Direct dynamics quasiclassical trajectory (QCT) calculations are performed to study the dynamics of model atom + polyatom reactions. In the first part of this thesis, we examine adiabatic dynamics of H/O reaction with simple alkanes, CD4 and C2H6. Overall good agreement with state-of-the-art experiments shows that the molecular motion is...
Okilactomycin and chrolactomycin are antitumor antibiotics isolated in 1987 and 2001, respectively. These tetracyclic natural products possess a unique 6-5 fused tetrahydropyrone-butyrolactone. The spirocenter is part of a highly functionalized cyclohexene ring, which together with the aforementioned 6-5 system compose the core of these molecules. A six carbon, 1,3-dialkyl-substituted carbon...
The work presented in this thesis describes investigations into linear and nonlinear optical properties of two-dimensional silver nanoparticle arrays. The linear optical measurements - extinction measurements were performed on two-dimensional square arrays of L-shaped silver nanoparticles fabricated by electron beam lithography in order to study the effect of dipole coupling...
Interfaces and surfaces are ubiquitous in the environment. Heterogeneous binding events and reactions control the transport and speciation of dissolved pollutants in groundwater. Many heterogeneous processes occur at mineral oxide/water interfaces, and can be controlled either by the mineral oxide, or organic molecules bound to the surface. The prevalent natural...
Preventing the build-up of indoor pollutants represents an emerging goal in environmental chemistry. Heterogeneous catalysis provides an attractive method of remediating indoor air pollution, but optimization through rational catalyst design requires a detailed understanding of the catalytic surface and surface-pollutant interactions. In this work, a chemical ionization mass spectrometry (CIMS)...
Small molecule organic materials based on perylene- and naphthalene- diimide are synthesized and characterized for use as semiconductor thin films in organic field-effect transistors. The orbital energetics of the materials are investigated via electrochemical, spectroscopic, and computational techniques. The thin film solids are characterized by x-ray diffraction techniques and surface...
The overarching goal of this work is to understand nanometer scale junctions and electron transport through molecules in these junctions. Calculations detailing quantum interference in the electron transport through molecules, and the control of these features, show great potential for use as discrete electronic elements. Concurrent work on the fabrication...
The idea that structure determines the properties of a material is a powerful concept in chemistry and in all fields in which chemistry is important, including engineering, medicine, and materials science. My research aims to better understand the structure-property relationships of a class of materials known as metal–organic frameworks (MOFs)....
The nonlinear optical technique, second harmonic generation (SHG), is applied here for the first time to probe single and double strand DNA (ssDNA and dsDNA) chemically attached to fused quartz/water interfaces. DNA interfaces are often a critical functional component of biodetection, thus, the development of molecular biosensors requires a thorough...
The safe and efficient storage of hydrogen is possibly the chief obstacle to its use as a fuel on a large scale. Metal-organic frameworks (MOFs) are well poised to provide unique solutions to hydrogen storage, and gas storage in general, a result of their crystalline, porous networks that present the...
Au nanoprisms are a new type of inorganic nanoparticle that is particularly interesting because these particles can be made in high yield, are composed of a metal with well known surface chemistry, exhibit strong, architecture and environment-sensitive optical features, and have well-defined crystallographic facets. All of these features make Au...
My thesis focuses on the design and synthesis of lanthanide coordination complexes as Zn(II)-responsive magnetic resonance imaging (MRI) contrast agents. These agents produce an increase in MR intensity upon binding of Zn(II) through water modulation to Gd(III) chelates. To this end, several Zn(II)-responsive contrast agents have been synthesized and studied...
Particulate methane monooxygenase (pMMO) is a membrane-bound metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria. The nature of the pMMO active site and the overall metal content are controversial, with spectroscopic and crystallographic data suggesting the presence of a mononuclear copper center, a dinuclear copper center, a trinuclear center,...
Copper serves as a cofactor for many proteins and enzymes involved in important biological processes, but at the same time, excessive copper is toxic to cell. Thus, the intracellular copper concentration must be tightly controlled such that copper is provided to essential enzymes but does not accumulate to toxic levels....
