group phenol is altered for a series of chiral phosphate, phosphonate, and phosphinate esters. The stereoselectivity of wild-type, G60A, and I106G/F132G/H257Y PTE is enhanced as the pKa value of the leaving group phenol increases for phosphate, phosphonate, and phosphinate esters. In addition to improving the stereoselectivity of phosphotriesterase, mutations that affect the size of the active site of PTE are screened to identify a mutant enzyme that preferentially hydrolyzes the opposite isomer of wild-type PTE. The rate constants and stereoselectivity ratios for a number of active site mutants have been determined. H254Y/L303T PTE reverses the stereoselective preference of phosphonate and phosphinate substrates. The PTE stereoselectivity of O-methyl, O-phenyl acetylphenyl phosphate is reversed 970-fold by I106G/F132G/H257Y. A reversal mutant was resolved for phosphate, phosphonate, and phosphinate esters.

This dissertation concerns the syntheses and characterization of supramolecules with quadruply bonded Mo2 4+ units, Mo2(DAniF)3 + (DAniF = N,N'-di-p-anisylformamidinate) or cis- Mo2(DAniF)2 2+, and chiral organometallic Rh2 4+ units, including racemic cis-Rh2(C6H4PPh2)2 2+ and pure enantiomers of cis-Rh2(C6H4PPh2)2 2+. Molecular pairs of dimolybdenum units in which Mo2(DAniF)3 + units are linked by cyclic diamidate anions or dioxolene anions have been investigated. Linkers impact the electronic communication between the dimetal units in various ways. The symmetry and the energy of the frontier orbitals of the linker are among the factors which influence significantly the properties of the molecular pairs. Nature has provided us a great opportunity to study quantitatively the equilibrium between neutral supramolecules with cis-Mo2(DAniF)2 2+ units. Studies of the concentrationdependent and temperature-dependent equilibria between a molecular triangle and square as well as a molecular loop and triangle using 1H and 19F NMR spectra provide quantitative values for the thermodynamic equilibrium constant K, as well as ∆Hº, and ∆Sº for the equilibria. The synthesis and characterization supramolecular compounds containing chiral cis- Rh2(C6H4PPh2)2 2+ units, including three racemic triangles and pure enantiomers of three triangles, a carceplex with T symmetry and two loops are also presented.

Recently, Iwamoto[1] has proposed a passive-matrix LCD called VA-STN-LCD (Verically Aligned Super Twist Nemetic LCD), in which excellent electro-optic (EO) performance under high-multiplexing conditions has been demonstrated. It was pointed out that such a high EO performance was realized by achieving a pretilt angle of about 80 degree. In this study, we want to learn the different EO characteristic of separate pretilt angle and separate chiral-doped concentration of Negative Dielectric Anisotropy nemetic liquid crystal in vertically aligned cell.

A novel holographic model of chiral symmetry breaking has been proposed by Kuperstein and Sonnenschein by embedding non-supersymmetric probe D7 and anti-D7 branes in the Klebanov-Witten background. We study the dynamics of the probe flavours in this model in the presence of finite temperature and a constant electromagnetic field. In keeping with the weakly coupled field theory intuition, we find the magnetic field promotes spontaneous breaking of chiral symmetry whereas the electric field restores it. The former effect is universally known as the ``magnetic catalysis" in chiral symmetry breaking. In the presence of an electric field such a condensation is inhibited and a current flows. Thus we are faced with a steady-state situation rather than a system in equilibrium. We conjecture a definition of thermodynamic free energy for this steady-state phase and using this proposal we study the detailed phase structure when both electric and magnetic fields are present in two representative configurations: mutually perpendicular and parallel. / text

In this dissertation, two exactly solvable models from the Kitaev class [Ann. Phys. 321, 2 (2006)] of exactly solvable models are analysed. In the second chapter, Kitaev models and their generic properties are reviewed. Majorana fermions are introduced and discussed. Then their relationship with the solution of Kitaev models are discussed which involves the emergence of a Z₂ gauge symmetry and anyonic particles of both Abelian and non-Abelian varieties. The third chapter, which is based on the research article [Phys. Rev. B (Rapid Comm.) 83, (2011)], examines the Kitaev model on the kagome lattice. A rich phase diagram of this model is found to include a topological (gapped) chiral spin liquid with gapless chiral edge states, and a gapless chiral spin liquid phase with a spin Fermi surface. The ground state of the current model contains an odd number of electrons per unit cell which qualitatively distinguishes it from previously studied exactly solvable models with a spin Fermi surface. Moreover, it is shown that the spin Fermi surface is stable against weak perturbations. The fourth chapter is based on the article [Phys. Rev. B 84,(2011)] and analyses a disordered generalisation of the Yao-Kivelson [Phys. Rev. Lett. 99,247203 (2007)] chiral spin-liquid on the decorated honeycomb lattice. The model is generalised by the inclusion of random exchange couplings. The phase diagram was determined and it is found that disorder enlarges the region of the topological non-Abelian phase with finite Chern number. A study of the energy level statistics as a function of disorder and other parameters in the Hamiltonian show that the phase transition between the non-Abelian and Abelian phases of the model at large disorder can be associated with pair annihilation of extended states at zero energy. Analogies to integer quantum Hall systems, topological Anderson insulators, and disordered topological Chern insulators are discussed. / text

