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Design And Synthesis Of Stimuli-Responsive Polymeric Nanogels Towards Therapeutic Translation, Mallory R. Gordon 2018 University of Massachusetts Amherst

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 ...


Block-Copolymer Assisted Fabrication Of Anisotropic Plasmonic Nanostructures, Calbi J. Gunder 2018 Missouri State University

Block-Copolymer Assisted Fabrication Of Anisotropic Plasmonic Nanostructures, Calbi J. Gunder

MSU Graduate Theses

The anisotropic nanostructures of noble metals are of great interest for plasmonic applications due to the possibility of tuning the localized surface plasmon resonance (LSPR) across the UV-VIS-NIR without sacrificing the linewidth as well as to achieve larger local field enhancement. Here, we report a simple and promising fabrication method of anisotropic gold nanostructures film using polystyrene-b-2vinylpyridine (PS-b-P2VP) block copolymers (BCP) as a template. In this approach, PS-b-P2VP spherical micelles were first synthesized as a template followed by selective deposition of Au precursor inside P2VP core of the micelles using ethanol solution of Au salt. Subsequently, heat treatment of the ...


Biorenewable Polymer Thermoplastic Biocomposites, Mitchel M. Michel 2018 Iowa State University

Biorenewable Polymer Thermoplastic Biocomposites, Mitchel M. Michel

Graduate Theses and Dissertations

Biorenewable fillers have recently gained a greater focus in research to produce composites because of their unique properties, abundance, and diversity. These biorenewable fillers can include various terrestrial based plants naturally grown throughout the world. The focus of this work was on the natural fiber feedstocks that are created as waste streams from a wide range of industries, in particular agave fibers. Creating a composite composed of fibrous materials would have potential benefits that include cutting costs of composite products, decrease in density, increased strength and durability, and utilizing plant fiber waste streams for cost recovery. However, these natural fibers ...


Surface Functionalization Of Fabrics And Threads For Smart Textiles, Morgan Baima 2018 University of Massachusetts Amherst

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 ...


Investigating The Role Of Topological Frustration On Morphology Of Novel Multiblock Copolymers, Rohit Gupta 2018 University of Massachusetts Amherst

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 ...


Study Of The Effect Of Steric Bulk Of Side Chains On The Properties Of Conjugated Polymers, Bei Zhang 2018 University of Kentucky

Study Of The Effect Of Steric Bulk Of Side Chains On The Properties Of Conjugated Polymers, Bei Zhang

Theses and Dissertations--Chemistry

Donor-acceptor conjugated polymers opened a new era for conjugated polymer research due to the abundant selection and combination of different conjugated units. This class of polymers function as semiconductor materials with potential application in plastic consumer electronics. The frontier molecular orbital energies of the polymers are generally determined by the selection of donor and acceptor units in the backbone structure, and their substituents. The side chains attached to the backbone not only affect the solubility of the materials, but also their self-assembly and morphological characteristics, which indirectly govern optoelectronic properties. It is important therefore to consider backbone architectures and the ...


Nanocomposite Gel Study Of Surface-Initiated Block Copolymer By Ring-Opening Metathesis Polymerization And Lignin-Based Polymers Directly From Pyrolysis Lignin Via Raft Polymerization, Yuerui Huang 2018 Iowa State University

Nanocomposite Gel Study Of Surface-Initiated Block Copolymer By Ring-Opening Metathesis Polymerization And Lignin-Based Polymers Directly From Pyrolysis Lignin Via Raft Polymerization, Yuerui Huang

Graduate Theses and Dissertations

This thesis introduced two of my research projects: the nanocomposite gels study of surface-initiated block copolymer, and lignin based polymer that directly through pyrolysis lignin. The purpose for the nanocomposite gels study is finding the factors that will affect the gel formation. For the pyrolysis lignin polymerization study, the purpose is to use functionalized pyrolytic lignin directly though polymerization process to obtain lignin based polymer.

The nanocomposite gels study is based on the research results from Sri-Harsha Kalluru’s Ph. D work. Kalluru successfully synthesized the exfoliated block copolymer from norbornene and cyclopentene, which could form gel when mixed with ...


