Thesis (Ph.D.)--Brown University, 2008. / Vita. Advisor : Brian Moulton. Includes bibliographical references.

Thesis (Ph.D.)--Drexel University, 2008. / Includes abstract and vita. Includes bibliographical references (leaves 438-442).

Thesis (Ph. D.)--Drexel University, 2007. / Includes abstract and vita. Includes bibliographical references (leaves 275-279).

Thesis (Ph. D.)--Syracuse University, 2006. / "Publication number AAT 3251791."

In Chapter 1 the syntheses of a series substituted $(\eta\sp5$-cyclopentadienyl)dicarbonyliridium complexes using chlorodicarbonyl(pyridine)iridium as a starting material are described, giving yields as a high as 94%. Ring substituted compounds synthesized by this route include: chloro, benzyl, pentabenzyl, acetyl, carbomethoxy, methyl, benzoyl, trimethylsilyl, cyano, N,N-dimethylamino, tetraphenyl, N,N-dimethylamino-ethyl, (tetramethyl)N,N-dimethylaminoethyl, methoxyethyl, and pentamethyl. Also examined were the effects of the ring substituent on the asymmetric and symmetric carbonyl stretching frequencies as well as the $\sp{13}$C NMR chemical shift of the carbonyl carbon. In addition the photolysis of the pentamethyl, trimethylsilyl, dimethylaminoethyl and tetramethyldimethylamino substituted cyclopentadienyl-dicarbonyliridium compounds were studied. In Chapter 2 are presented the synthesis and polymerization properties of a series of pendent amino-substituted cyclopentadienyl titanium trichloride compounds. Specifically prepared were the picolyl and diisopropylaminocyclopentadienyl, dimethylaminoethyl, pyridylethyl and diisopropylaminoethylindenyl titanium trichlorides and triisopropoxides. In addition phenylethylcyclopentadienyltrichlorotitanium was prepared. As part of the synthetic process, three new thallium reagents were prepared and characterized. Their synthetic usefulness was demonstrated by the preparation of several new organometallic compounds of rhodium, titanium, and iridium. The catalytic properties of the pendent coordinating titanium compounds were explored by polymerizing ethylene, propylene and styrene. The polymers obtained were characterized by molecular weight via viscosity measurement and GPC and tacticity via $\sp{13}$C NMR and DSC. In Chapter 3 is described a search for new late transition metal coordination and organometalic compounds which could polymerize olefins to create high molecular weight polyolefins and co-polymerize olefins and carbon monoxide to create polyketones. Specifically diimine, $o,o\sp\prime$-dimethylaminomethylphenyl, dipyridyl, and benzamidinate compounds of nickel and palladium were prepared and tested for their ability to polymerize ethylene and propylene and co-polymerize hexene or propylene and carbon monoxide. The synthesis and catalysis were only partially successful giving one molecule (R-DABNiBr$\sb2)$ that proved to be highly active for the polymerization of oefins. In addition $o,o\sp\prime$-dimethylaminomethylphenylnickel bromide appears to oligomerize both hexene-CO and propylene-CO. In connection with our search for new nickel catalysts, (diphenylphosphinylcyclopentadienylbromonickel) $\sb2$ and (diphenylphosphinylcyclopentadienylmethylnickel) $\sb2$ were prepared and characterized by NMR and X-ray crystallography. Polymer samples obtained from various polymerization runs were characterized by $\sp{13}$C NMR, GPC and DCS.