Described in this thesis is the isolation of two microorganisms containing a nitrile hydratase and amidase to effect the enantioselective hydrolysis of a-substituted nitriles to their corresponding amides and acids. Isolate NP3854 was identified as an atypical Rhodococcus sp. The nitrile hydratase proved to be non-selective for all the substrates tested. However, carboxylic acids with excellent enantiomeric excess were obtained from a large number of amides. X R~CN H nitr-il-e--h-y-d-r.a~tase ~X amidas.e RH CONH2 X R~"""CO H H 2 Optically active acids with an enantiomeric excess of, generally, >98 %, were obtained when X = NH2, Me and Cl, but proved to be racemic for OH and Br. R could be a variety of aromatic, cyclic and acyclic alkyl residues without adversely affecting the enantioselectivity. The pH-activity profile was determined for the amidase of NP3854 using propionamide as the substrate. From this data, coupled with inhibition studies, it may ,.tentatively be suggested that the amidase has a histidine residue in the active site, which may act as a general base for a serine amino acid. The pH-activity profile was determined for 2-amino-2-phenylacetamide 2b, and this suggested that the unprotonated form of the amine acted as the substrate. Within a pH range of 3 - 9 the enantiomeric excess remains high (>98 %) and experimentally invariant. The amidase was found to have a temperature optimum of 60°C and could tolerate 20 % THF with a loss of only 15 % activity. Attempts made to hydrolyse 4,5,6-amino nitriles and amides to the corresponding amino acids and isolate any reaction intermediates failed. This was presumed to be due to the large fraction of the unprotonated amine due to the higher pKa (- 9 - 10).

Synthetic efforts toward fumonisin analog were described. These are accomplished via amino acid Schiff base methodology. These efforts can be divided three major phases. First, tandem reductive alkylation with DIBAL/TRIBAL and different types of organo-lithium or Grignard nucleophiles provided threo-amino alcohol with excellent stereoselecitivites (2-27:1). The reductive alkylation utilized most hydrocarbon nucleophiles, e.g. alkyl-, vinyl-, alkenyl-, phenyl-, and dienyl-, and afforded high selectivites unless donor solvents (e.g. THF and Et2O) were used. Second, syntheses of the protected threo-γ-amino-β-hydroxy aldehydes and their stereoselectivities were introduced. The reductive alkylated threo-amino allyl alcohol was transformed via Brown’s hydroboration/oxidation protocol with 9-BBN, followed by TEMPO oxidation to give the resultant aldehydes in reasonable yields. Then, TBDPS and Schiff base protected aldehyde was coupled with phenyl- and decyl Grignard reagents to obtain predominant 3,5-anti-diols (ca. 80:20 anti:syn), characterized by ¹³C NMR analysis of Rychnovsky’s 1,3-acetonide groups. Products can be useful analogues for fumonisin and 5-hydroxy-sphingosine due to their structural similarity. Third stage involved the synthesis of C₁₁-C₂₀ fragment analog of fumonisin. Chiral auxiliaries (e.g. Evans and Myers) were administrated for stereoselective methylation, Sharpless asymmetric dihydroxylation in the presence of (DHQ)2PHAL catalyst was performed to form 1,2- syn-diols, and the manipulation of protection/deprotection and Finklestein reaction furnished C₁₁-C₂₀ fragment analog of fumonisin.

The racemic (±)-2,4-di-tert-butyl-6-(((2-(dimethylamino)cyclohexyl)(methyl) amino)methyl)phenol ((±)-(NNMeOtBu)H), (±)-2,4-di-tert-butyl-6-((2-(dimethylamino) cyclohexylamino)methyl)phenol ((±)-(NNHOtBu)H), and (±)-2-(((2-(dimethylamino) cyclohexyl)(methyl)amino) methyl)phenol ((±)-(NNMeOH)H) are chiral ancillary NNO proligands, which synthesis was adapted from a published procedure. Reaction of (±)-(NNMeOtBu)H ((±)-2), (±)-(NNMeOH)H ((±)-3) and (±)-(NNHOtBu)H ((±)-1) with ZnEt2 successfully yielded the corresponding zinc ethyl complexes (±)-5, (±)-6 and (±)-7 respectively; the enantiomerically pure (R,R)-5 was synthesized from (R,R)-2. NMR spectroscopy experiments and X-ray crystallography allowed identification of two stereoisomers for (±)-5, which were observed in solution and in the solid state. The two stereoisomers, 5-α and 5-β, are in equilibrium in solution, with 5-β being thermodynamically favored. The zinc ethyl complexes were found to be unreactive towards weakly acidic alcohols (methanol, ethanol, isopropanol). However, the zinc chloride complex (±)-(NNMeOtBu)ZnCl ((±)-8) and the zinc phenoxide (NNMeOtBu)ZnOPh ((±)-9 and (R,R)-9) could be isolated and characterized. Comparison of the reactivity of both (±)-5 and the reported L₁ZnEt (L₁ = 2,4-di-tert-butyl-6- {[(2'-dimethylaminoethyl) methylamino]methyl}phenolate) in presence of pyridine led to the proposal of a dissociative mechanism explaining the fundamental difference between the two zinc ethyl species. Polymerization of rac-lactide catalyzed by 9 showed that the complex, in its racemic or enantiomerically pure version, has a slow activity and is not stereoselective.

No description available.

No description available.