Part I: Design of Photo-Responsive Molecules towards Biomedical ApplicationsThe use of light to control systems provides numerous advantages such as spatiotemporal precision, non-invasive penetration, and precise energy input. Specifically, molecules that undergo photoinduced cleavage, photoremovable protecting groups (PPGs) have emerged as an active area of research due to their broad...
Formed through self-assembly of polynuclear node clusters and multitopic organic linkers, metal–organic frameworks (MOFs) are a class of three-dimensional crystalline materials. Due to their exceptional porosity, high surface areas, amenability to construction, chemical diversity, uniformly arrayed metal-containing nodes, and highly modular nature, MOFs are an ideal class of materials for...
The discovery of abundant reserves of shale gas over this past decade has reshaped the world’s energy landscape. It has renewed interests in the activation and conversion of methane as well as other light alkanes. While the oxidative coupling of methane (OCM) and oxidative dehydrogenation (ODH) of ethane and propane...
Chemical modifications of oligonucleotides (ONs) have advanced these molecules towards clinical approvals. On their own, native ONs have poor pharmacokinetic properties, such as rapid degradation by nucleases and poor cell uptake, which limit their potential therapeutic applications. Chemical modifications of ONs can increase their stability, alter their interactions with cells,...
The development of new catalytic methodologies for the precision synthesis of carbon-carbon bonds is central to the advancement of synthetic organic chemistry. Significant focuses of these efforts are made on the enantio- and diastereoselective synthesis of carbon frameworks, especially as chemists and biologists become more aware of the impact 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...
Thermoelectric modules that convert heat into electrical energy are attractive for improving global energy management. This thesis reports the synthesis and characterization of two new families of lead and tin chalcogenide alloys and focuses on the impact of the grain boundaries, phase segregation, and atomic vacancies on the electronic and...
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...
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,...
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...
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,...
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...
Organic solar cells (OSC) are a next generation solar energy technology that offers the advantages of scalable fabrication, light weight, flexibility, and earth-abundant starting materials. Despite tremendous advances in OSC power conversion efficiency (PCE) over the last decade, active layer material selection and optimization is still largely empirical. In order...
Extensive study of nanomaterial chemical and optical properties has enabled their integration into a variety of applications. However, less thoroughly investigated are the heat generation and dissipation processes of nanomaterials following optical excitation. These phenomena are of immense importance as thermal energy can distort a material’s structure, which has profound...
This thesis describes a novel demonstration of quantum teleportation, a protocol within the broader field of quantum information science, carried out by an electron transfer reaction within a molecular system. As described in Chapter 1, quantum information science has potential impacts in computation, communication, and cryptography. This field relies on...
Theoretical investigation of photochemical processes in molecules is a nontrivial task. Ab initio calculations that completely describe such processes are often intractable to perform given today’s hardware. Thus, to gain insight into common areas of interest, such as in transition metal photochemistry and organic photovoltaics, less accurate but more feasible...
The Controlled, Site-Isolated Synthesis of Polyelemental Nanostructures in Polymer Nanoreactors Pengcheng Chen Polyelemental nanoparticles are an attractive class of materials due to their potential applications, which span the fields of catalysis, plasmonics, electronics, magnetics, targeted drug delivery, and bio-imaging. However, conventional synthetic methods for such structures are limited, especially when...
Organic semiconductors have shown great promise for optoelectronic applications, particularly solar photovoltaics. Critical to their success is the ability to understand and manipulate the relationship between molecular structure and bulk properties. Substantial progress on understanding structural influences on electronic properties has been made for the conjugated polymers and small molecules...
This thesis describes fundamental photophysical studies of quantum dot (QD)-molecule complexes, aimed at discovering strategies for enhancing the efficiency of QD-photocatalyzed and QD-sensitized multi-electron catalytic reactions, for the purpose of solar fuels production. Photosensitization of molecular catalysts that are active for reactions such as the reduction of carbon dioxide or...
Organic semiconductors are an active area of research with great promise for delivering next generation electronics and clean energy technologies. As the field matures, understanding the connection between molecular structure, materials’ properties, and device performance will be critical in finding the right material for an intended application. An effective strategy...