Single molecule tracking studies of flow-aligned mesoporous silica monoliths: pore order and pore wall permeability

Doctor of PhilosophyDepartment of ChemistryDaniel A. HigginsThis dissertation describes single-molecule tracking (SMT) studies for the quantitative characterization of one-dimensional (1D) nanostructures in surfactant-templated mesoporous silica monoliths prepared within microfluidic channels. Single molecule diffusion of fluorescent probe molecules within the cylindrical mesopores reflects microscopic morphologies and mass-transport properties of the materials with high temporal and spatial resolution. The pore organization and materials order are initially investigated as a function of sol aging prior to loading into the microfluidic channels. Mesopores in these materials are templated by Cetyltrimethylammonium bromide (CTAB). Wide-field fluorescence videos depict 1D motion of the dyes within the individual mesopores. Orthogonal regression analysis of these motions provides a measure of the mesopore orientation. Channels filled prior to gelation of the sol produce monoliths incorporating large monodomains with highly aligned mesopores. In contrast, channels filled close to or after gelation yield monoliths with misaligned pores that are also more disordered. Two-dimensional (2D) small angle X-ray scattering (SAXS) experiments support the results obtained by SMT. These studies help to identify conditions under which highly aligned mesoporous monoliths can be obtained and also demonstrate the utility of SMT for characterization of mesopore order. The non-ionic surfactant Pluronic F127 is also utilized as the structural-directing agent. The diffusive motions of PDI dyes that are uncharged, cationic and anionic are explored by SMT and fluorescence correlation spectroscopy (FCS). The SMT studies for the uncharged dye show development of 1D diffusion along the flow direction while charged dyes exhibit predominant isotropic diffusion, with each of these behaviors becoming more prevalent as a function of aging time after filling of the microfluidic channels. SMT studies from silica-free F127 gels suggest that partitioning plays a important role in governing the diffusion behavior of the PDI dyes within the surfactant-filled mesopores. FCS results exhibit similar mean diffusion coefficients for all three dyes that suggest these dyes diffuse through similar sample regions. These studies demonstrate that the silica pore walls in the mesoporous silica monoliths remain permeable after gelation and that partitioning of solute species to different regions within the pores plays an important role in restricting the dimensionality of their diffusive motio

Fabrication of Complex 3D Micro-Scale Scaffolds and Drug Delivery Devices using Dynamic Mask Projection Microstereolithography

Microstereolithography (μSL) technology can fabricate three-dimensional (3D) tissue engineered scaffolds with controlled biochemical and mechanical micro-architectures. A μSL system for tissue engineering was developed using a Digital Micromirror Device (DMDTM) for dynamic pattern generation and an ultraviolet (UV) lamp filtered at 365 nm for crosslinking the photoreactive polymer solution. The μSL system was designed with x-y resolution of ~2 μm and a vertical (z) resolution of ~1 μm. To demonstrate the use of μSL in tissue engineering, poly(propylene fumarate) (PPF) was synthesized with a molecular weight of ~1200 Da. The viscosity of the PPF was reduced to ~150 cP (at 50 o C) by mixing with diethyl fumarate (DEF) in the ratio of 7:3 (w/w). Finally, ~2 % (w/w) of (bis(2,4,6- trimethylbenzoyl) phenylphosphine oxide (BAPO) was added to the solution to serve as a photoinitiator. Cure depth experiments were performed to determine the curing characteristics of the synthesized PPF, and the resulting system and photopolymer were used to construct a variety of 3D porous scaffolds with interconnected pores between 100 and 150 μm and a micro-needle array with height of ~800 μm and individual tip diameters of ~20 μm. SEM and microscope images of the micro-architectures illustrate that the developed μSL system is a promising technology for producing biodegradable and biocompatible microstructures.Mechanical Engineerin

Enhanced magnetic and thermoelectric properties in epitaxial polycrystalline SrRuO3 thin film

Transition metal oxide thin films show versatile electrical, magnetic, and thermal properties which can be tailored by deliberately introducing macroscopic grain boundaries via polycrystalline solids. In this study, we focus on the modification of the magnetic and thermal transport properties by fabricating single- and polycrystalline epitaxial SrRuO3 thin films using pulsed laser epitaxy. Using epitaxial stabilization technique with atomically flat polycrystalline SrTiO3 substrate, epitaxial polycrystalline SrRuO3 thin film with crystalline quality of each grain comparable to that of single-crystalline counterpart is realized. In particular, alleviated compressive strain near the grain boundaries due to coalescence is evidenced structurally, which induced enhancement of ferromagnetic ordering of the polycrystalline epitaxial thin film. The structural variations associated with the grain boundaries further reduce the thermal conductivity without deteriorating the electronic transport, and lead to enhanced thermoelectric efficiency in the epitaxial polycrystalline thin films, compared with their single-crystalline counterpart.Comment: 24 pages, 5 figure

Short-Term Effects of Ginkgo biloba Extract on Peripapillary Retinal Blood Flow in Normal Tension Glaucoma

