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Porphyrin and BODIPY molecular rotors as microviscometers
Kimball, Joseph Daniel, III
Kimball, Joseph Daniel, III
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[Fort Worth, Tex.] : Texas Christian University,
Date
2015
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Abstract
Viscosity, a fluids internal resistance to flow and resist molecular diffusion, is a fundamental property of fluid media. Determining the bulk viscosity of a fluid has been easy to relatively simple to accomplish for many years, yet in the recent decade there has been a focus on techniques to measure a fluids microviscosity. Microviscosity differs from bulk viscosity such that microviscosity is the friction experienced by a single particle interacting with its micron-sized local environment. Macroscopic methods to evaluate the viscosity are well established, but methods to determine viscosity on the microscale level remains unclear. This work determines the viability of three molecular rotors designed as probes for microviscosity in organic media, ionic liquids, and in the cellular microenvironment. Understanding microviscosity is important because it one of the main properties of any fluid and thus has an effect on any diffusion related processes.^A variety of mass and signal transport phenomena as well as intermolecular interactions are often governed by viscosity. Molecular rotors are a subclass of intramolecular charge transfer fluorophores which form a lower energy twisted state. This results in a charge separated species which is highly sensitive to its surrounding microenviroments viscosity as high viscosity limits its ability to form this twisted state. Once excited, there are deactivation routes which the excited fluorophore can undergo: radiative and non-radiative. Both were studied in this work. In the case of a radiative decay, as seen in porphyrin dimer, the energy is released in the form of a photon and is seen as a shifted band in the emission structure. The conformation of the porphyrin dimer was found to be influenced differently by ionic liquids as compared to molecular solvents, indicating the microheterogenous nature of ionic liquids play a role in the conformation.^For non-radiative decays, BODIPY dyads and triads were investigated. The triad has an extinction coefficient in the range of 200,000 M-1 cm-1, making it an extremely useful and sensitive fluorescent molecular rotor. Their fluorescent lifetimes were proven to correlate linearly with viscosity. Thus they were both encapsulated into lipds to determine their viability for cellular studies. The dyes were readily uptaken into three cancer cell lines, SKOV3, Calu 3 and Du 145. The lifetimes were then recorded using FLIM to map the viscosity of the cellular cytoplasm, mitochondria, lysosomes and other various organelles. A longer than expected lifetime in the cytoplasm was observed. This could be due to binding onto cytoplasmic proteins distributed throughout the cytoplasm, not due to viscosity as the theory of molecular rotors predicts.
Contents
Subject
Subject(s)
Porphyrins.
Boron compounds.
Fluorescence.
Fluorescence microscopy.
Viscosity.
Boron compounds.
Fluorescence.
Fluorescence microscopy.
Viscosity.
Research Projects
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Dissertation
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Department
Physics and Astronomy