Glycerol-Based Polymers And Their Pathway To Industrial Relevance, Michael John Forrester 2018 Iowa State University

Glycerol-Based Polymers And Their Pathway To Industrial Relevance, Michael John Forrester

Graduate Theses and Dissertations

The work disclosed in this thesis is a discussion of the properties and implementation of glycerol-based materials with an emphasis on poly(acrylated glycerol). The first work discussed is the production and characterization of acrylated glycerol polymers. Because of the current abundance of glycerol, there is a large potential for materials and chemicals derived from glycerine. In this work we look at making and studying thermoplastic poly (glycerol-acrylate). In order to prevent these materials from rapidly producing thermosets, a type of polymerization chemistry known as reversible addition fragmentation chain transfer, or RAFT, is utilized. RAFT polymerization is a type of ...


Synthesis And Catalytic Testing Of A Proline Functionalized Amphiphilic Block Copolymer, Eric Firestone 2018 Eastern Michigan University

Synthesis And Catalytic Testing Of A Proline Functionalized Amphiphilic Block Copolymer, Eric Firestone

Master's Theses and Doctoral Dissertations

Catalysts are reagents used to reduce the amount of energy that a reaction needs to execute, allowing it to proceed at a higher rate while not being consumed. The use of catalyst functionalized amphiphilic copolymer allows easier recovery of the catalyst at the end of the synthesis and allows for the reaction. In water, under appropriate conditions, the amphiphilic block copolymers will form micelles and allow the reaction to occur on the interior of the micelle. The synthesis of amphiphilic copolymer with a hydrophobic O-methacryloyl-trans-4- hydroxy-L-proline and methyl methacrylate end and a hydrophilic acrylic acid end was characterized. The polymer ...


Light-Harvesting And Light-Responsive Materials For Optoelectronic And Biological Applications, youngju bae 2018 University of Massachusetts Amherst

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 ...


Film Stabilizaiton And Photophysics Of Unconventional Conjugated Polymers, Kara Martin 2018 University of Massachusetts Amherst

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 ...


Impact Of Chemical Doping On The Thermoelectric Charge Transport Of Organic Semiconductors, Connor J. Boyle 2018 University of Massachusetts Amherst

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 ...


Synthesis Of Novel Zwitterionic Polymers: From Functional Surfactants To Therapeutics, Matthew Skinner 2018 University of Massachusetts Amherst

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 ...


Polymeric Peptide Mimics For Protein Delivery, Coralie Backlund 2018 University of Massachusetts Amherst

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 ...


The Balance Between Dipole-Dipole Interactions And Steric Exclusion On Ordering In Cationic Polymers, Chinomso Nwosu 2018 University of Massachusetts Amherst

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 similar ...


Direct Measurement Of Rupture Force Of Single Triazole Molecule By Atomic Force Microscope And Solid Phase Synthesis Of Monodisperse Polyethylene Glycols, Ashok Khanal 2018 Michigan Technological University

Direct Measurement Of Rupture Force Of Single Triazole Molecule By Atomic Force Microscope And Solid Phase Synthesis Of Monodisperse Polyethylene Glycols, Ashok Khanal

Dissertations, Master's Theses and Master's Reports

This dissertation includes two topics, which are related to each other: (1) Rupture force measurement of single triazole molecule by atomic force microscope (AFM) and (2) Solid phase stepwise synthesis of polyethylene glycols (PEGs).

The reaction of an alkyne and an azide to form a 1,2,3- triazole has found wide applications. However, the stability of triazole under mechanical stress is unclear. We investigated the cycloreversion at the single molecular level using atomic force microscopy. A mica surface functionalized with a molecule containing a 1,2,3-triazole moiety in the middle and an activated ester at the end was ...


