The preparation of ring‐banded spherulites in poly(3‐butylthiophene) via controlled solvent evaporation of solution‐cast films is reported. The spherulites display unusual concentric ring‐banded structures under both polarized and unpolarized lights. The size of the ring‐banded spherulites is 300 ± 100 µm in diameter and the periodicity of the bands is 15 ± 2 µm. The periodic bands of the spherulite consist of alternating ridge and valley surface patterns and the crystalline lamellae in the bands are more or less parallel to the radial growth direction of the spherulites. Local lamellar bending and branching are observed analogous to that of classical non‐conjugated polymers. A possible diffusion‐induced rhythmic growth mechanism is proposed to interpret the formation of periodic banding of the spherulite.
The DNA base excision repair (BER) glycosylase MUTYH prevents DNA mutations by catalyzing adenine (A) excision from inappropriately formed 8-oxoguanine (8-oxoG):A mismatches. The importance of this mutation suppression activity in tumor suppressor genes is underscored by the association of inherited variants of MUTYH with colorectal polyposis in a hereditary colorectal cancer syndrome known as MUTYH-associated polyposis, or MAP. Many of the MAP variants encompass amino acid changes that occur at positions surrounding the two-metal cofactor-binding sites of MUTYH. One of these cofactors, found in nearly all MUTYH orthologs, is a [4Fe-4S] cluster coordinated by four Cys residues located in the N-terminal catalytic domain. We recently uncovered a second functionally relevant metal cofactor site present only in higher eukaryotic MUTYH orthologs: a Zn ion coordinated by three Cys residues located within the extended interdomain connector (IDC) region of MUTYH that connects the N-terminal adenine excision and C-terminal 8-oxoG recognition domains. In this work, we identified a candidate for the fourth Zn coordinating ligand using a combination of bioinformatics and computational modeling. In addition, using in vitro enzyme activity assays, fluorescence polarization DNA binding assays, circular dichroism spectroscopy, and cell-based rifampicin resistance assays, the functional impact of reduced Zn chelation was evaluated. Taken together, these results illustrate the critical role that the "Zn linchpin motif" plays in MUTYH repair activity by providing for proper engagement of the functional domains on the 8-oxoG:A mismatch required for base excision catalysis. The functional importance of the Zn linchpin also suggests that adjacent MAP variants or exposure to environmental chemicals may compromise Zn coordination, and ability of MUTYH to prevent disease.
The directed assembly of conjugated polymers into macroscopic organization with controlled orientation and placement is pivotal in improving device performance. Here, the supramolecular assembly of oriented spherulitic crystals of poly(3‐butylthiophene) surrounding a single carbon nanotube fiber under controlled solvent evaporation of solution‐cast films is reported. Oriented lamellar structures nucleate on the surface of the nanotube fiber in the form of a transcrystalline interphase. The factors influencing the formation of transcrystals are investigated in terms of chemical structure, crystallization temperature, and time. Dynamic process measurements exhibit the linear growth of transcrystals with time. Microstructural analysis of transcrystals reveals individual lamellar organization and crystal polymorphism. The form II modification occurs at low temperatures, while both form I and form II modifications coexist at high temperatures. A possible model is presented to interpret transcrystallization and polymorphism.
Piezoelectric nanogenerators (PNGs) are a new class of energy harvesting materials that show potential as a direct energy source for low powered electronics. Recently, piezoelectric polymers have been utilized for PNG technology due to low toxicity, high flexibility, and facile solution processing which provide manufacturing opportunities such as screen printing. Throughout the last decade, countless projects have focused on how to enhance the energy harvesting capabilities of these PNGs through the incorporation of nanoparticle fillers, which have been reported to enhance the piezoelectric properties of the film either directly through their intrinsic piezoelectric properties or through acting as surfaces for the interfacial nucleation of piezoelectric polymer crystals. Herein, two systems of PNGs formed from piezoelectric copolymers poly(vinylidene fluoride-co-hexafluropropylene) or poly(vinylidene fluoride-co-trifluoroethylene) mixed with high aspect ratio zinc oxide nanowires, hydroxyl functionalized multi-walled carbon nanotubes, or carboxylic acid functionalized single walled carbon nanotubes were investigated. Variations of filler type and loading are tested to determine influences on film morphology and piezoelectric properties. Power harvesting tests are conducted to directly determine the effect of nanoparticle addition on the output power of the non-poled devices. Both copolymer systems are found to exhibit a non-linear increase in output power with the increase of nanoparticle filler loading. The crystal polymorph properties of both systems are investigated by Fourier transform infrared spectroscopy. The microstructure of the poly(vinylidene fluoride-co-trifluoroethylene) films are further examined using X-ray diffraction, differential scanning calorimetry, polarized optical microscopy, and atomic force microscopy to determine the mechanism behind the increased power harvesting capabilities. As well, explanations for perceived output power from "self-poled" films are briefly explored. v ACKNOWLEDGMENTS I would like to thank Dr. Thomas Yong-Jin Han at Lawrence Livermore National Laboratory for his mentorship throughout my research project. With his support I learned a great amount about project management and the importance of being a critically thinking researcher. I would like to thank the members of my project team and the Functional Materials Synthesis and Integration group for help with planning, running experiments, and providing feedback for my project. A special thanks to Logan Bekker for training, Caitlyn Cook for project guidance, Tim Yee for SEM, and James Cahill for XRD testing. To have the opportunity to work alongside my peers at the lab has been a truly humbling and inspiring experience.
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