Chapter 1 describes the homopolymerization of styrene and the copolymerization of ethylene and styrenic comonomers mediated by the single-site bimetallic "constrained geometry catalysts" (CGCs), (µ-CH2CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](TiMe2)}2 [EBICGC(TiMe2)2; Ti2], (µ-CH2CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](ZrMe2)}2 [EBICGC(ZrMe2)2; Zr2], (µ-CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](TiMe2)}2 [MBICGC(TiMe2)2; C1-Ti2], and (µ-CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](ZrMe2)}2 [MBICGC(ZrMe2)2; C1-Zr2], in combination with the borate activator/cocatalyst Ph3C+B(C6F5)4- (B1). Under identical styrene homopolymerization conditions,...
Metal nanoprisms are a novel class of anisotropic nanomaterials with unique optical properties dependent on their size, shape, and composition. Silver nanoprisms are of particular interest because their surface plasmon resonance bands are readily tunable in the visible and near-IR region. The objectives of this thesis research focus on photochemical...
Conjugated organic molecules and polymers hold significant promise for use as active materials in electronic devices. Employing such "soft" materials can decrease cost of device fabrication, while enabling unique properties such as mechanical flexibility, large-area coverage, and highly tunable materials properties. A primary roadblock to the realization of this dream...
Chemical vapor deposition (CVD) is a well-developed technique for growing thin films of a wide variety of materials, which relies on the development of new and better performing metal-organic precursors. To this end, three studies have been conducted into the compatibility of sulfur and phosphine containing ligands with low- and...
This thesis summarizes our research efforts on the application of the nano-structured anodic aluminum oxide (AAO) membrane in heterogeneous catalysis. Procedures for growing the AAO membrane in the center of an aluminum disc have been developed by appropriately masking the disk's perimeter during the anodization and etching steps. The remaining...
Metallic nanostructures are able to confine and manipulate electromagnetic fields because light can couple to free electron oscillations called surface plasmons (SPs). These plasmons exist on metal surfaces as localized (short-range) or as propagating (long-range) modes depending upon the size and geometry of the nanostructure. This dichotomy is primarily an...
This thesis investigates singlet exciton fission, a physical process that converts one singlet exciton to a pair of triplet excitons. Singlet fission was discovered nearly forty years ago, but the mechanism for this process is still not well understood. Recent work has suggested that singlet fission may be capable of...
This thesis attempts a combined theoretical/experimental investigation of two fundamental scaling laws in charge transfer reactions: how the rate of those reactions varies as a function of distance between an electron donor and an electron acceptor and how the rate varies as a function of the number of distinct pathways...
The work described in this dissertation focuses on the optical characterization of micron-sized structures with mesoscale (100-1000 nm) features to investigate of the optical analog to the quantum corral. Lithographically patterned arrays of metallic rings and ellipses were used to study how light can be manipulated and confined within these...
The contents of this dissertation are divided into two sections: (1) the preparation and characterization of quaternary rare-earth chalcogenides and oxychalcogenides and (2) the localized surface plasmon resonance (LSPR) spectroscopy of metallic nanoparticles fabricated by nanosphere lithography (NSL).
Single crystals of CsTmCoS3, CsYbCoS3, CsHoCoSe3, CsYbCoSe3, and CsYbZnSe3 have been prepared...
Theoretical analysis of DNA bridge-mediated electron transfer (ET) led to the proposal that photoinduced ET might occur via either superexchange or hopping mechanisms. Electron transfer has been proposed to occur via a superexchange mechanism at short distances and via a hopping mechanism at longer distances. However, a crossover in mechanism...
This dissertation describes the use of alkanethiols and polymers for the development of lithographic affinity and resist array templates that can be utilized for directing the assembly of biological molecules, for building up multilayered polyelectrolyte thin films, and for fabricating metal solid-state nanostructures. The first two chapters of the work...
Two new methods have been developed employing silicon-containing molecules in novel organic transformations. The first strategy utilizes Lewis base-activation of triethoxysilylalkynes to deliver mild acetylide nucleophile equivalents. The second approach involves the use of enolate additions to acylsilanes to generate β-silyloxy homoenolate intermediates.
Lewis base-catalyzed activation of triethoxysilylalkynes promotes the...
This dissertation focuses on the utilization of two coordination chemistry-based synthetic approaches, which provide the ability to rapidly and quantitatively assemble sophisticated supramolecular cofacial porphyrin complexes. Significantly, by adopting a coordination chemistry-based approach, the porphyrin-porphyrin interactions can be regulated in situ via the addition or removal of chemical effector molecules....
The first section of this thesis focuses on applications of DNA-modified gold nanoparticles (AuNPs) while the second part addresses the fundamental properties that arise from conjugating DNA to inorganic AuNPs. Two types of applications are discussed. The first application utilizes the colorimetric properties of AuNPs to screen duplex and triplex...
