Two framework oxide materials of the MO₃ network type have been synthesized and structurally characterized by synchrotron and X-ray powder diffraction and the Rietveld method in the temperature range 25~500 K. The results show one of them to be a low thermal expansion material. Theoretical studies of negative thermal expansion...
Contaminant transport in ground water is an important environmental process that
affects a host of natural systems. Transport of contaminants is affected by many
processes, including aqueous complexation, adsorption, and redox reactions. One of the
most important components of an aquifer that controls transport is iron-oxide. In this
study, the...
A spectrometer, here denoted a Simple, Low-power, Inexpensive. Microcontroller-based or SLIM spectrometer. was developed that exploits the small size and low cost of solid-state electronic devices. This approach results in customizable spectrometers that are considerably less expensive and smaller than traditional instrumentation. The performance of the SLIM spectrometer was evaluated...
The rhenium dithiodiolate, Hydrido-tris-(3 ,5-dimethyl- 1 -pyrazol yl) borato(ethane- 1 ,2-dithiodiolato)(oxo)rheni um(V), and Hydrido-tris-(3 ,5-dimethyl- 1 -pyrazolyl)borato(phenylethanedithiodiolato)(oxo)rhenium(V), were synthesized by reductive cyclocondensation of alkane-1,2-dithiols with Tp'Re0₃ in a one pot fashion. The rhemium monothiodiolate, Hydrido-tris-(3 ,5-dimethyl- 1 -pyrazolyl) borato(ethane- 1 ,2-monothiodiolato)(oxo)rhenium(V), and Hydrido-tris-(3 ,5- dimethyl- 1 -pyrazolyl)borato(propanemonothiodiolato)(oxo)rhenium(V), were also synthesized...
Exploratory synthesis plays an important role in the quest to discover new materials. There are very few structurally characterized alkali metal containing bismuth vanadates. Hybridization of the 6s and 6p orbitals of Bi[superscript 3+] and the resulting lone electron pair yields some very interesting stereochemistry and steric related properties. Some...
In situ reduction of hydrido-tris-(3,5-dimethylpyrazolyl)borato(trioxo) rhenium(V) with triphenylphosphine or triethylphosphite leads to a reactive rhenium(V) species that catalytically deoxygenates epoxides at 75-105°C. The reaction is stereospecific, except for trans- and cis-butene oxide which formed minor amounts of the opposite isomer. A variety of different functional groups were tolerated and even...
Enzymes play an important role in the environment, they breakdown natural-occurring and anthropogenic molecules so that they can be transported into cells and utilized. Enzyme assays are routinely used in soil science and oceanography to measure the activities of specific processes and to serve as general indicators of microbial activity....
The challenges prompted by miniaturization of chromatographic systems have led scientists to explore new avenues in the synthesis of stationary phases. Packed capillary columns have found limited application in routine analysis due to a number of technical difficulties, most of which are attributable to the frits. New column designs insure...
For a number of reasons, miniaturization of chromatographic columns has been a general trend over the past three decades. Methods designed to enhance selectivity and efficiency can offer improved separation power and speed, expanding on the advantages of miniaturized columns. This dissertation describes novel approaches in this direction, focusing on...
PART I. Asymmetric syntheses of both natural (+)- and nonnatural (-)-byssochlamic acid via a [2+2] photoaddition-cycloreversion strategy are described. X-ray crystallographic analysis of the cyclohexylamine salt 99 showed that the structure of the monomethyl ester 100 from esterase hydrolysis of 44 was originally misassigned as 56. The enantiomeric relationship of...
In situ, reduction of Cp*ReO₃ by PPh₃ to form (Cp*ReO)₂(μ-O)₂ allows catalytic deoxygenation of epoxides, however, conproportionation between Reⱽ and Reⱽᴵᴵ species to form clusters of ((Cp*Re)₃(μ-O)₆}²⁺(ReO₄⁻)2 and new compound {(Cp*Re)₃(μ²-O)₃(μ³-O⁾³ReO₃}⁺(ReO₄⁻) leads to removal of rhenium from the catalytic cycle and loss of activity, The epoxide deoxygenation mediated by (Cp*ReO)₂(μ-O)₂...
Benzylsuccinate (BSA), methylbenzylsuccinate (methylBSA), and ethylbenzylsuccinate (ethylBSA) are unambiguous anaerobic biotransformation products from toluene, xylenes, and ethylbenzene decay, respectively, and may be used to indicate intrinsic bioremediation is occurring at hydrocarbon-contaminated sites. In order to improve upon current methods that detect and quantify anaerobic hydrocarbon metabolites in field samples, solid-phase-extraction...
E. coli thioredoxin (TRX) was modified by the episulfonium ion derived from S-(2-chloroethyl)glutathione (CEG) or S-(2-chloroethyl)cysteine (CEC). The alkylation site was located at Cys-32, which was confirmed by tandem mass spectrometry. Two forms of native TRX, Oxi- and Red-TRX, and two modified TRXs, GS- and Cys-TRX, were examined by hydrogen/deuterium...
Recombinant human macrophage colony stimulating factor beta (rhm-CSFβ) is a glycoprotein that stimulates the proliferation, differentiation and survival of cells belonging to the monocyte-macrophage lineage. It contains nine inter-subunit and intra-subunit disulfide bonds and represents an excellent model system for studying disulfide bond formation during protein folding because the assembly...
Neurofilament proteins are intermediate filaments found in the neuronal cytoskeleton. Phosphorylation of these proteins is considered important for the assembly and stability of the filaments. Accurate molecular weights have been difficult to measure, largely because the high degree of phosphorylation results in M[subscript r]'S that are significantly greater than dictated...
The melt intercalation of poly(ethylene oxide) (PEO) between layers of MoO₃ and MPS3 (M=Mn,Cd) is obtained by heating the ground mixture and LiₓMoO₃, KₓMn₁-ₓ/₂PS₃, or KCd₁-ₓ/₂PS₃. The products are characterized by powder X-ray diffraction (XRD). Below the melting temperature of PEO (66 °C), intercalation rates and yields are low. By...
In this dissertation, I present electronic spectroscopy of a few biologically relevant species and their complexes with solvent molecules in the gas phase using a variety of techniques, including resonantly enhanced multiphoton ionization (REMPI), laser induced fluorescence (LIF), and zero kinetic energy (ZEKE) photoelectron spectroscopy. My work on several methylated...