Hyaluronic acid, HA, is a naturally occurring linear polysaccharide comprised of N-acetyl glucosamine and glucuronic acid. It is ubiquitous in tissues where it serves numerous biological functions. HA is polydisperse having average molecular weights that range on the order of 105 to 10 7 daltons depending upon the tissue from which it is derived and its method of purification. As with any polymer preparation, the molecular weight distribution, MWD, is important to a complete understanding of the characteristics and performance of the preparation. Size exclusion chromatography, SEC, is the most commonly employed means to determine the MWD of a polymer preparation. It is shown that SEC cannot be relied upon for the accurate and reproducible analysis of the MWD of large MW HA. Commercially available polymer standards used to calibrate SEC systems have hydrodynamic volumes that are considerably smaller than HA. HA analyzed under extreme conditions of NaCl concentration and pH that were shown to cause contraction of the molecule still had a hydrodynamic volume much greater than polymer standards. Conventional calibration with standards can be subject to error from extrapolation and unable to detect elution in the totally excluded volume. Viscosity measurements in a dual capillary viscometer demonstrated shear thinning of large MW HA at shear rates that are common inside the plumbing of SEC systems and on line viscometers. A model of shear inside an SEC column is derived in terms of the flowrate, column diameter, and particle diameter. The shear inside the column is shown to be sufficient to reduce the viscosity of large MW HA complicating the MWD analysis of HA by SEC. Chromatographic analysis based on separation in pressure driven flowing streams have fundamental limitations with shear sensitive polymers, such as HA, due to shear, which arises from parabolic flow profiles. Capillary electrophoretic methods have a flow profile that is flat and theoretically should have no shear. It is proposed that capillary electrochromatography utilizing a size exclusion stationary phase may provide the optimum tool for the analysis of large MW HA and other shear sensitive polymers.

Thesis (Ph. D.)--Rutgers University, 2010. / "Graduate Program in Chemistry." Includes bibliographical references.

To replicate functionality and isolation provided by enzyme active sites, flavin was covalently incorporated into a silicate sol-gel. The isolation provided by the sol-gel cybotactic region replicates the sequestered nature of an enzyme active site. To establish specific hydrogen bond mediated recognition of the flavin within the sol-gel matrix, flavin incorporated gels were co-functionalized with a diacyl diaminopyridine based receptor. Host-guest interactions were established via quenching of the flavin fluorophore by the receptor. To continue this active site model, an aromatic unit was incorporated into flavin sol-gels. π-stacking interactions serve to modulate flavin cofactor reactivities within the active site. To quantify the individual effect of π-stacking on the flavin nucleus, fluorescence spectroscopy was used as a spectroscopic probe. Solvochromic flavin responds to changes in solvent polarity in its microenvironment and this is registered with either a hypsochromic (blue, lowering of polarity) or bathochromic (red, increase in polarity) shift of the second absorption (π, π*) in its UV/vis spectrum. Red or blue shifts correspond to the ability of solvent molecules to re-orientate themselves around the excited isoalloxazine nucleus, maximizing solvation interactions. Surface structure and performance of sol-gels and “MCM” type materials are closely linked. Current spectroscopic probes have proved limited and so the solvochromic and amphiphilic properties of flavin were utilized as a noninvasive probe of silica based materials. Quinones are found in a wide variety of biological processes often involving an accompanying proton transfer mechanism, culminating in the formation of the reduced QH2 species. Thiourea based receptors can form a hydrogen bond mediated chelate complex with the radical anion of ubiquinone. Proton transfer to the ubiquinone radical anion via this specific form of recognition was probed. Cyclic voltammetry (CV) and simultaneous electrochemistry electron paramagnetic resonance (SEEPR) studies were used to investigate this process. One way in which the characteristic properties Buckminsterfullerenes (C60) can be further investigated is via immobilization of C 60 onto a physical support. The ability of C60 to undergo thermoreversible Diels-Alder type cycloaddition reactions was exploited in order to immobilize the fullerene on a diene-functionalized polymeric support.

Thesis (M.S.)--Rutgers University, 2008. / "Graduate Program in Chemistry." Includes bibliographical references (p. 63-64).

Thesis (Ph.D.)--Brown University, 2008. / Source: Dissertation Abstracts International, Volume: 69-06, Section: B, page: 3587. Adviser: Paul G. williard. Includes bibliographical references.