The overarching theme of this thesis is the development of non-natural oligomers for use in biological applications. Chapter I details the synthesis and studies of modified peptide nucleic acid (PNA) oligomers. PNA is a synthetic oligonucleotide mimic that binds to natural nucleic acids with extremely high affinity and specificity, making...
This dissertation describes the invention and development of a new nanolithographic method: On-Wire Lithography (OWL). OWL is a simple, reproducible, and high-throughput procedure for the synthesis and lithographic processing of metal nanowires (i.e. Au, Ag, Pt, Ni, and Cu) that allows researchers to control the morphology and feature size of...
Surfaces and interfaces, which are ubiquitous in the environment, control the mobility,speciation, and ultimate fate of groundwater species. The presented work provides insight into the interfacial behavior of three environmental pollutants: hexavalent chromium, oxytetracycline, and morantel. Model surfaces are employed for these studies, including (1-102) α-Al<sub>2</sub>O<sub>3</sub> and a carboxylic acid-terminated...
Metal oxide surfaces are generally recognized as active substrates for many catalytic reactions. Density Functional Theory (DFT) has been found as a useful computational tool to investigate the geometry, energy, electronic structure of reactive oxide surfaces and their interaction with small molecules and fragments. In this thesis, primary efforts have...
This dissertation covers the synthesis and study of peptide nucleic acids (PNAs), specifically, derivatives of PNA containing amine-bearing sidechains or cyclopentane portions. PNAs are non-natural nucleic acids that have far reaching potential in therapeutics and nucleic acid detection. Despite immense potential and widespread application, improving on the design and applications...
Alkenylsilanes of varying chain lengths are investigated as simultaneous chain transfer agents + comonomers in organotitanium-mediated olefin polymerization processes. Ethylene + alkenylsilane polymerizations were carried out with activated Me2Si(Me4C5)(NtBu)TiMe2 and (-CH2CH2-3,3'){(5-indenyl )[1-Me2Si(tBuN)]}2Ti2Me4 precatalysts. Alkenylsilane incorporation levels follow the trend C8H15SiH3 < C6H11SiH3 ≈ C4H7SiH3 < C3H5SiH3. Long-chain branching levels versus...
Nanoplasmonics is an emerging branch of photonics that studies the optical properties of noble metals. Nanostructured noble metal materials, which can strongly interact with light and support various plasmon modes, are exceptional candidates for nanophotonic devices. This work describes the latest advances in the fabrication of ordered silver nanoparticles or...
The work presented here describes investigations into the optical properties of single silver nanoparticles. The contents of this thesis are divided into two parts: (1) single nanoparticle localized surface plasmon resonance (LSPR) spectroscopy and sensing and (2) approaches to combining LSPR spectroscopy with atomic force and transmission electron microscopies. Part...
The work presented in this dissertation is centered on experimental efforts to maximize the sensitivity of surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) toward their application in ultrasensitive nanoscale chemical analysis. The work focuses on fundamental studies of the plasmonic properties of silver nanostructures, and how those properties...
Theoretical studies on electronic structure governing charge transport properties are investigated to understand and improve the prediction of electron charge carrier organic semiconductors used in field-effect transistors. Perfluorinated oligothiophene semiconductors have shown experimental n-type behavior, but placement of fluorinated aryl groups changes charge polarities. Models were developed to investigate how...
This thesis consists of the synthesis and photophysical characterization of chlorophyll- and porphyrin- based multichromophore arrays designed for the purpose of studying energy and charge transfer therein. The first series of arrays consists of donor-acceptor dyads in which various arylene diimide electron acceptors are attached through a phenyl group to...
Part 1. The complex folded structures associated with RNA allow for specific protein-RNA interactions and also create binding sites for small molecules. Developing organic molecules that can bind RNA with high affinity and specificity is a challenge that must be overcome for RNA to be considered a viable drug target....
The porphyrazines (pzs), a class of porphyrin derivatives, have shown potential as therapeutic and imaging agents due to a combination of their near-IR absorbance/fluorescence and their enhanced chemical flexibility. Cell viability/proliferation assays and fluorescence microscopy were carried out in both tumor and normal cells to characterize the biological activity of...
This dissertation describes the development and use of novel chemical affinity templates to direct the assembly and preserve the activity of biological molecules in surface- and solution-based biomolecular assays. The majority of work described herein focuses on advancing biological nanoarray technology to enable the study of fundamentally important biological processes...
