Metalloenzymes catalyze remarkable reactions in Nature using transition metal ions. Common earth-abundant metals like copper, iron, zinc, and magnesium catalyze reactions that are the basis of life. These metal sites lend their chemistries to facilitate these reactions, making studying the structure and properties important in understanding the enzymes' abilities and...
The invention of GdIII-based magnetic resonance imaging (MRI) probes substantially expanded the capability of MRI in visualizing details in tissue. Building upon the achievement of GdIII-based complexes, more ideal probes should feature contrast that is responsive to biomarkers, such as redox status and ion concentrations. The abnormality of these biomarkers...
Magnetic Resonance Imaging is a non-invasive modality that allows for deep-tissue imaging. Contrast agents decrease image acquisition time and increase the intrinsic contrast between different types of tissue. A new family of enzyme-activated contrast agents is emerging that has the ability to report on enzymatic processes in vivo. Towards this...
My thesis focuses on the design and synthesis of lanthanide coordination complexes as Zn(II)-responsive magnetic resonance imaging (MRI) contrast agents. These agents produce an increase in MR intensity upon binding of Zn(II) through water modulation to Gd(III) chelates. To this end, several Zn(II)-responsive contrast agents have been synthesized and studied...
Contained in the following dissertation are detailed investigations regarding the thermodynamics of small molecule activation by metalloporphyrin complexes isolated within metal-organic frameworks (MOFs). Chapter 1 provides a description of the role metalloporphyrin complexes play in biological systems and the challenges associated with studying small molecule activation by metalloporphryin sites in...
Chapter 1 describes the homopolymerization of styrene and the copolymerization of ethylene and styrenic comonomers mediated by the single-site bimetallic "constrained geometry catalysts" (CGCs), (µ-CH2CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](TiMe2)}2 [EBICGC(TiMe2)2; Ti2], (µ-CH2CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](ZrMe2)}2 [EBICGC(ZrMe2)2; Zr2], (µ-CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](TiMe2)}2 [MBICGC(TiMe2)2; C1-Ti2], and (µ-CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](ZrMe2)}2 [MBICGC(ZrMe2)2; C1-Zr2], in combination with the borate activator/cocatalyst Ph3C+B(C6F5)4- (B1). Under identical styrene homopolymerization conditions,...