Synthesis and Applications of One- and Two-Dimensional Polymer-Carbon Nanomaterial Composites

[摘要] This dissertation describes the synthesis of polymer and carbon nanomaterial composites and their applications in drug delivery, chemical sensing, and catalytic oxidative patterning. The first part studies polyethylene glycol functionalized oxidized single-walled carbon nanotubes (PLPEG/ox-SWCNT) as a drug nanocarrier to prolong the circulation of two mitochondria targeting radiomitigators TPP-IOA and XJB-5-131. In in vivo tests with mice exposed to a single total body irradiation of 9.25 Gy, the PL-PEG/ox-SWCNT nanocarrier prolongs the circulation ofTPP-IOA without developing apparent toxicity and exhibits radiation mitigating effects, slightly better than that of free TPP-IOA. The in vivo drug effect of the XJB-5-131 conjugate is inconclusive. The stability of Doxorubicin-loaded PL-PEG/ox-SWCNT is investigated under oxidative bursts that occur in neutrophils and macrophages. Myeloperoxidase-catalyzed and peroxynitrite-mediated oxidations of the drug conjugate are studied ex vivo, and the in vitro tests in B16 melanoma cells and tumor-activated myeloid cells are conducted. Both ex vivo and in vitro results indicate that the nanocarrier protects Doxorubicin from the oxidative degradation. The second part of the dissertation discusses the synthesis and applications of twodimensionalpolymers. A novel crystalline polybenzobisimidazole-based two-dimensional supramolecular polymer (2DSP-PBBI) is synthesized by condensation/precipitationpolymerization under solvothermal conditions. The surface morphology of 2DSP-PBBI is analyzed with electron and atomic force microscopy, revealing planar surfaces formed by hydrogen bonding. An iron(III)-coordinated porphyrin-based covalent organic framework (Fe-DhaTph-COF) is synthesized for the fabrication of oxidatively patterned graphite in the presence of H2O2 and/or NaOCl. The vertical channel created by patterning is ~3 nm in depth, and liquidexfoliation of the patterned graphite provides few-layer porous graphene. Although the shapeand size of the pores are not uniform, this study demonstrates that metallated COFs can beutilized as surface catalysts and master templates for patterning.

[发布机构] the University of Pittsburgh