UV Raman spectroscopy is a powerful tool to investigate hydrocarbons-zeolite systems, including the coke formation mechanism during MTH reactions, the sorbet-framework interactions and the quantitative analysis of catalytic reactions.
First, methanol, dimethyl ether and ethylene reactions were carried out on H-MFI with different Si/Al atomic ratios to study the coke...
The work described here includes both fundamental and application based studies centered around the use of plasmonic sensors. Fundamental studies focus on probing the optical properties of nanosphere lithography (NSL) fabricated Ag nanoparticles, while surface-enhanced Raman spectroscopy (SERS) sensors are applied to identify and characterize artists' red dye and red...
The [(salen)CrCl + LB] catalyst system was found to be a highly active catalyst system for the [aziridine + CO<sub>2</sub>] coupling reaction, and exhibited a marked preference for the formation of 5-substituted oxazolidinone product, especially in the absence of cocatalyst. The activity of this catalyst system is optimized by modifying...
A catalytic, multi-component coupling reaction for the synthesis of nitrogen-containing heterocycles has been developed, via the reaction of an imine, &#945;-diazoester and unsaturated coupling partner in the presence of a copper(I) or rhodium(II) transition metal catalyst with excellent diastereo-selectivities and high yields. The transition metal-catalyzed decomposition of a diazo compound...
High relaxivity contrast agents are of great importance in the advancement of magnetic resonance imaging diagnostics for use in biomaterials. Biomaterials that are implanted into the body, with the goal of repairing or regenerating lost or damaged tissue, need to be tracked noninvasively, over time. I have completed work using...
Two new strategies have been developed to accomplish direct nucleophilic acylation reactions. In the first approach, acylsilanes are added to various electrophiles using N-heterocyclic carbenes as catalysts. The second method utilizes O-silyl thiazolium carbinols as stoichiometric acyl anion precursors to afford acylated products under mild reaction conditions.
N-heterocyclic carbenes generated...
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...
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...
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,...
This thesis document is comprised of three research projects. The first investigates the active vibrational modes involved in twisted intramolecular charge transfer in a Julolidine-BODIPY dyad using two-dimensional electronic spectroscopy along with DFT calculations. We identified two types of vibrations, compression and torsional motion, as playing an important role in...
Renewable energy technology, more so than ever before, is critical to the survival of humanity. For decades, concentrated efforts into designing and developing such novel devices resulted in the innovation of solar-driven photovoltaics that were competitive with nonrenewable alternatives. This thesis explores the dynamic behavior of alternative material candidates that...
Many processes in nature and human-made settings rely on the unique properties of charged metal oxide:aqueous interfaces. Despite their ubiquity, these buried interfaces are challenging to study, since any analytical technique aiming to overcome the relatively small number density of interfacial versus bulk species must be highly sensitive and surface-selective....
This dissertation focuses on the study of the superionic state in multicomponent systems, where the smaller component exhibits delocalization and mobility while still maintaining system compactness through component attractions. Superionic behavior is widely observed in various systems and plays a crucial role in ceramic superionic conductors, which offer high ion...
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...
Clean water supplies are required for industry and general life. However, water shortages dueto pollution and human activity are increasingly common, and new, more efficient, materials need
to be made to increase clean water supplies. To do this, fundamental information on the interaction
of water with ions at the atomic...
The continuing increase in atmospheric CO2 to concentrations exceeding 400 ppm has attracted considerable attention from both scientists and policymakers. Industrial fossil fuel consumption generates a significant amount of CO2 emissions, and in particular, energy-intensive molecular separations that require thermal processes, such as distillation, drying, or evaporation, are responsible for...
Despite the increasing interest in biogenic secondary organic aerosols (SOAs), their role in the climate system remains the greatest source of uncertainty in global models. Cloud formation, critical for the net cooling effect provided by cloud cover, is dependent on the abundance of SOA particles and their ability to activate...
Metalloenzymes catalyze remarkable reactions in Nature using transition metal ions. Common earth-abundant metals like copper, iron, zinc, and magnesium catalyze reactions that are the basis of life. These metal sites lend their chemistries to facilitate these reactions, making studying the structure and properties important in understanding the enzymes' abilities and...
Recent progress in semiconductor synthesis and photophysics has revealed a host of new materials with exciting properties for applications in optoelectronic devices such as sensors, photovoltaics, solid state lighting, and more. One of the most significant recent additions to the field is the class of hybrid and inorganic materials that...
