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Full-Text Articles in Physical Sciences and Mathematics

Photothermal And Photochemical Strategies For Lightinduced Shape-Morphing Of Soft Materials, Alexa Simone Kuenstler Dec 2020

Photothermal And Photochemical Strategies For Lightinduced Shape-Morphing Of Soft Materials, Alexa Simone Kuenstler

Doctoral Dissertations

Engineering materials with the capability to transform energy from photons into mechanical work is an outstanding technical challenge with implications across myriad disciplines. Despite decades of work in this area, comprehensive understanding of how to prescribe shape change and work output in photoactive systems remains limited. To this end, this dissertation explores strategies to assemble photothermal and photochemical moieties in soft material systems to fabricate photoaddressable devices capable of specific shape changes upon illumination. Chapters 2 and 3 describe a methodology for spatially patterning plasmonic nanoparticles in liquid crystal elastomer fibers and sheets to specify local photothermally-induced strain profiles. Using …


Functionalized Materials From Atom Transfer Radical Processes, Sean Fischer Dec 2020

Functionalized Materials From Atom Transfer Radical Processes, Sean Fischer

Electronic Theses and Dissertations

This work is focused on the synthesis, characterization, and application of functionalized materials prepared from atom transfer radical processes. Atom transfer radical processes encompass both atom transfer radical addition (ATRA) and polymerization (ATRP) reactions, both of which are catalyzed by ppm amounts of copper complexes. The synthetic efforts of ATRA include increasing adduct selectivity through optimization of reaction conditions to generate small molecules in high to moderate yields. ATRA provides retention of the halogen moiety, which is an attractive functional group that can be further modified with other transformations. Specifically, the copper-catalyzed azide-alkyne [3+2] cycloaddition (CuAAC) allows for the realization …


Control Of Corrosion On Ss316l Using Surface Initiated Polymers, Alexander Rupprecht Dec 2020

Control Of Corrosion On Ss316l Using Surface Initiated Polymers, Alexander Rupprecht

Electronic Theses and Dissertations

Pitting corrosion is arguably one of the most destructive and dangerous forms of corrosion, resulting in damage to structures, the environment, and public health. In addition, damage caused to structures such as bridges, pipelines, and boats, corrosion also has a profound effect on the biomedical community. Implanted metallic devices (i.e., vascular stents and artificial joints) are prone to pitting corrosion caused by aggressive ions present in extracellular fluid. To provide a corrosion-resistant surface on SS316L, films of poly(styrene), poly(methyl acrylate), and poly(methyl methacrylate) were formed using surface-initiated atom transfer radical polymerization (SI-ATRP). The resulting hydrophobic polymer films had a fractional …


Transesterification Of Poly(Ethyl Glyoxylate): A Route To Structurally Diverse Polyglyoxylates, Rebecca E. Yardley, Amir Rabiee Kenaree, Xiaoli Liang, Elizabeth R. Gillies Oct 2020

Transesterification Of Poly(Ethyl Glyoxylate): A Route To Structurally Diverse Polyglyoxylates, Rebecca E. Yardley, Amir Rabiee Kenaree, Xiaoli Liang, Elizabeth R. Gillies

Chemistry Publications

Polyglyoxylates are a class of self-immolative polymers that depolymerize in solution and the solid state. The glyoxylic acid degradation product is a metabolite in the glyoxylate cycle and can also be processed in the liver in humans, making polyglyoxylates attractive for applications in the environment and in medicine. Although expanding the scope of available polyglyoxylates would enable new properties and applications, highly pure glyoxylate monomers are required for polymerization, and this level of purity is difficult to achieve for many potential monomers. To address this challenge, we report here the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed post-polymerization transesterification of poly(ethyl glyoxylate) (PEtG) as a …


Thermoresponsive Self-Immolative Polyglyoxylamides., Amir Rabiee Kenaree, Quinton E. A. Sirianni, Kyle Classen, Elizabeth R. Gillies Aug 2020

Thermoresponsive Self-Immolative Polyglyoxylamides., Amir Rabiee Kenaree, Quinton E. A. Sirianni, Kyle Classen, Elizabeth R. Gillies

Chemistry Publications

Thermoresponsive polymers with lower critical solution temperatures (LCSTs) are of significant interest for a wide range of applications from sensors to drug delivery vehicles. However, the most widely investigated LCST polymers have nondegradable backbones, limiting their applications


Phosphonium Versus Ammonium Compact Polyelectrolyte Complex Networks With Alginate-Comparing Their Properties And Cargo Encapsulation., Tristan D. Harrison, Alexandre J. Salmon, John R. De Bruyn, Paul J. Ragogna, Elizabeth R. Gillies Jul 2020

Phosphonium Versus Ammonium Compact Polyelectrolyte Complex Networks With Alginate-Comparing Their Properties And Cargo Encapsulation., Tristan D. Harrison, Alexandre J. Salmon, John R. De Bruyn, Paul J. Ragogna, Elizabeth R. Gillies

Chemistry Publications

Phosphonium and ammonium polymers can be combined with polyanions to form polyelectrolyte complex (PEC) networks, with potential application in self-healing materials and drug delivery vehicles. While various structures and compositions have been explored, to the best of our knowledge, analogous ammonium and phosphonium networks have not been directly compared to evaluate the effects of phosphorus versus nitrogen cations on the network properties. In this study, we prepared PECs from sodium alginate and poly[triethyl(4-vinylbenzyl)phosphonium chloride], poly[triethyl(4-vinylbenzyl)ammonium chloride], poly[tri(


Uniform Dispersion Of Nanoparticles In Pmma Waveguides For Luminescent Solar Concentrators, Daniel Korus May 2020

