Chemistry Commons^™

Polymer Mimetics For Soil Modeling And Detection Of Biomarkers, Md Ragib Hasan

LSU Doctoral Dissertations

The population of the world is increasing day by day and is expected to reach 9.8 billion by the year 2050. The ever-increasing demand for agricultural products is putting an unprecedented strain on the world's soils as the human population continues to expand. Soil degradation caused by over-farming and the agrochemicals (fertilizers, pesticides, etc.) used in agriculture is a growing problem, although its causes remain murky. In addition, little is understood about the molecular-level interactions of substances that are subsequently introduced to soils, such as agricultural chemicals (ACs). Therefore, it is expected that these constraints may be circumvented by the …

Synthesis Of Thiol-Acrylate Hydrogels For 3d Cell Culture And Microfluidic Applications, Anowar Hossain Khan

LSU Doctoral Dissertations

Globally cell culture is an $18.98 billion industry as of 2020, with an 11.6 percent annual growth rate. Drug discovery has an estimated worth of $69.8 billion in 2020 and is predicted to grow to $110.4 billion by 2025. Three-dimensional (3D) cell culture of cancer cells is one of the rapidly growing felids since it better recapitulates in vivo conditions compared to two-dimensional (2D) models. However, it is challenging to grow 3D tumor spheroids outside the body, and some of the existing technology can generate these spheroids outside the human body but poorly mimic in vivo tumor models. Therefore, there …

Kinetics, Characterization, And Applications In The Development Of Next-Generation Cure-On-Demand Polymeric Materials Through Frontal Polymerization, Daniel Paul Gary

LSU Doctoral Dissertations

Frontal polymerization (FP) is a process in which a front propagates in a localized reaction zone converting monomer into polymer. This work explored the kinetics and applications of FP for the development of cure-on-demand materials.

The kinetic effects of fillers on frontal polymerization have not been thoroughly explored. In Chapter 2, various fillers were used, and their effects on front velocity and front temperature were determined. Clay minerals are primarily used, but the thermal conductive effects of milled carbon fiber were also explored. It was found that some fillers inhibit frontal polymerization through radical scavenging, while others increased the front …

Characterization, Immobilization, And Polymer Related Applications Of Watermelon Seed Powder, A Practical Source Of Urease Enzyme, Anthony Quan Quoc Mai

LSU Doctoral Dissertations

Urease enzyme was crystallized almost a century ago, and to this day its intrinsic stability is not ideal for everyday applications. This work introduces a new process by which a naturally encapsulated material, watermelon seed powder (WMSP), is characterized for its stability and activity. WMSP enzymatic activity has been measured for over a year at various storage conditions—exposed to ambient atmosphere for a year, WMSP retained above 90% activity. In aqueous conditions, the enzyme maintained above 60% activity after two months; with the addition of a preservative that number stays at about 90%. There is a pH shift of the …

Development Of Engineered Soil Surrogates For Modeling Natural Soil Sorption Behavior, Ghada Yehia Abdalla

LSU Doctoral Dissertations

The land produces more than 95% of the global food supply, and with a continuously growing population, we need to optimize the use of the available agricultural land. Soil organic matter (SOM) is an essential component of soils, especially concerning their fertility and sorption behavior. The chemical composition of the SOM consists of lipids, lignin, and cellulose. However, the heterogeneous and complex nature of SOM, and real soils, makes their study challenging and introduces uncontrollable factors.

Therefore, structural mimics of natural soils with increasing complexity representing the real soil functionality were synthesized and evaluated for bulk properties related to their …

Structure And Dynamics Of Phospholipid Vesicles And The Dependence On Nanoscale Interactions With Molecules Of Varying Complexity, Lakshapathy Widanelage Judith Upeka De Mel

LSU Doctoral Dissertations

In this dissertation, molecular interactions and changes imposed by nano-scale structures on phospholipid vesicles were investigated. 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) large unilamellar vesicles (LUVs) were used as the model system. Understanding changes of the bilayer structure, interfacial properties, lipid dynamics, and self-assembly, allows bridging relationships between biological cell membrane structure and dynamics to cellular functionalities. For example, membrane curvature changes are linked to membrane protein functions, although the exact mechanisms of control are not yet understood. Moreover, the knowledge gained from vesicle models allows exploring novel strategies for drug delivery applications. To achieve this, DOPC LUVs were synthesized and characterized by a …

Synthesis And Investigation Of Amphiphilic Polypeptoids For Environmental And Biological Applications, Tianyi Yu

LSU Doctoral Dissertations

Polypeptoids are an emerging class of peptidomimetic polymers featuring N-substituted polyglycine backbones. Polypeptoids are cyto-compatible and backbone degradable, making them appealing to many biological applications. When the highly polar polyamide backbone is coupled with non-polar aliphatic side chains, polypeptoids can be considered as facial amphiphiles. Without extensive hydrogen bonding along the backbone, the conformation of polypeptoid is largely controlled by the N-substituent structures. The hydrophobicity-lipophilicity balance of polypeptoids can be readily tuned with the N-substituent structures as well as the molar ratio between the hydrophilic and hydrophobic segments in their copolymers. In view of these combined attributes, …

Influencing Factors On The Velocity And Temperature Of Propagating Fronts In Acrylate Composites, Samuel Morris Bynum

