Metal-organic frameworks (MOFs) are porous, crystalline materials synthesized by combining metal nodes and organic linkers through self-assembly. The diverse range of building blocks available allows for extensive tunability of MOFs, enabling the optimization of these materials for various applications, such as gas storage, separations, and catalysis. This study aimed to...
Interpenetrating polymer networks (IPNs) are multicomponent materials that enhance the compatibility of otherwise immiscible polymers by trapping the microstructure in a non-equilibrium state. By combining polymers with vastly different moduli, IPNs effectively disperse rigid polymers within a soft matrix, resulting in a reinforced elastomer. This approach significantly increases the modulus...
One of the greatest challenges in heterogeneous catalysis is the rational design and development of new catalytic systems, due to synthetic limitations in the design of solid catalysts and inhomogeneity of chemical sites at solid surfaces. This obfuscates understanding of catalyst behavior and slows improvements of processes. One approach to...
Pollution-intensive industrial manufacturing processes threaten the health of ecosystems and societies through toxic waste streams and energy intensive processes that lead to greenhouse gas emissions. Biological systems present more sustainable routes to many useful industrial chemicals by using enzymes at low temperatures, but the time and effort required to optimized...
Efficient and sustainable utilization of global resources represents a grand but achievablechallenge. By leveraging biology, we can transform abundant, but recalcitrant resources like lignin
to products ranging from fuel to medicine to polymers. Efforts to do so are expansive, but
challenges remain, due in no small part to the difficulty...
Conventionally cross-linked polymers, which comprise the vast majority of commercial thermosets, cannot be decross-linked after curing or flow upon heating. Therefore, they cannot be effectively recycled into high-value products at end-of-life. Their lack of recyclability is due to the permanent cross-links, which restrict the flow of the chains in the...
Shale gas is a critical energy resource that is comprised primarily of light gases that are expensive to transport. Because these gases are geographically spread-out and there is insufficient capacity to transport them to centralized processing facilities, they must often be flared, leading to great sources of resource waste and...
Cellular translation is responsible for the synthesis of proteins, a highly diverse class of macromolecules that form the basis of biological function. In Escherichia coli, harnessing and engineering of the biomolecular components of translation, such as ribosomes, transfer RNAs (tRNAs) and aminoacyl-tRNA synthetases, has led to both biotechnology products (i.e.,...
Protein-based biomaterials are widely used in biomedical applications and mechanical support because of their novel structural flexibility, biocompatibility and mechanical properties. Protein-based biomaterials outperform traditional synthetic materials in various environments as traditional materials lack the diverse chemical functionalities that proteins offer. Novel bioinspired techniques such as directed evolution offer the...
Protein-protein interactions are ubiquitous in living systems, and mediate important cellular processes from decision making to immunity against pathogens. Furthermore, protein-protein interactions are key to many protein therapeutics, pathogen diagnostics, and numerous synthetic biology applications. As a result, there has been significant effort to develop methods to express potential protein...
Conventional polymer networks are composed of strong, fixed covalent cross-links. The covalent cross-links render polymer networks with outstanding mechanical properties, heat stability, and chemical resistance; however, they also prevent polymer networks from being decross-linked or/and recycled into similar-value products at the end of their life, leading to environmental and economic...
No two cells in a population are identical to each other. Cell populations are almost universally heterogeneous, with their heterogeneity or variability often underlying complex emergent behavior and phenotypes. Heterogeneity presents a challenge to the discovery, characterization, and control of multicellular systems. Heterogeneity exists across multiple scales, ranging from the...
From energy to materials, hydrocarbon chemistry drives our world. Stemming from the petrochemical industry, our understanding of CxHy combinations has allowed society to flourish, and hydrocarbons will likely remain valuable species in our future even as we transition to greener carbon and hydrogen sources. Currently, one of the most efficient...
Oil paintings are complex works of art, even on the molecular level. Drying oils cure into a solid film through autoxidation and polymerization reactions and then degrade, leading to changes in material properties and film stability. This chemistry can be captured in a computational model and used by researchers in...
Enzyme substrate promiscuity has significant implications for metabolic engineering. The ability to predict the space of possible enzymatic side reactions is crucial for elucidating underground metabolic networks in microorganisms, as well as harnessing novel biosynthetic capabilities of enzymes to produce desired chemicals. Reaction rule-based cheminformatics platforms have been implemented to...
Chimeric antigen receptor (CAR) T-cell therapies marry advances in cellular engineering with personalized medicine to provide patient-specific, targeted cancer treatments. Though current CAR T-cell therapies successfully target blood cell cancers, treating solid tumors has proven to be more challenging. Solid-tumor CAR designs must overcome several challenges, including tumor microenvironment barriers...