Uniform Dispersion Of Nanoparticles In Pmma Waveguides For Luminescent Solar Concentrators, Daniel Korus

Scholars Week

With the rise of emissions-related climate change, novel renewable energy sources must be realized. At the same time, evolution of the electric distribution grid away from traditionally large, centralized producers toward smaller, decentralized sources drives the need for next generation technologies that can be more readily integrated into the built environment. Nanocrystal (NC)-doped luminescent solar concentrators (LSCs) are waveguides that absorb diffuse and direct broadband sunlight across their surface and direct narrow-bandwidth, high-brightness light to their edges, for conversion into electricity by coupled, bandgap-matched, photovoltaic (PV) cells. LSCs are insensitive to incident light orientation, partial shading, and can be integrated …


Discriminating Azo Dyes: Conjugated Polymers, The Inner Filter Effect, And Array Sensors, Erin Crater May 2020

Discriminating Azo Dyes: Conjugated Polymers, The Inner Filter Effect, And Array Sensors, Erin Crater

Honors Theses

Azo dyes are abundant pollutants that contaminate water supplies and threaten humans, biota, and ecosystem health. Their detection and discrimination are an incredible challenge due to the structural, chemical, and optical similarities between dyes, the complexity of the wastewater environment in which they are found, and their low environmental concentrations. In this work, the inner filter effect (IFE), combined with conjugated polymer array-based sensing, is utilized for the quantitative profiling of these pollutants. The array was constructed using three fluorescent, anionic conjugated polyelectrolytes whose varying spectroscopic properties led to distinct IFE patterns in the presence of the dyes. The unique …


Polymers For Extrusion‐Based 3d Printing Of Pharmaceuticals: A Holistic Materials–Process Perspective, Mohammad A. Azad, Deborah Olawuni, Georgia Kimbell, Abu Zayed Badruddoza, Md. Shahadat Hossain, Tasnim Sultana Feb 2020

Polymers For Extrusion‐Based 3d Printing Of Pharmaceuticals: A Holistic Materials–Process Perspective, Mohammad A. Azad, Deborah Olawuni, Georgia Kimbell, Abu Zayed Badruddoza, Md. Shahadat Hossain, Tasnim Sultana

Publications and Research

Three dimensional (3D) printing as an advanced manufacturing technology is progressing to be established in the pharmaceutical industry to overcome the traditional manufacturing regime of ʹone size fits for allʹ. Using 3D printing, it is possible to design and develop complex dosage forms that can be suitable for tuning drug release. Polymers are the key materials that are necessary for 3D printing. Among all 3D printing processes, extrusion‐based (both fused deposition modeling (FDM) and pressure‐assisted microsyringe (PAM)) 3D printing is well researched for pharmaceutical manufacturing. It is important to understand which polymers are suitable for extrusion‐based 3D printing of pharmaceuticals …


Polyacrylamide In Glycerol Solutions From An Atomistic Perspective Of The Energetics, Structure, And Dynamics, Scott D. Hopkins, Gideon K. Gogovi, Eric Weisel, Robert A. Handler, Estela Blaisten-Barojas Jan 2020

Polyacrylamide In Glycerol Solutions From An Atomistic Perspective Of The Energetics, Structure, And Dynamics, Scott D. Hopkins, Gideon K. Gogovi, Eric Weisel, Robert A. Handler, Estela Blaisten-Barojas

VMASC Publications

All-atom molecular dynamics is used to investigate the structural, energetic, and dynamical properties of polyacrylamide (PAM) oligomers of different lengths solvated in pure glycerol, a 90:10 glycerol–water mixture, and pure water. We predict that the oligomers’ globular structure is obtained only when the modeling strategy considers the solvent as a continuous background. Meanwhile, for all-atom modeled solvents, the glycerol solutions display a strong tendency of trapping the oligomers in instantaneous elongated random coiled structures that remain locked-in over tens of nanoseconds. In pure water, the oligomers acquire considerably shorter random coiled structures of increased flexibility. The all-atom force field, generalized …


Preparation And Characterization Of Light Sensitive Tetrafluoro-Lambda6-Sulfanyl-Containing Polymers, Kelly A. Bonetti Jan 2020

Preparation And Characterization Of Light Sensitive Tetrafluoro-Lambda6-Sulfanyl-Containing Polymers, Kelly A. Bonetti

Legacy Theses & Dissertations (2009 - 2024)

The addition of the pentafluorosulfanyl (SF5) group to an unsaturated organic starting material became popular in the 1960s, following the widening commercial availability of SF5Cl and SF5Br. However, the free radical reaction conditions required limited a broader appreciation of this critical advance. Moreover, while important thermal, photochemical and free-radical initiated addition reactions were reported, the unique photosensitivity of these compounds was not well understood. In 2012, a scalable synthetic route was developed affording aryl-SF5-containing derivatives via a novel aryl-SF4Cl intermediate. As a result, a heightened interest in hypervalent fluorinated sulfur containing materials was renewed. In 2014, the visible light addition …


Synthesis Of Bio-Based Polymer Products, Joshua Sukie Jan 2020

Synthesis Of Bio-Based Polymer Products, Joshua Sukie

Williams Honors College, Honors Research Projects

The project covers the synthesis of two bio-based polymers. One aspect of the research investigates the synthesis of materials for use in vegetable oil-based UV-curable coating, and the subsequent polymerization of the materials into a coating film. The second aspect of the research follows the synthesis of a functionalized cellulose material for use as a reinforcer in a vegetable oil-based composite. Both products are subsequently analyzed by various methods.