With the dual challenges of meeting global energy demand and mitigating anthropogenic climate change, significant effort is being applied to generating power from renewable sources. The dye-sensitized solar cell (DSC) is a photovoltaic technology capable of generating electricity from sunlight, but suffers losses in efficiency due to deleterious electron transfer...
Organic photovoltaics (OPVs) are an attractive solar energy technology for low-current applications. Herein is described the supramolecular design and methodology to manipulate intermolecular interactions in order to create an active layer in OPVs devices composed of crystalline and amorphous donor-acceptor domains, which has been proposed as the ideal morphology for...
Raman spectroscopy is an established and versatile molecular sensing technique, but it is limited by its modest chemical sensitivity. Surface-enhanced Raman spectroscopy (SERS) can amplify otherwise weak normal Raman signals up to nine to ten orders of magnitude, giving rise to its application in many molecular sensing problems, including those...
Interprotein electron transfer (ET) occupies a central role in both chemistry and biology, as it is important in a variety of functions including cellular respiration, metabolism, and energy transduction during photosynthesis. Consequently, understanding the protein-protein recognition and docking that controls interprotein ET is an important field of scientific research.
One...
Surface-enhanced Raman spectroscopy (SERS) is a powerful technique for characterizing molecular systems. It combines the chemical selectivity of vibrational spectroscopy with plasmonic signal enhancement to achieve the ultimate limit of detection--a single molecule. By overcoming the effects of ensemble averaging, single molecule SERS (SMSERS) probes distributions in molecular interactions and...
Metalloporphyrins fulfill incredibly diverse chemical roles in biology and photocatalysis, where they act as photosensitizers, redox sites, substrate binding sites, and facilitators of long range electron transfer. Metalloporphyrin chemistry is uniquely tuneable through conformation and functionalization of the porphyrin ring, choice of metal, and interaction with the environment as these...
The FDA approvals of afatinib and ibrutinib in 2013 led to a heightened interest in cysteine-reactive covalent inhibitors. However, there are few methods to discover new cysteine-reactive inhibitors for enzymes for which reversible binding scaffolds are not known. To this end, we rationally designed a chemical system to attach a...
The properties of crystalline materials are controlled by their composition and by their structure, however, the structure of a crystal is only partly controlled by its composition. Development of specifically directed inorganic syntheses will require an understanding of the dynamics of crystal phase forming processes, especially those processes involved in...
Human skin oils are significant scavengers of atmospheric oxidants in occupied indoor environments. Many techniques used to study gas-phase transformations of surface films indoors have been limited to off-line bulk analysis, although more surface-selective methodologies are emerging. Here, we present a multi-prong analytical approach to characterizing skin oil ozonolysis. Skin...
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...
A fundamental materials science question is “why and how will this material form?” The experimental,computation, and time resources necessary to answer this question consume significant resources due to the
predominantly trial-and-error based approaches common in materials research. This dissertation reintroduces
a number of fundamental thermodynamics-based tools for the study of...
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...
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...
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...
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 demand for low cost, unconventional electronics requires new materials with unique characteristics that the traditionally used silicon-based technologies cannot provide. Metal oxide semiconductors, such has amorphous indium gallium zinc oxide (a-IGZO), have made impressive strides as alternatives to amorphous silicon for electronics applications. However, to achieve the full potential...
Metal–Organic Frameworks (MOFs) is a class of material comprising organic linkers and inorganic, metal-ion-containing nodes, with diverse functionalities and wide-range of applications. Because of their porous nature and functional nodes and linkers, they are competent candidates for gas storage, separation, catalysis, and so on. Most MOFs, however, are intrinsically insulating,...
Quantum dots (QDs) are promising photocatalysts due to their large extinction coefficient, large surface area-to-volume ratio, and stability upon irradiation. QDs have been studied in photocatalytic hydrogen production, CO2 reduction, and reduction of small organic molecules such as nitrobenzene. This dissertation describes the application of QDs in two photocatalytic cross-coupling...
Secondary organic aerosol (SOA) particles are a class of highly abundant atmospheric constituents that represent a substantial fraction of carbon within the climate system. A subset of naturally-occurring SOA particles are formed through atmospheric oxidation of biogenic volatile organic compounds (BVOCs), forming oxygenated products of lower volatility that can partition...