Physical Sciences and Mathematics Commons^™

Metallacycle-Mediated Cross-Coupling As An Enabling Tool For Studies In Carbocycle Synthesis And Functionalization, Adam Barry Millham

Dartmouth College Ph.D Dissertations

Natural products, specifically complex, carbocyclic natural products, have served as the inspiration for novel methods development for decades. Over that time, metallacycle-mediated cross-coupling has arisen as a powerful means for the synthesis of fused carbocycles. This work details three methods for the synthesis and functionalization of carbocyclic motifs that have been enabled by Ti-mediated cross-coupling reactions. The first of these studies include a complementary method to the Pauson–Khand reaction for the synthesis of highly substituted cyclopentenones via Ti-mediated alkyne–β-ketoester coupling. The second project, a modern approach to steroidal tetracycles, will be discussed that features: (1) an alkoxide-directed metallacycle-mediated [2+2+2] annulation …

Efforts Towards The Asymmetric De Novo Synthesis Of Lanostanes And Euphanes, Htoo Tint Wai

Dartmouth College Ph.D Dissertations

Tetracyclic triterpenoids are ubiquitous in nature and biology, with members displaying a wide range of medically relevant properties and occupying rather distinct regions of chemical space. Members of this large class include well-known steroid hormones and sterols as well as structurally interesting subclasses such as lanostanes and euphanes, among others. Comprised of the tetracyclic skeleton with three stereodefined quaternary centers at ring-junction positions, lanostanes and euphanes present synthetic challenges that are different from those encountered in efforts targeting the structurally less complex steroid hormones. Lanostanes, in particular, stand as a historically important class of compounds as significant attention has been …

Converting Hydrazone-Based Photoswitches Into Functional Materials, Sirun Yang

Dartmouth College Ph.D Dissertations

The development of new classes of molecular switches with enhanced performance and brand-new functionalities enables practitioners to push the frontiers of adaptive materials. In the realm of photoswitches, the bistability of hydrazones (i.e., molecules that incorporate the C=N-NH functional group) allows for the kinetic trapping of polymer and supramolecular assemblies resulting in multistate actuation and emergent phenomena that are not tractable with other photoswitches. This property has transformed hydrazone photoswitches into powerful tools that can be used in understanding fundamental molecular interactions and how to apply them in modulating the physicochemical properties of materials.

Progressing from disordered to …

On The Thom Isomorphism For Groupoid-Equivariant Representable K-Theory, Zachary J. Garvey

Dartmouth College Ph.D Dissertations

This thesis proves a general Thom Isomorphism in groupoid-equivariant KK-theory. Through formalizing a certain pushforward functor, we contextualize the Thom isomorphism to groupoid-equivariant representable K-theory with various support conditions. Additionally, we explicitly verify that a Thom class, determined by pullback of the Bott element via a generalized groupoid homomorphism, coincides with a Thom class defined via equivariant spinor bundles and Clifford multiplication. The tools developed in this thesis are then used to generalize a particularly interesting equivalence of two Thom isomorphisms on TX, for a Riemannian G-manifold X.

Space-Efficient Algorithms And Verification Schemes For Graph Streams, Prantar Ghosh

Dartmouth College Ph.D Dissertations

Structured data-sets are often easy to represent using graphs. The prevalence of massive data-sets in the modern world gives rise to big graphs such as web graphs, social networks, biological networks, and citation graphs. Most of these graphs keep growing continuously and pose two major challenges in their processing: (a) it is infeasible to store them entirely in the memory of a regular server, and (b) even if stored entirely, it is incredibly inefficient to reread the whole graph every time a new query appears. Thus, a natural approach for efficiently processing and analyzing such graphs is reading them as …

Cysteine Metallochemistry And Metal Binding: Quantification Of The Thermodynamic Foundations Of Cellular Homeostasis, Matthew R. Mehlenbacher

Dartmouth College Ph.D Dissertations

Metals are required for life. Many metalloproteins contain cysteine in their metal-binding site (MBS) and cysteines are unique in that they are reactive, and strongly bind certain metals, which aid in metal selectivity and specificity. Using isothermal titration calorimetry (ITC), the thermodynamic foundation for metal binding, cellular protection, and transcriptional regulation, which all utilize cysteines in their MBS, are quantified.

