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Full-Text Articles in Chemistry

Film Stabilizaiton And Photophysics Of Unconventional Conjugated Polymers, Kara Martin Nov 2018

Film Stabilizaiton And Photophysics Of Unconventional Conjugated Polymers, Kara Martin

Doctoral Dissertations

Conjugated polymers offer a unique opportunity to develop high performing, flexible, lightweight, and large area electronic devices. With advances in conjugated polymer understanding and synthesis, the use of polymers as active layer materials in electronic applications, rather than just substrate materials, has become more promising. However, defects in morphological stability, as well as imperfect electronic understanding, are still present, limiting the use of these materials in commercializable electronics. Fundamental understanding of structure-property relationships can allow for facile synthetic solutions to major drawbacks of conjugated polymer integration in standard device architectures. Chapter 1 presents background research on the history of conjugated …


Investigating The Role Of Topological Frustration On Morphology Of Novel Multiblock Copolymers, Rohit Gupta Nov 2018

Investigating The Role Of Topological Frustration On Morphology Of Novel Multiblock Copolymers, Rohit Gupta

Doctoral Dissertations

Multiblock copolymers have gained considerable attention due to their ability to offer immense potential for designing soft materials with complex architectures for diverse applications. The enlarged parameter space offered by these multiblock copolymers gives access to a wide variety of multiply continuous morphologies which can be used to produce highly ordered nanostructures. The investigation on multiblock copolymers has been subjected to two critical limitations: (i) A suitable synthetic strategy for accessing these structures and (ii) computational tools which can help in application driven design of these molecules. In this dissertation, the goal was to develop methodologies for the synthesis of …


Impact Of Chemical Doping On The Thermoelectric Charge Transport Of Organic Semiconductors, Connor J. Boyle Nov 2018

Impact Of Chemical Doping On The Thermoelectric Charge Transport Of Organic Semiconductors, Connor J. Boyle

Doctoral Dissertations

The thermoelectric properties of organic semiconductors allow them to directly convert heat into electricity without the use of moving parts and to directly convert electricity into heat without the use of working fluids. These properties offer opportunities for the generation of electricity from non-conventional or renewable sources of heat and for refrigeration without the risk of leaking harmful working fluids at any length scale down to the nanoscale. Since organic materials are lightweight, flexible, and made from abundant resources, these opportunities could one day become affordable for widespread use and could be expanded to include specialized and otherwise difficult to …


The Balance Between Dipole-Dipole Interactions And Steric Exclusion On Ordering In Cationic Polymers, Chinomso Nwosu Oct 2018

The Balance Between Dipole-Dipole Interactions And Steric Exclusion On Ordering In Cationic Polymers, Chinomso Nwosu

Doctoral Dissertations

Structure-property correlations in charged polymers is an interesting facet of polymer science. Understanding the effects of intermolecular forces on the morphologies of polymers can lead to the design of membranes with desired structures to improve properties, for example ion conductivity. In random, comb-shaped polycations, competing intermolecular forces result in two different short-range orderings. Side-chain steric repulsion results in backbone-backbone morphology characterized by periodic spacing between polymer backbones. However, dipole - dipole attraction in these polycations can facilitate the formation of ionomer cluster morphology characterized by a spacing between clustered dipoles. Although both of these short-range orderings have disparate origins, their …


Surface Functionalization Of Fabrics And Threads For Smart Textiles, Morgan Baima Oct 2018

Surface Functionalization Of Fabrics And Threads For Smart Textiles, Morgan Baima

Doctoral Dissertations

The future of electronics is moving toward wearable devices and therefore requires a shift away from hard, inflexible materials towards fibers, threads, and fabrics that conform to the shape of the body. Therefore new methods for incorporating textiles as electronic components are needed to replace conventional processing techniques used with smooth, flat substrates like glass, silicon, and many polymers. Toward this end, this work investigates different methods that can be used to tune textile surfaces for electronic functionality, including weaving, solution grafting, and initiated chemical vapor deposition (iCVD). While all of these methods were used to make triboelectrically-active textiles, iCVD …


