Part I. Coenzyme B12 as a hydroformylation-type catalyst. Part II. Mechanisms of hydrogen transfer in the methylmalonyl coenzyme a mutase reaction

Part I

The mechanism of the hydroformylation reaction was studied. Using cobalt deuterotetracarbonyl and 1-pentene as substrates, the first step in the reaction, addition of cobalt tetracarbonyl to an olefin, was shown to be reversible.

Part II

The role of coenzyme B₁₂ in the isomerization of methylmalonyl coenzyme A to succinyl coenzyme A by methylmalonyl coenzyme A mutase was studied. The reaction was allowed to proceed to partial completion using a mixture of methylmalonyl coenzyme A and 4, 4, 4-tri-²H-methylmalonyl coenzyme A as substrate. The deuterium distribution in the product, succinyl coenzyme A, was shown to best fit a model in which hydrogen is transferred from C-4 of methylmalonyl coenzyme A to C-5’ of the adenosyl moiety of coenzyme B₁₂ in the rate determining step. The three hydrogens at the 5’-adenosyl position of the coenzyme B₁₂ intermediate are then able to become enzymatically equivalent before hydrogen is transferred from the coenzyme B₁₂ intermediate to form succinyl coenzyme A.

The optoelectronic swept-frequency laser and its applications in ranging, three-dimensional imaging, and coherent beam combining of chirped-seed amplifiers

This thesis explores the design, construction, and applications of the optoelectronic swept-frequency laser (SFL). The optoelectronic SFL is a feedback loop designed around a swept-frequency (chirped) semiconductor laser (SCL) to control its instantaneous optical frequency, such that the chirp characteristics are determined solely by a reference electronic oscillator. The resultant system generates precisely controlled optical frequency sweeps. In particular, we focus on linear chirps because of their numerous applications. We demonstrate optoelectronic SFLs based on vertical-cavity surface-emitting lasers (VCSELs) and distributed-feedback lasers (DFBs) at wavelengths of 1550 nm and 1060 nm. We develop an iterative bias current predistortion procedure that enables SFL operation at very high chirp rates, up to 10^16 Hz/sec. We describe commercialization efforts and implementation of the predistortion algorithm in a stand-alone embedded environment, undertaken as part of our collaboration with Telaris, Inc. We demonstrate frequency-modulated continuous-wave (FMCW) ranging and three-dimensional (3-D) imaging using a 1550 nm optoelectronic SFL.

We develop the technique of multiple source FMCW (MS-FMCW) reflectometry, in which the frequency sweeps of multiple SFLs are "stitched" together in order to increase the optical bandwidth, and hence improve the axial resolution, of an FMCW ranging measurement. We demonstrate computer-aided stitching of DFB and VCSEL sweeps at 1550 nm. We also develop and demonstrate hardware stitching, which enables MS-FMCW ranging without additional signal processing. The culmination of this work is the hardware stitching of four VCSELs at 1550 nm for a total optical bandwidth of 2 THz, and a free-space axial resolution of 75 microns.

We describe our work on the tomographic imaging camera (TomICam), a 3-D imaging system based on FMCW ranging that features non-mechanical acquisition of transverse pixels. Our approach uses a combination of electronically tuned optical sources and low-cost full-field detector arrays, completely eliminating the need for moving parts traditionally employed in 3-D imaging. We describe the basic TomICam principle, and demonstrate single-pixel TomICam ranging in a proof-of-concept experiment. We also discuss the application of compressive sensing (CS) to the TomICam platform, and perform a series of numerical simulations. These simulations show that tenfold compression is feasible in CS TomICam, which effectively improves the volume acquisition speed by a factor ten.