Mixing by cutting-and-shuffling (like that for a deck of cards or a Rubik's cube) is a paradigm that has not been studied in detail even though it can be applied in a variety of situations including the mixing of granular materials. Mathematically, cutting- and-shuffling is described by piecewise isometries (PWIs),...
Nanotechnology research broadly encompasses the exploration of the unique chemical,optical, electronic, or biological properties of materials with dimensions < 1 µm. Inorganic
nanoparticles are one such class of materials, with properties that are exceptionally sensitive to
particle size and structure. This is especially evident in the field of heterogeneous chemical...
Biological therapeutics have revolutionized the way we treat cancer due to their ability to target tumors discriminately, leaving healthy cells unaffected. However, our inability to tailor the structure of biologics may hamper their optimization for efficacy. This lack of programmability contributes to factors such as immunogenic responses, inability to penetrate...
This thesis focuses on identifying structure-property-performance relationships in supported nanoparticle catalysts, where an active catalyst material is supported on a high surface area substrate. Identifying these relationships in supported nanoparticle catalysts can be quite challenging, as the complex structure of these catalysts results in numerous potential sources for changes to...
Metal–organic frameworks (MOFs) are a class of crystalline materials composed of metal nodes connected by organic linkers. Due to their high degree of synthetic tunability, MOFs have been considered for a wide range of applications, including many that rely on a change in oxidation state. While most MOFs are generally...
Molybdenum oxides and sulfides are earth-abundant materials known to catalyze a wide array of reactions, including dehydrogenation, hydrotreating, and higher alcohols synthesis. In particular, alkane and alcohol dehydrogenation are of interest given recent shifts in the energy landscape away from traditional petroleum feedstocks and towards natural gas and renewable energy...
Metal-organic frameworks are crystalline, nanoporous materials formed by metal nodes connected by organic ligands. MOFs represent an exciting approach to materials design where a material with desired properties can be made by choosing the compatible nodes, linkers and topologies independently. MOFs are highly porous and have high surface areas...
Cells are primarily comprised of metal ions, small molecules, proteins, lipids, and nucleic acids. The ability to probe these molecules in single living cells can shed new light on chemical processes inside of cells or allow disease diagnosis based on molecular profiling. However, there exists a lack of tools that...
The Escherichia coli ribosome is a molecular machine capable of sequence-defined polymerization of -amino acids into proteins, a feat unmatched by any other current synthetic catalyst. It is complex in its structure, comprised of 3 RNA parts (the 5S, 16S, and 23S ribosomal RNAs) and 54 ribosomal proteins (r-proteins). Efforts...
By 2030, up to half of the world’s population is projected to suffer from water insecurity: a chronic scarcity of potable water due to rapidly warming temperatures, increased agricultural demand, and pollution. The health impacts of contaminated water are profound: hundreds of thousands of global deaths each year are ascribed...
While metabolic engineering can enable the sustainable bioproduction of new materials, efforts are often impeded by pathway bottlenecks. To mitigate the effects of toxic or reactive intermediates and resource competition resulting from heterologous pathway incorporation, bacterial microcompartments (MCPs) have recently been considered for engineered compartmentalization in bacterial host organisms. MCPs...
Two-step, solar thermochemical water splitting using nonstoichiometric oxides has emerged as an attractive approach for large-scale hydrogen production. Perovskite-structured oxides, with their wide tunability, offer the potential for high fuel productivity at moderate operating temperatures. Given the vast chemical space, the materials development effort is carried out here in combination...
Interfacial effects play a critical role in perturbing the properties of polymeric materials. The average properties of polymer materials with substantial specific interfacial area, e.g., ultrathin films, nanorods, and polymer nanocomposites, often deviate significantly from the bulk responses. Much of the past research has focused on systems in which free...
The need to rapidly develop and produce life-saving vaccines and therapeutics is critical for overcoming pandemics in a global economy. Recent advances in automation and cell-free systems have opened new avenues for expediting optimization and production of biologic vaccines and therapeutics. A key consideration for the development of protein biologics...
Granular mixing has received less attention than fluid mixing due to the unique properties of granular materials and the complexity of their flow behaviors. Unlike fluid flows, where a continuum perspective accurately captures flow behavior, neither a continuum nor a discrete perspective by itself can describe the global behaviors of...
Natural gas is likely to become one of the main sources of carbon-based chemicals in the next century due to rapidly increasing natural gas production levels. This has created new incentives to find materials that are active and selective towards alkane partial oxidation reactions that are relevant for natural gas...
Conventional cross-linked polymers are widely used owing to their outstanding stability and performance. However, permanent cross-links in these polymer networks prevent them from being recycled or reprocessed at the end of life, leading to major sustainability and economic losses. The recycling issue associated with polyurethane (PU) thermoset wastes exemplifies such...