In bacteria there are metalloprotein pathways that actively uptake mercury, which are regulated by the metalloregulatory protein MerR. MerR de-represses the transcription of these mer proteins in a metal-dependent manner. Using ITC, the thermodynamic foundation of the negative allosteric coupling …

Information Provenance For Mobile Health Data, Taylor A. Hardin

Dartmouth College Ph.D Dissertations

Mobile health (mHealth) apps and devices are increasingly popular for health research, clinical treatment and personal wellness, as they offer the ability to continuously monitor aspects of individuals' health as they go about their everyday activities. Many believe that combining the data produced by these mHealth apps and devices may give healthcare-related service providers and researchers a more holistic view of an individual's health, increase the quality of service, and reduce operating costs. For such mHealth data to be considered useful though, data consumers need to be assured that the authenticity and the integrity of the data has remained intact---especially …

Approaching Quantum-Limited Electrometry In The Single-Photon Regime, Sisira Kanhirathingal

Dartmouth College Ph.D Dissertations

Mesoscopic quantum systems currently serve as essential building blocks in many quantum information and metrology devices. This thesis investigates the potential of quantum-limited detection in a mesoscopic electrometer named the cavity-embedded Cooper pair transistor (cCPT). As one application, this charge detector can act as the basis for an optomechanical system in the single-photon strong coupling regime. The realization of this scheme would entail near quantum-limited, ultra-sensitive electrometry at the single-photon level, the feasibility of which is studied at length in this thesis.

On the one hand, we approach this question using a fundamental, first-principles study, where an operator scattering model …

Protecting Systems From Exploits Using Language-Theoretic Security, Prashant Anantharaman

Dartmouth College Ph.D Dissertations

Any computer program processing input from the user or network must validate the input. Input-handling vulnerabilities occur in programs when the software component responsible for filtering malicious input---the parser---does not perform validation adequately. Consequently, parsers are among the most targeted components since they defend the rest of the program from malicious input. This thesis adopts the Language-Theoretic Security (LangSec) principle to understand what tools and research are needed to prevent exploits that target parsers. LangSec proposes specifying the syntactic structure of the input format as a formal grammar. We then build a recognizer for this formal grammar to validate any …

The Three-Way Interplay Among Early Life Exposures, The Gut Microbiome, And Outcomes In Infancy, Yuka Moroishi

Dartmouth College Ph.D Dissertations

The bidirectional relationship between the gut microbiome and immune system plays an important role in host immune status: the immune system provides the gut microbiome the optimal environment to thrive in, and the gut microbiome helps regulate the immune system. This relationship is especially important in infants, whose immune system is still premature and rely on innate immunity.

We investigated the three-way interplay among early-life exposures, the developing gut microbiome, and outcomes in infancy from the general population in New Hampshire, US. We used prospective cohort data from the New Hampshire Birth Cohort study to 1) determine whether timing of …

Correlations And Reuse For Fast And Accurate Physically Based Light Transport, Benedikt Bitterli

Dartmouth College Ph.D Dissertations

Light transport is the study of the transfer of light between emitters, surfaces, media and sensors. Fast simulations of light transport play a pivotal role in photo-realistic image synthesis, and find many applications today, including predictive manufacturing, machine learning, scientific visualization and the movie industry. In order to accurately reproduce the appearance of real scenes, light transport must closely approximate the physical laws governing the flow of light. Physically based rendering is a set of principles for codifying these laws into a mathematical model, and is the predominant rendering methodology today.

The representational power of this model is limited to …

The Cavity-Embedded Cooper Pair Transistor As A Charge Detector Operating In The Nonlinear Regime, Bhargava Thyagarajan

Dartmouth College Ph.D Dissertations

The cavity-embedded Cooper pair transistor (cCPT) has been shown to be a nearly quantum limited charge detector operating with only a single intracavity photon. Here, we use the inherent Kerr nonlinearity to demonstrate a dispersive charge sensing technique inspired by the Josephson bifurcation amplifier. Operating in the bistable regime close to a bifurcation edge, the cCPT is sensitive to charge shifts of 0.09e in a single-shot readout scheme with a detection time of 3 μs and a detection fidelity of 94%. The readout is implemented with only ∼ 25 intracavity photons in the high oscillation amplitude state, still several orders …

Aspects On The Quantum Dynamics Of A System Coupled To A Bosonic Environment, Qidong Xu

Dartmouth College Ph.D Dissertations

In this work we study various aspects of the quantum dynamics for a system coupled to a Bosonic environment, which is described by a collection of quantum harmonic oscillators or a quantum field. We first consider two quantum mechanical oscillator system-bath models obtained by dimensionally truncating linearized gravity coupled to a massive scalar field and scalar QED, and we show that they separately map onto the phase damped oscillator model and the oscillator system subject to two-photon damping. The phase damped oscillator model also corresponds to the optomechanical system with an acoustic field environment, and we study the acoustic environment …

Information Entropic Content Of Astrophysical Spectra: Applications To Cosmology And Astrobiology, Sara Vannah

Dartmouth College Ph.D Dissertations

Astrophysics faces two critical challenges: the difficulty of observing very distant targets and the difficulty of interpreting science in diverse and often extreme environments that have not been replicated on Earth. In this thesis, we discuss two types of spectra — one from early universe cosmology and one from astrobiology — where improvements in telescope technology are just ushering in a wave of precise observations, addressing the first challenge. This accelerates the need for a solution to the second challenge. Traditional methods for analyzing these two spectra rely heavily on unsettled science, biasing results to match the input assumptions. In …