We develop chirped-wave phase-locking techniques, and apply them to coherent beam combining (CBC) of chirped-seed amplifiers (CSAs) in a master oscillator power amplifier configuration. The precise chirp linearity of the optoelectronic SFL enables non-mechanical compensation of optical delays using acousto-optic frequency shifters, and its high chirp rate simultaneously increases the stimulated Brillouin scattering (SBS) threshold of the active fiber. We characterize a 1550 nm chirped-seed amplifier coherent-combining system. We use a chirp rate of 5*10^14 Hz/sec to increase the amplifier SBS threshold threefold, when compared to a single-frequency seed. We demonstrate efficient phase-locking and electronic beam steering of two 3 W erbium-doped fiber amplifier channels, achieving temporal phase noise levels corresponding to interferometric fringe visibilities exceeding 98%.

Measurement of the neutron (^3He) spin structure function at low Q^2 : a connection between the Bjorken and Drell-Hearn-Gerasimov sum rules

The spin dependent cross sections, σT_1/2 and σT_3/2 , and asymmetries, A_∥ and A_⊥ for ³He have been measured at the Jefferson Lab's Hall A facility. The inclusive scattering process ³He(e,e)X was performed for initial beam energies ranging from 0.86 to 5.1 GeV, at a scattering angle of 15.5°. Data includes measurements from the quasielastic peak, resonance region, and the deep inelastic regime. An approximation for the extended Gerasimov-Drell-Hearn integral is presented at a 4-momentum transfer Q² of 0.2-1.0 GeV².

Also presented are results on the performance of the polarized ³He target. Polarization of ³He was achieved by the process of spin-exchange collisions with optically pumped rubidium vapor. The ³He polarization was monitored using the NMR technique of adiabatic fast passage (AFP). The average target polarization was approximately 35% and was determined to have a systematic uncertainty of roughly ±4% relative.

The electrical and magnetic properties of amorphous Pd-Cu-P alloys

The amorphous phases of the Pd-Cu-P system has been obtained using the technique of rapidly quenching from the liquid state. Broad maxima in the diffraction pattern were obtained in the X-ray diffraction studies which are indicative of a glass-like structure. The composition range over which the amorphous solid phase is retained for the Pd-Cu-P system is (Pd_100-xCu_x)₈₀P₂₀ with 10 ≤ x ≤ 50 and (Pd₆₅Cu₃₅)_100-yP_y with 15 ≤ y ≤ 24 and (Pd₆₀Cu₄₀)_100-yP_y with 15 ≤ y ≤ 24.

The electrical resistivity for the Pd-Cu-P alloys decreases with temperature as T² at low temperatures and as T at high temperatures up to the crystallization temperature. The structural scattering model of the resistivity proposed by Sinha and the spin-fluctuation resistivity model proposed by Hasegawa are re-examined in the light of the similarity of this result to the Pt-Ni-P and Pd-Ni-P systems. Objections are raised to these interpretations of the resistivity results and an alternate model is proposed consistent with the new results on Pd-Cu-P and the observation of similar effects in crystalline transition metal alloys. The observed negative temperature coefficients of resistivity in these amorphous alloys are thus interpreted as being due to the modification of the density of states with temperature through the electron-phonon interaction. The weak Pauli paramagnetism of the Pd-Cu-P, Pt-Ni-P and Pd-Ni-P alloys is interpreted as being modifications of the transition d-states as a result of the formation of strong transition metal-metalloid bonds rather than a large transfer of electrons from the glass former atoms (P in this case) to the d-band of the transition metal in a rigid band picture.

Photoelectrochemistry of GaAs and Si liquid junctions

A quantitative study has been performed on the stability of GaAs surfaces in a 0.10 M K₂Se-0.01 M K₂Se₂ aqueous solution. In this electrolyte, n-type GaAs electrodes displayed significant photocorrosion in competition with faradaic charge transfer to Se^2-. Chemisorption of group VIIIB metal ions onto the GaAs surfaces yielded improved current-voltage behavior of the GaAs photoanodes, and also resulted in a significant reduction in photocorrosion. This behavior implies that the chemisorbed metal ions act to increase the rate of hole transfer to the Se^2- species. Related experiments on n-GaAs, pGaAs, and Sn-doped In₂O₃ electrodes in Te^2-/- aqueous solutions have also been performed.

