Tacrolimus is an immunosuppressant drug approved by the FDA for the prevention of organ transplant rejection. However, the use of this drug is hindered by its narrow therapeutic window and extreme insolubility in water. Due to these properties, the currently used tacrolimus preparations must be administered once or twice daily...
Two distinct strategies were explored for the enantioselective synthesis of α-heteroatom substituted alkyl boronic esters by stereoselective reagent-controlled homologation using transient chiral carbenoid reagents CHYMX (Y = heteroatom, X = nucleofuge, M = electrofuge). In the first case, a stereospecific reagent-controlled homologation (sStReCH) approach to α-alkoxyalkylboronates using α-metalated S,O- and...
Radiation exposure to the brain can occur from a variety of events, including space missions, nuclear accidents, and clinical treatments. The effects of high dose radiation are well studied, but those of lower dosage are more elusive. Decline of memory and cognition is observed in patients exposed to low dose...
While properties are extremely important from an application point of view, it is crucial to have a detailed understanding of the underlying structural influence. Once a concrete correlation between the structure and the observed property is established, rational design of novel materials with optimized properties can be realized. These optimized...
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...
Pyroprocessing is an advanced technology for recycling used nuclear fuel. Pyrochemical processes encompass a wide range of chemical, physical, and electrochemical methods to partition fission products and other components from used nuclear fuel, which allows for the reuse of the actinides in nuclear fuel. This dissertation investigates two chemical systems...
In this work, three isomeric forms of N, N'-diethyl, N, N'-ditolyldipicolinamide (EtTDPA) were synthesized. The elements thorium through americium, which make up a significant portion of the actinides in used nuclear fuel (with the exception of curium), and two fission products, molybdenum and technetium, were tested for their ability to...
Automation of computational chemistry, while only an engineering feat, has the potential to accelerating computational research be removing all by the science. The work in this thesis mainly discusses fundamental understanding of complex chemical systems. What is not obvious are the numerous tasks necessary for this fundamental understanding. Under the...
The rhenium (V) complex Tp'ReO₂ (Tp' = hydrido-tris-(3,5-
dimethylpyrazolyl)borate), generated in situ from PPh₃ reduction of
Tp'Re0₃, reacts with small ring heterocycles such as epoxides and
episulf ides. The strained trans-cyclooctene ring provides an unusual
thermodynamic bias against direct atom transfer, but trans-cyclooctene
oxide still produces substantial amounts of trans-cyclooctene....