Biological systems comprise diverse collections of cellular and non-cellular components with intricate relationships and dynamic interactions. To gain system-level understanding, we must be able to accurately model these systems, both experimentally and computationally. Agent-based models (ABMs) in particular are a uniquely intuitive, modular, and flexible framework capable of supporting multi-scale,...
The effective capture and detoxification of chemical warfare agents (CWAs) is a pressing need in the modern world. Materials are needed for both the destruction of weapon stockpiles and personal protection via fabric coatings or respirators. Attractive candidates for these applications include metal–organic frameworks (MOFs) – highly crystalline materials composed...
Label-free assays, and particularly those based on the combination of mass spectroscopy with surface chemistries, enable high-throughput experiments of a broad range of reactions. However, these methods can still require the incorporation of functional groups that allow immobilization of reactants and products to surfaces prior to analysis. In this thesis,...
Since their introduction nearly a century ago, protein vaccines and therapeutics have revolutionized our ability to prevent and treat human disease. However, existing production processes for biopharmaceuticals are technically complex and rely on living cells, which necessitates highly centralized manufacturing in large-scale production facilities, specialized equipment, and cold-chain distribution. With...
Complex fluids are ubiquitous, from natural materials to manufactured products. Understanding their behavior under flow is vital for engineering these materials. Extensional flow, despite being industrially relevant and often producing dominant impacts upon complex fluids, is an underserved topic compared to shear flow due to a lack of reliable apparatuses...
Metal-organic frameworks (MOFs) are a class of nanoporous materials with highly tunable pore shape and chemistry. They are synthesized in a "building block" approach to form crystalline porous materials, which have been explored for diverse applications including gas storage and separations. Given the enormous size of the MOF design space,...
Biomass has the potential to be our country’s leading renewable source of energy. Specifically, fast pyrolysis is a promising method for the conversion of biomass to valuable fuels and chemicals. Given that fast pyrolysis has a residence time of about two seconds, computational methods are particularly useful in obtaining product...
Supported transition metal oxides are an important class of catalysts with a wide range of industrially relevant applications. However, commonly used synthesis techniques to prepare these catalysts often result in a complex mixture of surface species. This inhomogeneity makes it difficult to understand what specific structures might be responsible for...
Organismal development depends upon countless cell decisions to adopt particular fates at the appropriate time and place. These decisions are executed by systems of biochemical reactions called regulatory networks. Elucidating the general principles underlying the structure and function of these networks is vital to understanding all developmental processes, as well...
This thesis centers around the development and application of novel high throughput lithography tools. These advances help: 1) establish the field of nanocombinatorics, where massive libraries (termed megalibraries) of materials can be prepared in a positionally encoded manner and then screened for functional activity, and 2) advance stereolithographic 3D printing...
Currently, platelet transfusions, possessing profound clinical importance in the clotting of blood and healing of wounds, are entirely derived from human volunteer donors. This approach is limited by a 5-day shelf life, the potential risk of contamination, and differences in donor/recipient immunology. In vivo, platelets are formed when bone marrow...
Metal nanoparticles supported on oxides are versatile systems. Ordered arrays of multimetallic nanoparticles of different sizes and surface densities can be synthesized using block copolymer-mediated nanolithography techniques. Metal nanoparticles on planar supports like silica can be utilized for catalyst discovery. Under reaction conditions and at high temperatures, the changing surface...
Nucleic acids not only are the building blocks of life but also a class of attractive macromolecular therapeutics. However, the delivery of therapeutic oligonucleotides into cells has been a major challenge due to their large size and highly negatively charged backbone. Spherical nucleic acids (SNAs) are a class of emerging...
Conventional polymer network materials, e.g., rubber tires, cannot be efficiently recycled for high-value applications because of their permanent network structures. Therefore, at the end of use, none or only a small fraction of the economic value can be recovered from these materials. Scrapped tires demonstrate well this issue along with...
Recent advances in combinatorial chemistry, synthetic biology, and ‘omics’ research require high-throughput methods for performing and analyzing thousands to millions of reactions in one day. However, it is a challenge to engineer high-throughput systems that can autonomously conduct and analyze such a large number of reactions in a generalizable and...
As the global population grows, consumption of water, energy, and food will also increase, placing stresses on these sectors, raising the importance of the Water-Energy-Food Nexus (WEFN). However, operation of WEFN systems are currently not sustainable. It is thus crucial to design WEFN systems to be sustainable from local to...
Polymers permeate almost all facets of modern life. For end use applications, these materials are typically processed into products at elevated temperatures under which molten polymers are subjected to flow. Particular interest lies in the flow-induced crystallization behavior of polymer melts under extensional flow, which is a flow type dominant...