The majority carrier (electrons) transfer rate constant at a highly doped n⁺-Si/Co(Cp)₂Cl-methanol junction has been measured directly using the chronoamperometry electrochemical technique. The reduction reaction rate of Co(Cp)₂+ was 0.03 cm-s^-1 at the Si electrode, and was more than 100 times slower than at a hanging mercury electrode. The slower rate was attributed to the smaller optical and static dielectric constants, and the lower density of electrons of the semiconductor. The experimental results were compared to the Marcus theory of charge transfer.

The unique properties of high purity Si/liquid junctions have been investigated under illumination conditions in which the photogenerated carrier concentration exceeds the dopant concentration. Under these high injection conditions, negligible electric fields exist at the semiconductor/liquid interface, and carrier motion is driven by diffusion. Studies of the current-voltage properties of the Si in methanol solutions containing various redox couples suggested that high efficiency photoelectrochemical cells could be established through selective collection of carriers at the semiconductor/liquid junction. The quasi-Fermi levels of electrons and holes were measured directly against the solution potential. Steady-state and transient photovoltage measurements, and theoretical modeliug of the carrier transport, generation, and recombination dynamics indicated that the quasi-Fermi levels were flat across the semiconductor sample. The recombination velocities at the Si/liquid junctions have also been measured, and were shown to vary with the solution potential following the Shockley-Read-Hall theory on recombination.

Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

I. Proton magnetic resonance of polynucleotides and transfer RNA. II. Electron spin relaxation studies of manganese (II) complexes in acetonitrile

Part I. Proton Magnetic Resonance of Polynucleotides and Transfer RNA.

Proton magnetic resonance was used to follow the temperature dependent intramolecular stacking of the bases in the polynucleotides of adenine and cytosine. Analysis of the results on the basis of a two state stacked-unstacked model yielded values of -4.5 kcal/mole and -9.5 kcal/mole for the enthalpies of stacking in polyadenylic and polycytidylic acid, respectively.

The interaction of purine with these molecules was also studied by pmr. Analysis of these results and the comparison of the thermal unstacking of polynucleotides and short chain nucleotides indicates that the bases contained in stacks within the long chain poly nucleotides are, on the average, closer together than the bases contained in stacks in the short chain nucleotides.

Temperature and purine studies were also carried out with an aqueous solution of formylmethionine transfer ribonucleic acid. Comparison of these results with the results of similar experiments with the homopolynucleotides of adenine, cytosine and uracil indicate that the purine is probably intercalating into loop regions of the molecule.

The solvent denaturation of phenylalanine transfer ribonucleic acid was followed by pmr. In a solvent mixture containing 83 volume per cent dimethylsulf oxide and 17 per cent deuterium oxide, the tRNA molecule is rendered quite flexible. It is possible to resolve resonances of protons on the common bases and on certain modified bases.

Part II. Electron Spin Relaxation Studies of Manganese (II) Complexes in Acetonitrile.

The electron paramagnetic resonance spectra of three Mn⁺² complexes, [Mn(CH₃CN)₆]⁺², [MnCl₄]^-2, and [MnBr₄]^-2, in acetonitrile were studied in detail. The objective of this study was to relate changes in the effective spin Hamiltonian parameters and the resonance line widths to the structure of these molecular complexes as well as to dynamical processes in solution.

Of the three systems studied, the results obtained from the [Mn(CH₃CN)₆]⁺² system were the most straight-forward to interpret. Resonance broadening attributable to manganese spin-spin dipolar interactions was observed as the manganese concentration was increased.

In the [MnCl₄]^-2 system, solvent fluctuations and dynamical ion-pairing appear to be significant in determining electron spin relaxation.

In the [MnBr₄]^-2 system, solvent fluctuations, ion-pairing, and Br- ligand exchange provide the principal means of electron spin relaxation. It was also found that the spin relaxation in this system is dependent upon the field strength and is directly related to the manganese concentration. A relaxation theory based on a two state collisional model was developed to account for the observed behavior.