LSU Doctoral Dissertations

Thermal frontal polymerization is a type of polymerization in which a localized reaction zone propagates through an unstirred system. It is incumbent upon the production and transport of heat produced as a result of the exothermic reaction associated with free-radical polymerization. First discovered in the 1970s, frontal polymerization has been since utilized to produce a variety of different materials, utilizing a variety of different chemistries. The temperature of the propagating front and the velocity at which it propagates can be influenced via chemical or physical means. We show that through careful selection of monomers and control of the concentration of …

Modeling And Simulations Of Peptoids, Pu Du

LSU Doctoral Dissertations

Polypeptoids, or poly-N-substituted glycines, are a class of sequence defined polymers that are structural mimics of polypeptides. Polypeptoids currently have received a growing interest due to their improved thermal stability, larger chemical diversity, and easier synthetic pathways as compared to peptides. Their lack of backbone hydrogen bonding and stereochemistry coupled with their easily tunability make them an ideal prototypical model system to study the effect of secondary/non-covalent interactions on self-assembly in solution. In order to develop a molecular level understanding of the effect of secondary interactions on polypeptoid self-assembly, systematic studies were carried out using molecular dynamics simulations on several …

Hierarchical Conjugated Polymer Systems Prepared By Controlled Chain-Growth Polymerization, Chunwa Peter Kei

LSU Doctoral Dissertations

π-Conjugated polymer materials may have a significant economic impact on society by providing means for designing affordable, flexible, and portable organic electronic devices. Their successful commercialization will depend on major scientific advancements, which will challenge human society to seek out ever more detailed and fundamental processes to command. Controlled polymerization affords such a power; allowing for the design of meticulous and precisely defined systems granting detailed insight into structure-property relationships in the polymer materials and bettering understanding of novel physical phenomena.

This dissertation primarily focuses on development and preparation of well-defined hierarchically organized macromolecular systems. The novel chain-growth polymerization methodologies …

Sequence-Defined Ionic Peptoid Block Copolymers: Synthesis And Solution Self-Assembly, Garrett Leigh Sternhagen

LSU Doctoral Dissertations

This work covers efforts to develop a peptoid-based model system for systematically studying the role of ionic functional groups in determining the structure of ionic block copolymer (BCP) self-assemblies in water. A key challenge in the study of polyelectrolytes is the lack of synthetic control over the location of ionic monomers along a polymer chain. We developed a model system based on sequence-defined ionic peptoid BCPs having discrete chain length and precisely positioned ionic monomers along the chain to specifically address this issue. In Chapter 1, synthetic strategies to access well-defined polypeptoids and their application in BCP synthesis are reviewed. …

Free-Radical Polymerization Of Acid-Containing Deep Eutectic Solvents, Kylee Fazende

LSU Doctoral Dissertations

The forefront of this study explored polymerization, specifically thermally-initiated, free-radical frontal polymerization of (meth)acrylic acid monomers while the monomers acted as a hydrogen bond donor of a deep eutectic solvent. These frontal polymerizations were shown to exhibit unusual front velocities and, in some cases, lower front temperatures than the frontal polymerization of the neat monomers or systems containing inert analogs in the place of the hydrogen bond acceptor of these monomer-containing deep eutectic solvents. The frontal polymerization will occur with a range of initiator concentrations including ones that were too low for the pure monomer systems to sustain a front. …

Higher Energy Gap Control Of Fluorescence In Conjugated Polymers, Chien-Hung Chiang

LSU Doctoral Dissertations

Chemo- and biosensors based on fluorescent conjugated polymer benefit from greater detection sensitivity due to amplification of the electronic perturbations produced by analyte binding. This amplification stems from the exciton-transporting properties of conjugated polymers. A conventional design paradigm relies on the analyte binding events which generate sites of lower energy relative to the polymer energy: either fluorescence quenching sites (turn-off sensors) or bathochromically shifted fluorophores (turn-on sensors). In both type sensors, the excitons migrate to the lower-energy site created by analyte binding.

This dissertation primarily focused the investigation of an alternative paradigm when analyte binding creates higher energy gap sites …

Synthesis, Characterization, And Assessment Of Cationic Polypeptoids Toward Gene Delivery And Development Of Air Stable N-Substituted N-Thiocarboxyanhydrides, Jessica Michelle Simpson

LSU Doctoral Dissertations

Peptoids are a class of peptidomimetic polymers, which have attracted much attention over the years. Due to their structural similarity to peptides, this group of polymers affords good biocompatibility making them of interest for biomedical applications. This dissertation is largely about the design, synthesis, and characterization of cationic polypeptoids for biological applications, particularly nonviral gene delivery. The dissertation will also cover the development, characterization, and polymerization behavior of a new, air stable N-thiocarboxyanhydride (NTA) monomer.

Introducing functionality, such as small biomolecules and organic compounds can provide distinctive properties to the polymers. Chapter 1 introduces gene therapy and concepts pertinent …

Synthesis And Characterization Of Covalent Adaptable Networks Comprised Of Dynamic Imine And Aminal Covalent Bonds, Albert Chao

LSU Doctoral Dissertations

The dissertation is about the design, synthesis and characterization of materials comprised of covalent adaptable networks (CANs). There are three chapters within this dissertation.

Chapter 1 contains a short overview of conventional thermosets and thermoplastics. A new strategy of combining advantages from thermosets and thermoplastics is utilizing dynamic covalent chemistry (DCC) for material design. Dynamic covalent bonds are able to undergo dynamic exchange which allow the material to adapt to a new state when under stimuli such as stress or strain. Material comprised of such reversible networks is called covalent adaptable networks (CANs). These types of reversible covalent bonds followed …