Browsing by Author "Badami, Anand Shreyans"
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- Bioresorbable Electrospun Tissue Scaffolds of Poly(ethylene glycol-b-lactide) Copolymers for Bone Tissue EngineeringBadami, Anand Shreyans (Virginia Tech, 2004-10-01)Poly(α-hydroxy esters) are a class of biocompatible resorbable polyesters including poly(lactic acid) (PLA) and poly(glycolic acid) (PGA) that are FDA-approved for clinical use. Preliminary tissue culture studies have demonstrated that these poly(α-hydroxy esters) support bone tissue development both in vitro and in vivo, but biocompatibility issues still exist. Tissue scaffolds fabricated from these materials by current methods have biocompatibility limitations because they are chemically and topographically inert to cells. The chemical composition of these scaffolds does not influence cell behavior (i.e. proliferation, differentiation) and their surface topography is on a scale length larger than a cell, which is too large to affect cell adhesion or orientation. It is hypothesized that poly(α-hydroxy ester) tissue scaffolds can be made more bioactive by (1) incorporating poly(ethylene glycol) (PEG) into the polymer interface to promote osteoblastic differentiation and (2) controlling topography to direct cell behavior. The novel processing technique of electrospinning allows the fabrication of nanofiber scaffolds with topographical features the size of focal adhesion contacts capable of influencing cell behavior. Thus, the overall objective of this research project is to characterize electrospun PEG-PLA diblock copolymers as substrates for bone tissue engineering. To accomplish this, PEG-PLLA and PEG-PDLLA diblock copolymers were synthesized with target molecular weights of 42,000 g/mol (PEG:2000, PLLA or PDLLA:40,000). Next, these two polymers and commercially available PLLA and PDLLA were electrospun to form scaffolds with fibers of diameters 0.14 to 2.1 μm. Finally, cell culture studies were performed to characterize cell morphology, proliferation, and osteoblastic differentiation. Results indicate electrospun fiber scaffolds limit cell spreading and persist in cell culture for two weeks. Analysis of cells cultured over 14 days revealed that there were no differences in cell density between polymers with and without PEG. Cell density increased with fiber diameter, indicating that fiber diameter affects cell adhesion and proliferation and suggesting that cells may migrate into scaffolds with large diameter fibers. In contrast to cell density, ALP activity, an indicator of osteoblastic differentiation, was unaffected by fiber diameter.
- Morphological and Structure-Property Analyses of Poly(arylene ether sulfone)-Based Random and Multiblock Copolymers for Fuel CellsBadami, Anand Shreyans (Virginia Tech, 2007-10-15)The commercialization of proton exchange membrane (PEM) fuel cells depends largely upon the development of PEMs whose properties are enhanced over current perfluorinated sulfonic acid PEMs. Understanding how a PEM's molecular weight and morphology affect its relevant performance properties is essential to this effort. Changes in molecular weight were found to have little effect on the phase separated morphologies, water uptake, and proton conductivities of random copolymers. Changes in block length, however, have a pronounced effect on multiblock copolymers, affecting surface and bulk morphologies, water uptake, proton conductivity, and hydrolytic stability, suggesting that multiblock copolymer PEM properties may be optimized by changes in morphology. A major goal of current proton exchange membrane fuel cell research involves developing high temperature membranes that can operate at ~120 °C and low humidites. Multiblock copolymers synthesized from 100% disulfonated poly(arylene ether sulfone) (BPSH100) and naphthalene polyimide (PI) oligomers may be an alternative. At block lengths of ~15 kg/mol they displayed no morphological changes up to 120 °C or even higher. Water desorption was observed to decrease with increasing block length. The copolymers exhibited little to no water loss during a 200 °C isotherm in contrast to random BPSH copolymers and Nafion. A BPSH100-PI multiblock copolymer with large block length appears to have morphological stability and retain water at temperatures exceeding 120 °C, suggesting its candidacy as a high temperature PEM. A growing number of alternative PEM research efforts involve multiblock copolymer chemistries, but little emphasis is placed on the methods used to couple the oligomers. Fluorinated linkage groups can help increase block efficiency during coupling, but their effect on a PEM is not well-known. The choice of linkage type, hexafluorobenzene (HFB) vs. decafluorobiphenyl (DFBP), appears to have small but observable influences on multiblock copolymers with disulfonated and unsulfonated poly(arylene ether sulfone) oligomers. DFBP linkages promote greater phase separation than HFB linkages, resulting in increased stiffness, decreased ductility, and increased proton conductivity at low humidities. DFBP linkages also promote more surface enrichment of fluorine, causing changes in surface morphology and slightly increased water desorption, but determining the impact on actual fuel cell performance requires further research.