Polymeric Peptide Mimics For Protein Delivery, Coralie Backlund Jul 2018

Polymeric Peptide Mimics For Protein Delivery, Coralie Backlund

Doctoral Dissertations

The plasma membrane is a major obstacle in the development and use of biomacromolecules for intracellular applications. Consequently, proteins with intracellular targets represent an enormous, yet under studied avenue for therapeutics. Extended research has aimed at facilitating intracellular delivery of exogenous proteins using protein transduction domains (PTDs), which allow transport of bioactive molecules into cells. Synthetic polymers, inspired by PTDs, provide a well-controlled platform to vary molecular architecture for structure activity relationship studies. Specifically, this thesis focuses on the use of ring-opening metathesis, a facile and efficient polymerization technique, through which we can vary structural parameters to optimize delivery of …


Synthesis Of Novel Zwitterionic Polymers: From Functional Surfactants To Therapeutics, Matthew Skinner Mar 2018

Synthesis Of Novel Zwitterionic Polymers: From Functional Surfactants To Therapeutics, Matthew Skinner

Doctoral Dissertations

This dissertation describes the synthesis, characterization, and investigation of novel zwitterionic polymers containing phosphorylcholine (PC), sulfobetaine (SB), and functional choline phosphate (CP) zwitterions for use as surfactants, self-assembled nanomaterials, and therapeutics. Facile, reproducible, and modular chemistries were utilized for incorporating zwitterions into a range of polymer backbones, and strategies were developed for overcoming difficult challenges encountered in zwitterionic polymer synthesis, especially related to the varying solubility of zwitterions, hydrophobic polymers, and functional comonomers. Synthetic strategies utilized in this work give access to well-defined materials with narrow molecular weight distributions, tunable compositions and architectures, and versatile chemical functionality. Chapter 2 describes …


Design And Synthesis Of Stimuli-Responsive Polymeric Nanogels Towards Therapeutic Translation, Mallory R. Gordon Mar 2018

Design And Synthesis Of Stimuli-Responsive Polymeric Nanogels Towards Therapeutic Translation, Mallory R. Gordon

Doctoral Dissertations

In the application of delivery of therapeutics, nanostructures of various composition have been employed due to their capacity to act as a host for lipophilic payloads. Advances in the synthetic preparation, size, morphology, and chemical or physical characteristics of polymers have impacted their development and versatility. A detailed understanding of polymeric nanoparticle host-guest properties is crucial to their practical translation to specific delivery applications. Further, these features must be highly tailorable to overcome biological barriers, stably encapsulate their therapeutic contexts, and exhibit payload release selectively in the target environment. In this dissertation, we aim to rationally design polymeric nano-scale assemblies …


Molecular Design, Characterization, And Implementation Of Organic Semiconducting Oligothiophenes, Benjamin Cherniawski Mar 2018

Molecular Design, Characterization, And Implementation Of Organic Semiconducting Oligothiophenes, Benjamin Cherniawski

Doctoral Dissertations

This work describes new self-assembly strategies and realizes new directions for rational side chain design in organic semiconductors. I examined the synthesis and structure property relations of monomers and dimers of a benchmark organic semiconductor system using a variety of linear alkyl side chains. I observed critical onsets for packing trends based on alkyl side chain length in both monomers and dimers. Monomer systems exhibited a pronounced even-odd effect manifesting directly from side chain length. In the dimer systems, I observed spontaneous bimolecular crystal formation with PC61BM which undergoes an order-to-disorder transition at small side chain lengths. Combining …


Light-Harvesting And Light-Responsive Materials For Optoelectronic And Biological Applications, Youngju Bae Mar 2018

Light-Harvesting And Light-Responsive Materials For Optoelectronic And Biological Applications, Youngju Bae

Doctoral Dissertations

In photodynamic therapy, several critical standards are required of photosensitizers including high singlet oxygen quantum yield, biocompatibility in dark, and long term photochemical stability. In addition, current PDT systems lack active targeting strategies to tumor cells, and instead mainly rely on the natural distribution of PS in the body following injection and application of near-infrared light treatment in the tumor region. This thesis describes a series of BODIPY-based molecules that were designed, synthesized and studied as photosensitizers with high singlet oxygen generation capacity through utilizing the heavy atom effect. Additionally, aqueous solubility and active targeting capability were introduced by photosensitizer …