Commercial agriculture and industrial manufacturing have contaminated freshwater sources with persistent organic pollutants, heavy metals, and radioactive species. Effective mitigation of this pollution is paramount to safeguarding human health, animal and aquatic life, and the environment. Conventional adsorbents such as activated carbon, metal oxides, resins, and polymers attain moderate to...
Self-assembled monolayers for matrix-assisted laser desorption/ionization mass spectrometry (SAMDI-MS) is a platform that combines self-assembled monolayers of alkanethiolates on gold and MALDI mass spectrometry analysis to report mass changes resulting from surface reactions. The synthetic flexibility of the monolayer and the use of mass spectrometry as a generalizable readout method...
Despite prevention and treatment, substantial risk for cardiovascular disease(CVD) remains in the population and CVD has been the leading global cause-of-death in past years.While high-density lipoprotein (HDL) markers such as HDL cholesterol (HDL-C) and HDL efflux (a cholesterol-transport-function assay) are associated with decreased risk of CVD, the mechanism of this...
Continuous and coordinated materials discovery efforts have amassed a wealth of knowledge concerning many general classes of materials. The number of known phases of all structure-types, however, is far less than number of possible materials dictated by the elements on the periodic table. Recently, with improved computational abilities and well-developed...
This dissertation seeks to explore how physical forces, notably through the use of magnetic nanoparticles and applied fields, can influence the structural outcomes of colloidal crystals engineered with DNA. Chapter 1 describes how both DNA and magnetic fields can direct the assembly of nanoparticles into periodic and sometimes crystalline materials....
The lanthanides, with their limited orbital effects and high oxophilicity, represent a class of catalytic metals highly distinguished from more commonly-utilized transition metals. Homogeneous lanthanide catalysts often afford high catalytic rates and impressive selectivity. However, challenges regarding the synthesis and utilization of highly air- and water-sensitive organo-lanthanide complexes have limited...
Electrochemical cell devices are increasingly being sought for energy conversion and storage applications due to their high efficiencies and their potential for operating free of greenhouse gas (GHG) emissions. Solid Acid Electrochemical Cells (SAECs), which most commonly employ CsH2PO4 (CDP) as the electrolyte component, are uniquely suited to meet the...
This dissertation investigates the use of organic and semiconductor nanomaterials as chromophores in solar fuels production and energy transfer-mediated [2+2] cycloadditions. A series of novel N-annulated perylene chromophore amphiphiles was synthesized via a modular synthesis. These perylene amphiphiles were found to self-assemble in aqueous solution, forming extended ribbon-like nanostructures that...
Discrete molecules, linear and branched polymers, and disordered cross-linked networks are well studied objects of chemical synthesis. However, two-dimensional polymers (2DPs) have been long missing from this continuum of molecular architectures, both in chemical synthesis and in Nature. Recently, new polymerization strategies and characterization methods have enabled the unambiguous realization...
Raman spectroscopy is an analytical technique that utilizes inelastic scattering of light to obtain structural information of analyte molecules. The weak intrinsic process of Raman scattering, however, can be greatly enhanced when molecules are placed on or near a surface of noble metal with nanostructures. Discovered over 40 years, surface-enhanced...
The objective of molecular imaging is to noninvasively visualize biochemical events in a living system at the cellular level. Magnetic resonance imaging (MRI) is a promising modality for this goal due to its excellent resolution, unlimited depth penetration, and absence of harmful ionizing radiation. MRI techniques frequently use Gd(III)-based contrast...
This dissertation describes investigations into the two primary mechanisms by which the optical bandgap of colloidal quantum dots (QDs) may be post-synthetically modified: (i) by the quantum-confined Stark effect and (ii) by exciton-delocalizing surface capping ligands. This work demonstrates that through the use of ligand-exchange strategies that enable either of...
It is said across numerous disciplines, from biology to architecture to software engineering, that “form ever follows function.” This adage highlights the intimate relationship between structural characteristics and functional properties in many disparate fields of work. Here, we discuss how the catalytic activity and compressibility of metal–organic frameworks (MOFs) are...
Deciphering the targets of axonal projections plays a pivotal role in interpreting neuronal function and pathology. Neuronal tracers are indispensable neurobiology tools for elucidating advanced functions and interactions between different subregions of the brain. Commercially available neuronal tracers include small molecule dyes, viruses, and synthetic nanoparticles. Among these options, viral...
Total synthesis of natural products provides an avenue for investigation of complex chemical scaffolds, not only delivering access to biologically impactful molecules but also lending a deeper understanding of their inherent chemical reactivity. Expansion of reaction methodology, optimization of biological activity, and absolute structural confirmation can all be accomplished via...
Organic chromophores show great promise for energy and optoelectronic devices, due to their synthetic tunability and low production costs. In order to achieve this potential, their fundamental photophysical processes must be better understood. It has long been documented that chromophore packing at the molecular level has dramatic effect on electronic...
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...
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...
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...
Over the past 15 years, there have been significant developments in expanding the singlet fission (SF) library and understanding the SF mechanism. SF has been a topic of interest in recent years due to its potential applications in organic photovoltaics. During SF, a singlet exciton energetically down-converts into two triplet...