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...
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...
Understanding the characteristics of interfaces between materials and solvent media such as structure, chemistry, and charge remains crucial to determining the properties and performance of numerous systems and technologies. This thesis focuses specifically on characterizing the interactions of water at oxide interfaces. A large collection of questions remains unanswered about...
Amyloid beta oligomers (AβOs) are a key instigator of neurodegeneration in Alzheimer’s disease (AD). The work presented in this thesis includes three disease-modifying approaches to disrupt pathological AβO-related mechanisms in AD: (1) inhibiting AβO buildup, (2) blocking AβO-induced tau phosphorylation, and (3) neutralizing AβOs. These three approaches were tested in...
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...
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...
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...
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...
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...
Amyloid beta oligomers (AβOs) are a key instigator of neurodegeneration in Alzheimer’s disease (AD). The work presented in this thesis includes three disease-modifying approaches to disrupt pathological AβO-related mechanisms in AD: (1) inhibiting AβO buildup, (2) blocking AβO-induced tau phosphorylation, and (3) neutralizing AβOs. These three approaches were tested in...
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...
DNA is extremely versatile and powerful, both as a construct in biological applications and as a ligand in materials design due to the fact that its recognition properties can be programmed through sequence and length. Spherical nucleic acids (SNAs), nanoparticles surrounded by a dense shell of DNA or RNA, are...
Wireless power strategies are critical to system level implementation of bio-integrated devices. To achieve mechanically robust, manufacturable systems, batteries are often integrated as an on-board power source to support sensing, wireless communication and signal conditioning. Unfortunately, most sources of battery power use hazardous and environmentally harmful materials, which frustrate incorporation...
Understanding the photophysical processes of organic materials is important for utilizing them as functional photonic materials. Typical photophysical processes include intersystem crossing, charge transfer (CT), symmetry-breaking charge separation (SB-CS), singlet fission (SF), etc. There are serval factors that can lead to different photophysical processes, such as the molecular energy levels,...
Industrial processes heavily rely on catalysts to control product selectivity and lower energy barriers required for chemical transformations. Catalysts are most commonly solid heterogeneous catalysts that facilitate separations from reaction mixtures and enhance recyclability. Heterogeneous catalysts used in industrial processes exhibit efficacious results, but in certain instances drawing structure-function relationships...
This thesis presents results on photophysics and spin dynamics of photoactive organic molecules that possess one unpaired electron spin in the ground state and two or three unpaired spins upon photoexcitation. The excited state dynamics of the systems were studied using transient optical absorption spectroscopies and non-Boltzmann population on the...
Understanding the mechanisms associated with chemical catalysis is vital for not only the rational improvement of their capabilities, but also for the advancement of the fundamental knowledge affiliated with the systems in question. These new insights can help predict new reactivities towards more challenging substrates which will allow for easier...
Carbon nanomaterials, such as graphene and graphene oxide, have outstanding mechanical strength, stiffness, and toughness that surpass those of materials currently used to build structures. However, these properties are limited to the nanoscale and have not yet been attained in macroscopic composites containing carbon nanomaterials. To integrate the mechanical properties...
Proteins are the nanoscale building blocks of life. Their sophisticated but well-defined architectures result in complex biological functions, including ones involved in metabolism, photosynthesis, transcription, translation, and immunity. To study and improve upon the natural functions of proteins, it is desirable to develop methodology for organizing proteins into targeted architectures....
Per- and polyfluoroalkyl substances (PFAS) are man-made compounds containing multiple carbon–fluorine bonds. The unique properties of this strong bond simultaneously make PFAS useful for a number of industrial and consumer applications, toxic to living organisms, and difficult to remediate. Because the pervasive pollution of water sources with PFAS occurs at...
Organic photovoltaics offer an opportunity to make solar cells more affordable and widely accessible using cheap, solution-processable light-absorbing layers. In order to realize new technologies, a fundamental understanding of organic chromophore photophysics is required to overcome efficiency limitations. Throughout this doctoral work, I investigated the kinetic and physical characteristics of...
The construction of new C–C bonds remains a central facet of organic chemistry due to its critical role in the synthesis of pharmaceutical compounds and organic materials. Mild and selective methodologies are often required for efficient formation of these bonds in natural product total synthesis, medicinal chemistry campaigns, and more....
