Intramolecular conflict : conformation and self-assembly of architecturally complex macromolecules in solution

The solution behavior of linear polymer chains is well understood, having been the subject of intense study throughout the previous century. As plastics have become ubiquitous in everyday life, polymer science has grown into a major field of study. The conformation of a polymer in solution depends on the molecular architecture and its interactions with the surroundings. Developments in synthetic techniques have led to the creation of precision-tailored polymeric materials with varied topologies and functionalities. In order to design materials with the desired properties, it is imperative to understand the relationships between polymer architecture and their conformation and behavior. To meet that need, this thesis investigates the conformation and self-assembly of three architecturally complex macromolecular systems with rich and varied behaviors driven by the resolution of intramolecular conflicts. First we describe the development of a robust and facile synthetic approach to reproducible bottlebrush polymers (Chapter 2). The method was used to produce homologous series of bottlebrush polymers with polynorbornene backbones, which revealed the effect of side-chain and backbone length on the overall conformation in both good and theta solvent conditions (Chapter 3). The side-chain conformation was obtained from a series of SANS experiments and determined to be indistinguishable from the behavior of free linear polymer chains. Using deuterium-labeled bottlebrushes, we were able for the first time to directly observe the backbone conformation of a bottlebrush polymer which showed self-avoiding walk behavior. Secondly, a series of SANS experiments was conducted on a homologous series of Side Group Liquid Crystalline Polymers (SGLCPs) in a perdeuterated small molecule liquid crystal (5CB). Monodomain, aligned, dilute samples of SGLCP-b-PS block copolymers were seen to self-assemble into complex micellar structures with mutually orthogonally oriented anisotropies at different length scales (Chapter 4). Finally, we present the results from the first scattering experiments on a set of fuel-soluble, associating telechelic polymers. We observed the formation of supramolecular aggregates in dilute (≤0.5wt%) solutions of telechelic polymers and determined that the choice of solvent has a significant effect on the strength of association and the size of the supramolecules (Chapter 5). A method was developed for the direct estimation of supramolecular aggregation number from SANS data. The insight into structure-property relationships obtained from this work will enable the more targeted development of these molecular architectures for their respective applications.

Radio-aware service-level scheduling to minimize downlink traffic delay through Mobile Edge Computing

One of the most challenging problems in mobile broadband networks is how to assign the available radio resources among the different mobile users. Traditionally, research proposals are either speci c to some type of traffic or deal with computationally intensive algorithms aimed at optimizing the delivery of general purpose traffic. Consequently, commercial networks do not incorporate these mechanisms due to the limited hardware resources at the mobile edge. Emerging 5G architectures introduce cloud computing principles to add flexible computational resources to Radio Access Networks. This paper makes use of the Mobile Edge Computing concepts to introduce a new element, denoted as Mobile Edge Scheduler, aimed at minimizing the mean delay of general traffic flows in the LTE downlink. This element runs close to the eNodeB element and implements a novel flow-aware and channel-aware scheduling policy in order to accommodate the transmissions to the available channel quality of end users.

Charles Henry Gilbert (1859-1928), Naturalist-in-Charge, and Chauncey Thomas, Jr. (1850-1919), Commanding: Conflict Aboard the U. S. Fish Commission Steamer Albatross in 1902

Charles Henry Gilbert (1859-1928) was a pioneering ichthyologist who made major contributions to the study of fishes of the American West. As chairman of the Department ofZoology at Leland Stanford Junior University in Palo Alto, Calif., during 1891-1925, Gilbert was extremely devoted to his work and showed little patience with those ofa different mindset. While serving as Naturalist-in-Charge of the U.S. Fish Commission Steamer Albatross during her exploratory expedition to the Hawaiian Islands in 1902, Gilbert engaged in an acrimonious feud with the ship's captain, Chauncey Thomas, Jr. (1850-1919), U.S.N., over what Gilbert perceived to be an inadequate effort by the captain. This essay focuses on the conflict between two strong figures, each operatingf rom different world views, and each vying for authority. Despite the difficulties these two men faced, the voyage of the Albatross in 1902 must be considered a success, as reflected by the extensive biological samples collected, the many new species of animals discovered, and the resulting publication of important scientific papers.