Preparation And Characterization Of Poly(Ethylene Oxide)(Mw 35k And 100k)/ Silica Nanoparticle Composites, Reem Alfinaikh 2017 Atlanta University Center

Preparation And Characterization Of Poly(Ethylene Oxide)(Mw 35k And 100k)/ Silica Nanoparticle Composites, Reem Alfinaikh

Electronic Theses & Dissertations Collection for Atlanta University & Clark Atlanta University

In recent years, polymer-inorganic nanoparticle compositions have been a subject of considerable interest in order to achieve desired chemical, physical properties and mechanical properties. In this study a polymer nanocomposites have been prepared by incorporating silica nanoparticles (~20 nm) as fillers into poly(ethylene oxide) matrix. The composites of poly(ethylene oxide) and silica nanoparticles were prepared by solution blending. The product composites were powders. The thermal properties of the composites were investigated using the Differential Scanning Calorimetry. The Nuclear Magnetic Resonance (13C solid state, T), Atomic Force Microscopy, X-ray diffraction and Fourier Transform Infrared Spectroscopy were used ...


Liquid Organic Electrolytes: Blends Of Low Molecular Weight Methoxyoligooxyethylene (Mpegs)/Litfsi Salt, Rasha Alshahrani 2017 Atlanta University Center

Liquid Organic Electrolytes: Blends Of Low Molecular Weight Methoxyoligooxyethylene (Mpegs)/Litfsi Salt, Rasha Alshahrani

Electronic Theses & Dissertations Collection for Atlanta University & Clark Atlanta University

Blends containing methoxyoligooxyethyleneglycol (MPEGs) (MW 350 and 550) and bis(trifluoromethane)sulfonimide lithium (LiTFSI) salt were prepared by solution blending process using tetrahydrofuran (THF) as a solvent. The ionic conductivity of the blends of different compositions were determined at four temperatures i.e. 25°C, 40°C, 60°C and 70°C. A maximum ionic conductivity value of 3.9x10-3 S cm-1 at 25°C was obtained for the blends containing MPEG-350 at an ethylene oxide to lithium salt ratio of 1:10. The ionic conductivity increases with increasing temperature and shows that the ion transport is aided ...


Construction And Evaluation Of Novel Molecularly Imprinted Polymers (Mips) Using Helical Poly(3-Methyl-4-Vinylpyridine), Fatmah Alshareef 2017 Atlanta University Center

Construction And Evaluation Of Novel Molecularly Imprinted Polymers (Mips) Using Helical Poly(3-Methyl-4-Vinylpyridine), Fatmah Alshareef

Electronic Theses & Dissertations Collection for Atlanta University & Clark Atlanta University

A novel chiral helical imprinted polymer (MIP) has been prepared by bulk copolymerization of 3-methyl-4-vinylpyridine and a crosslinker using chiral S-mandelic acid as template. The resulting MIPs after removing the template show optical activity that is derived from the presence of chiral helical structures of poly(3-methyl-4-vinylpyridine) (P3M4VP) embedded within the MIP matrix. The basic functional monomer 3-methyl-4-vinylpyridine (3M4VP) was utilized with the acidic template to ensure good interaction between the template and the polymer. Divinylbenzene (DVB) and ethyleneglycoldimethacrylate (EGDMA) with widely varying degree of rigidity, flexibility, and polarity were selected as crosslinking agents. Using two different crosslinkers, it was ...


Cellulose Nanofiber-Reinforced Impact Modified Polypropylene: Assessing Material Properties From Fused Layer Modeling And Injection Molding Processing, Jordan Elliott Sanders 2017 University of maine

Cellulose Nanofiber-Reinforced Impact Modified Polypropylene: Assessing Material Properties From Fused Layer Modeling And Injection Molding Processing, Jordan Elliott Sanders

Electronic Theses and Dissertations

The purpose of this research was to investigate the use of cellulose nanofibers (CNF) compounded into an impact modified polypropylene (IMPP) matrix. A IMPP was used because it shrinks less than a PP homopolymer during FLM processing. An assessment of material properties from fused layer modeling (FLM), an additive manufacturing (AM) method, and injection molding (IM) was conducted. Results showed that material property measurements in neat PP were statistically similar between IM and FLM for density, strain at yield and flexural stiffness. Additionally, PP plus the coupling agent maleic anhydride (MA) showed statistically similar results in comparison of IM and ...


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