PURPOSE: Based on the vascular theory of glaucoma pathogenesis, we wanted to evaluate the effect of Ginkgo biloba extract (GBE) on peripapillary blood flow in patients with normal tension glaucoma (NTG). METHODS: Thirty patients with NTG were randomly placed in the GBE-treated or control groups. The GBE-treated group received 80 mg GBE orally, twice a day for four weeks, and the control group received a placebo twice a day for four weeks. Complete ocular examinations including visual field, Heidelberg retina flowmeter, and systemic examinations were performed on the first study day and on the day treatment was completed. RESULTS: After GBE treatment, the mean blood flow, volume, and velocity increased at almost all points, and there was a statistically significant increase in blood flow at almost all points, in comparison to the placebo. Blood volume significantly increased only in the superior nasal and superior temporal neuroretinal rim areas. GBE also significantly increased blood velocity in areas of the inferior temporal neuroretinal rim and superior temporal peripapillary area. CONCLUSIONS: GBE administration appears to have desirable effect on ocular blood flow in NTG patients.ope

Effect of the Phosphorus Gettering on Si Heterojunction Solar Cells

To improve the efficiency of crystalline silicon solar cells, should be collected the excess carrier as much as possible. Therefore, minimizing the recombination both at the bulk and surface regions is important. Impurities make recombination sites and they are the major reason for recombination. Phosphorus (P) gettering was introduced to reduce metal impurities in the bulk region of Si wafers and then to improve the efficiency of Si heterojunction solar cells fabricated on the wafers. Resistivity of wafers was measured by a four-point probe method. Fill factor of solar cells was measured by a solar simulator. Saturation current and ideality factor were calculated from a dark current density-voltage graph. External quantum efficiency was analyzed to assess the effect of P gettering on the performance of solar cells. Minority bulk lifetime measured by microwave photoconductance decay increases from 368.3 to 660.8 mu s. Open-circuit voltage and short-circuit current density increase from 577 to 598 mV and 27.8 to 29.8mA/cm(2), respectively. The efficiency of solar cells increases from 11.9 to 13.4%. P gettering will be feasible to improve the efficiency of Si heterojunction solar cells fabricated on P-doped Si wafers.open1

A case report of primary breast angiosarcoma with fatal pulmonary hemorrhage due to thrombocytopenia

Primary angiosarcomas of the breast are rare malignancy that account for fewer than 0.04% of all malignant breast tumors. The prognosis is poor. Surgery is the first line of treatment for angiosarcoma. Adjuvant chemotherapy and radiotherapy have been tried, but their efficacy remains controversial. Here we present the case of a 47-year-old woman with a palpable left breast mass that was diagnosed as a primary angiosarcoma. The patient underwent modified radical mastectomy with adjuvant chemotherapy and radiotherapy. Postoperatively, eighteen months later, the angiosarcoma recurred. The patient returned complaining of dyspnea and hemoptysis and was found to have a large pleural effusion. She developed a gradual onset of thrombocytopenia that persisted despite platelet transfusions. Finally, the patient died of respiratory failure secondary to pulmonary hemorrhage

Comparative Study for the Differentiation of Allergic and Irritant Contact Dermatitis in Mice

Our study was performed to compare the differences between allergic and irritant contact dermatitis in BALB/c mice. Allergic reaction was induced by a sensitizing regimen of 2,4-dinitro-l-fluorobenzene (DNFB) and irritant reaction by 10% sodium lauryl sulfate (SLS). The following differences were noted: 1) the mice with irritant reaction showed an earlier peak of ear swelling, 2) increasing number of Langerhans cells (LCs) in allergic reaction but decreasing number of LCs in irritant reaction was observed at 48 hr after challenge of DNFB or SLS, and 3) induction of Ia (+) keratinocytes was found only in allergic reaction. It was suggested that Ia (+) keratinocytes play an active role in the mechanism of allergic contact dermatitis

The possible roles of hyperpolarization-activated cyclic nucleotide channels in regulating pacemaker activity in colonic interstitial cells of Cajal

BACKGROUND: Hyperpolarization-activated cyclic nucleotide (HCN) channels are pacemaker channels that regulate heart rate and neuronal rhythm in spontaneously active cardiac and neuronal cells. Interstitial cells of Cajal (ICCs) are also spontaneously active pacemaker cells in the gastrointestinal tract. Here, we investigated the existence of HCN channel and its role on pacemaker activity in colonic ICCs. METHODS: We performed whole-cell patch clamp, RT-PCR, and Ca(2+)-imaging in cultured ICCs from mouse mid colon. RESULTS: SQ-22536 and dideoxyadenosine (adenylate cyclase inhibitors) decreased the frequency of pacemaker potentials, whereas both rolipram (cAMP-specific phosphodiesterase inhibitor) and cell-permeable 8-bromo-cAMP increased the frequency of pacemaker potentials. CsCl, ZD7288, zatebradine, clonidine (HCN channel blockers), and genistein (a tyrosine kinase inhibitor) suppressed the pacemaker activity. RT-PCR revealed expression of HCN1 and HCN3 channels in c-kit and Ano1 positive colonic ICCs. In recordings of spontaneous intracellular Ca(2+) [Ca(2+)](i) oscillations, rolipram and 8-bromo-cAMP increased [Ca(2+)](i) oscillations, whereas SQ-22536, CsCl, ZD7288, and genistein decreased [Ca(2+)](i) oscillations. CONCLUSIONS: HCN channels in colonic ICCs are tonically activated by basal cAMP production and participate in regulation of pacemaking activity