Triplet excited state chemistry has enabled a range of important organic transformations by accessing reaction pathways inaccessible to photoredox chemistry. Such photoreactions are triggered by triplet photosensitizers, which absorb visible-light photons and transfer the energy to the substrate or to a co-catalyst through triplet-triplet energy transfer (TT EnT). The most...
As the interest in rational synthesis for solid-state materials accelerates, there is an urgent need to understand the design principles concealed within these reactions. In situ material synthesis provides such an avenue to not only uncover these assembling rules, but also for finding new materials even in seemingly familiar phase...
Biomedical imaging is an essential part of medicine that enables the non-invasive observation of biological phenomena. This, in turn, allows for more accurate and earlier diagnoses, monitoring of therapies, and even fundamental research into biological processes. Molecular imaging, a fast-growing subdiscipline of biomedical imaging, seeks to image biochemical processes at...
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...
Soft functional materials are fundamentally interesting from a chemistry standpoint and have exciting applications in robotics, chemical and biomolecule sensing, and biomedical engineering. In addition, soft materials are also useful in lithography, particularly cantilever-free scanning probe lithography (CFSPL). Because of their low modulus, biocompatibility, stimuli responsiveness, malleability, and other characteristics,...
Among the most valuable applications of organometallic chemistry is its implementation in the field of catalysis. Many industrial processes rely heavily on catalysis, employing organometallic complexes in the production of commodity chemicals, fine chemicals, materials, and even in the discovery and development of pharmaceuticals. Through decades of intense study, homogeneous...
In an era of personalized medicine, the clinical community has become increasingly focused on understanding diseases at the cellular and molecular level. Magnetic resonance imaging (MRI) is a powerful imaging modality for acquiring anatomical and functional information. However, it has limited applications in field of molecular imaging due to low...
Two-dimensional (2D) hybrid halide perovskites have been the response to their exciting but woefully unstable 3D counterparts. These 2D perovskites have been shown to have respectable stabilities as photovoltaic absorbers, yet they lag behind the 3D perovskites in terms of efficiency. With the need to catch up to the efficiencies...
The ubiquitous role of water in biochemical, electrochemical, and geochemical systems has driven scientific interest in studying the fundamental hydrogen-bonding interactions that water molecules exhibit in the presence of different materials.Specifically, we focus on the interactions characterizing water at the interface between two bulk media, as these are essential to...
This work examines important heterogeneous processes of organic molecules on surfaces, in the contexts of atmospheric and indoor environments. In large forest ecosystems, biogenic secondary organic aerosols (SOAs) constitute a dominant fraction of organic particulate matter in the atmosphere. The formation of SOAs starts from the emission of volatile organic...
The translation of proteins as effective intracellular drug candidates is limited by the challenge of cellular entry and their vulnerability to degradation. To advance their therapeutic potential, cell-impermeable proteins can be readily transformed into protein spherical nucleic acids (ProSNAs) or encapsulated into liposomal spherical nucleic acids (L-SNAs), structures defined by...
The use of light to understand detailed electronic structure and chemical properties of a molecule through light-matter interaction is fundamentally essential to design and analyze any chemical system. Over the past decades, rapid developments on optics and laser techniques improved the detection efficiency of multiphoton processes with more detailed chemical...
Proteins are known to have diverse biomedical functions and excellent catalytic performance; however, they are also fragile outside living cells, challenging their use in industrial applications. Metal-organic frameworks (MOFs) are highly porous crystalline materials that consist of metal cluster nodes and organic linkers. With their rigid structures, MOFs can effectively...
Noble metal nanoparticles (NPs) have shown promise as imaging agents, drug delivery platforms, and plasmonic sensors. Anisotropic gold NPs, such as gold nanostars, have particularly received attention due to their shape-dependent optical and spectral properties. With their 3D anisotropic structure with branches protruding into different directions and high surface areas,...
Recent progress in the field of nanomaterials has enabled significant advances in optoelectronic devices such as solar cells, light-emitting diodes, photocatalysts, and sensors. Nanoparticles feature superior optical and electronic properties that arise from quantum confinement and therefore cannot be attained used bulk materials. However, further developments in the field of...
Metallic conductivity and broken inversion symmetry were long thought to be contraindicated properties, under the assumption that long-range Coulombic interactions (screened by free charge carriers) were necessary for coordinated polar displacements. Within the past decade, the discovery of polar metals has prompted a rethinking of the relationship between metallicity and...