Semiconductor nanocrystals possess unique photophysical properties that make them desirable for many optoelectronic applications such as photovoltaics, LEDs, and quantum computing. When the size of a semiconductor is reduced to below the excitonic Bohr radius of the material, its carriers becomes quantum confined resulting in drastic changes to optical, electronic,...
Early transition metal organometallics chemisorbed on extremely Brønsted acidic sulfated metal oxides such as sulfated alumina (AlS) and sulfated zirconia (ZrS) produce highly active single-site catalysts for olefin polymerization, alkene and arene hydrogenation, and alkane hydrogenolysis, typically with a large percentage of catalytically significant sites. The low support conjugate basicity...
The physical boundary layer, or interface, between two different phases of matter is the site of chemical and physical processes that are critical to many research fields. Many of these interfaces contain electric charge, which influences the structure and composition of the interfacial region and the interactions between the interface...
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...
Oligonucleotides can be used to modulate the regulation of pathological genes that are associated with various diseases. However, due to biological barriers, efficient delivery of oligonucleotides, especially to extrahepatic tissues, remains a challenge. To overcome these barriers, multiple delivery strategies have been developed, ranging from medicinal chemistry to nanotechnology. Nanoparticle-based...
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...
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...
Polyolefins are the most versatile and widely used polymers worldwide. Depending on the polymer microstructure, polyolefins can exhibit a wide range of useful and tailored properties and applications. Metal-catalyzed coordinative olefin polymerization plays a center role in advancing polyolefin synthesis. This dissertation explores two strategies to modulate the polymer microstructures...
Spherical Nucleic Acids (SNAs) are unique class of nanomaterial characterized by a dense nucleic acid shell conjugated to a nanoparticle core. This radial orientation of oligonucleotides and architecture distinguishes SNAs from the components from which they are comprised. Specifically, unique chemical and biological properties emerge that are not observed with...
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...
In this thesis, I present the development and benchmarking of several theoretical methods designed to enable the rigorous modeling of magnetic properties of molecules containing one or a few heavy atoms, particularly single-molecule magnets. The new methods use a full four-component treatment of relativity, allowing spin–orbit effects to be taken...
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...
Nanoparticle synthesis is capable of producing particles with any combination of structure, chemistry, size, shape, and surface. All of the different combinations of these physical properties can produce nanoparticles with almost countless materials properties suited for many applications. Given this interest in using nanoparticles in so many different fields, including...
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...
One of the central challenges in solid-state chemistry is synthetic control over structure. Owing to limited reactivity of Pb with transition metals at ambient pressure and high temperature as well as the variety of properties that emerge from the few known binary transition-metal–Pb compounds, this research focuses on accessing and...
Heterogenous catalysis is the pillar of chemical production and a crucial aspect for optimization toward a sustainable future. To improve the current design of heterogeneous catalysts of maximal activity and product selectivity, gaining fundamental understanding of the catalytic active sites is crucial. The nature of active sites has been the...
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...
Neurons are sensitive to the mechanical properties of their environment and show better growth, survival and differentiation when they are cultured in soft environments with mechanical properties similar to those of the brain compared to other tissues. Within the central nervous system (CNS), there is also a range of mechanical...
Single-use plastic waste pollution will cause significant harm to the environment if left unaddressed. One possible mitigation strategy is to develop processes, e.g. catalytic hydrogenolysis, that can convert (i.e. upcycle) waste plastics into value-added products capable of participating in a circular economy. Platinum (Pt) catalysts on strontium titanate nanocuboid supports...
Oxide/aqueous and metal/metal oxide interfaces are essential for environmental remediation, catalysis, and corrosion inhibition, in addition to their potential implementation as energy transducers, consumer electronics, and coating products. While these interfaces are critically important, they are difficult to access experimentally under aqueous flow conditions. This thesis describes results obtained with...