Cyclodextrin-based polymers (CDPs) are adsorbents based on supramolecular receptor chemistry and have emerged as a promising technology for organic micropollutant remediation. Micropollutants are small organic molecules which contaminate water systems from human related activities. The occurrence of micropollutants in water sources is associated with many negative health, economic, and ecological...
Surface-enhanced Raman scattering (SERS) spectroscopy has been demonstrated to be a powerful analytical tool. Its chemical specificity, rapidity, and portability make it an attractive technique for biosensing, but its application to this field has been limited by the fundamental distance dependence of the surface-enhancement effect. Many biological molecules of interest...
This dissertation describes the study of photoinduced charge transfer between QDs and molecular acceptors as a probe of the defects within ligand shells of QDs and as means to photocatalyze redox reactions. For charge transfer reactions to occur between QDs and molecules in bulk solution, the molecules must interact with...
Hybrid Organic-inorganic halide perovskites are emerging semiconducting materials that have shown over 23% in power conversion efficiency (PCE) for solar cells. The most prominent materials, three-dimensional (3D) perovskites, have limited scope for structural engineering and exhibit instability when encounter with moisture and heat. Here, we focus on studying the structure-property...
Triplet excited state chemistry has enabled a range of important organic transformations by accessing reaction pathways inaccessible to photoredox chemistry. Such photoreactions are triggered by triplet photosensitizers, which absorb visible-light photons and transfer the energy to the substrate or to a co-catalyst through triplet-triplet energy transfer (TT EnT). The most...
Molecules are highly social: they recognize one another and form bonds with those they are attracted to and repel those they are not. Some molecules establish strong bonds, while others form weak, transient associations. These interactions are ubiquitous in Nature and are integral to life. For at the basis of...
Crystalline and Framework materials make up a broad class of structures which are known for their precise and regular nature. Because these materials have predictable structures and compositions to their networks, they are widely used for several applications including electronics, optics, and catalysis. While these materials are of particular interest,...
Many transcription factors (TFs) regulate oncogenic processes and are therefore desirable targets for drug intervention. However, few TF inhibitors have been developed to date due to a lack of specificity and few TF binding pockets. The Meade Lab has overcome these challenges by using cobalt-based complexes that disrupt Cys2His2 zinc...
A fundamental understanding of the photophysics involved in solar energy capture and conversion is crucial to the development of carbon-neutral energy technologies. Taking inspiration from nature, the photosynthetic reaction center (PSRC) is often modeled by simpler versions of its elements to allow for better control over the system and for...
Soft materials are inherently fluxional, with morphologies and behaviors that are dictated by their solvation state. Thus, many organic systems cannot be reliably imaged by static dry state or cryogenic-transmission electron microscopy (TEM). This motivated us to pursue liquid cell (LC) TEM method development to study our own materials and...
Oxidation is an important process in synthesizing a broad range of useful products such as polymers, pharmaceuticals, and fine chemicals. While H2O2 is a highly attractive oxidant for oxidative chemistry due to its high percentage of oxygen and environmentally friendly water byproduct, it is often used in excess due to...
Part I:Current approaches to synthesize π-conjugated polymers are dominated by thermally driven, transition-metal-mediated reactions. Herein we7 show that electron-deficient Grignard monomers readily polymerize under visible-light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption...
Atomic layer deposition (ALD) is a gas-phase synthesis technique employed to manufacture thin films and metallic nanoparticles of various compositions and sizes, as well as individual, isolated species on various supports. An understanding of the dynamic surface chemistry that takes place during various ALD processes is vitally important for achieving...
Cobalt(III) Schiff-base complexes (Co(III)-sb) have been utilized in the literature as antibacterial, antiviral, and inhibitory agents. Recent work has utilized their ability to displace endogenous metals from metalloproteins that exhibit aberrant gain of function pathologies in human disease. Specifically, in this dissertation Co(III)-sb has been applied as inhibitors of pathogenic...
Uranium is a unique, multifaceted element that possesses rich chemistry and promise for challenging reactions. Pressing demands within nuclear stockpile stewardship and the nuclear energy sector call for development of this relatively understudied element. Uranium metal–organic frameworks (U-MOFs), a class of nanoscale hybrid materials, harness the exceptional attributes of uranium...
Self-Assembled Monolayers for MALDI-TOF Mass Spectrometry (SAMDI-MS) is a technique that combines self-assembling molecules of alkane disulfides on gold and MALDI-TOF mass spectrometry. By using well-defined monolayers with functionalizations that both prevent non-specific adsorption onto the surface and presents immobilization handles, it is possible to pull out analytes of interest,...
Metal-organic frameworks (MOFs) are a class of highly modular materials with welldefined three-dimensional architectures, permanent porosity, and diverse chemical functionalities, which show promise for a wide range of applications, including gas storage and separation, drug delivery, chemical sensing, and catalysis. Nanoparticle forms of MOFs have similar properties but are dispersible...
Photovoltaic devices containing organic semiconducting chromophores are a promising technology for the conversion of solar energy into electricity. Research into the molecular design and processing of these materials has propelled the power conversion efficiency of laboratory-fabricated organic polymer solar cells (PSCs) to over 17%, which exceeds the 10% threshold deemed...
Proteins are the nanoscale building blocks of life. Their sophisticated but well-defined architectures result in complex biological functions, including ones involved in metabolism, photosynthesis, transcription, translation, and immunity. To study and improve upon the natural functions of proteins, it is desirable to develop methodology for organizing proteins into targeted architectures....
Per- and polyfluoroalkyl substances (PFAS) are man-made compounds containing multiple carbon–fluorine bonds. The unique properties of this strong bond simultaneously make PFAS useful for a number of industrial and consumer applications, toxic to living organisms, and difficult to remediate. Because the pervasive pollution of water sources with PFAS occurs at...