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Measuring and Modeling NMR and Emission Spectra to Gain New Insight into Challenging Organic Compounds
Title
Measuring and Modeling NMR and Emission Spectra to Gain New Insight into Challenging Organic Compounds.
Creator
Powell, Jacob, Harper, James, Campiglia, Andres, Beazley, Melanie, Richardson, David, Blair, Richard, University of Central Florida
Abstract / Description
The advancement of theoretical methods in recent years has allowed the calculation of highly accurate spectroscopic parameters. Comparing these values to the corresponding experimental data can allow molecular structures to be elucidated. This dissertation details the use of experimental and theoretical data from nuclear magnetic resonance (NMR) and fluorescence spectroscopy to determine structure. Herein the NMR focus is on measuring (&) modeling chemical shift anisotropy and one-bond carbon...
Show moreThe advancement of theoretical methods in recent years has allowed the calculation of highly accurate spectroscopic parameters. Comparing these values to the corresponding experimental data can allow molecular structures to be elucidated. This dissertation details the use of experimental and theoretical data from nuclear magnetic resonance (NMR) and fluorescence spectroscopy to determine structure. Herein the NMR focus is on measuring (&) modeling chemical shift anisotropy and one-bond carbon-carbon J-coupling constants (1JCC). The fluorescence analysis models vibrationally resolved fluorescence spectra.Chemical shift anisotropy techniques were used to study two conflicting crystal structures of the n-alkyl fatty acid, lauric acid. These two crystal structures differ only in their COOH conformation. Lattice-including density functional theory (DFT) refinements of each crystal structure failed to match experimental data leading to the proposal of a third crystal structure with a hydrogen disordered COOH moiety. This disorder strengthens the hydrogen bond providing a new rationalization to the long observed non-monotonic melting behavior of fatty acids having even and odd numbers of carbons.The INADEQUATE is a NMR experiment that directly establishes the skeleton of organic compounds by measuring the 1JCC throughout a molecule. The low occurrence of 13C-13C pairs (1 in 10,000) and breaks in connectivity due to the presence of heteroatoms causes challenges to INADEQUATE analysis. Here, the insensitivity problem is overcome using analysis software that automatically processes data and identifies signals, even when they are comparable in magnitude to noise. When combined with DFT 1JCC predictions,configuration and confirmations of the natural products 5-methylmellein and hydroheptelidic acid are elucidated.Vibrationally resolved fluorescence spectra of high molecular weight PAHs can be accurately calculated through time-dependent density functional theory (TD-DFT) methods. Here, the theoretical spectral profiles of certain PAHs are shown to match experimental high- resolution fluorescence spectra acquired at cryogenic temperatures. However, in all cases, theoretical spectra were systematically offset from experimental spectra. To decrease these uncertainties spectra were empirically corrected and an automated scheme employed to match theoretical spectra with all possible experimental spectra. In all cases the theoretical spectra were correctly matched to the experimental spectra.
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Date Issued
2017
Identifier
CFE0006953, ucf:51680
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006953
OPTICAL AND PHYSICAL PROPERTIES OF CERAMIC CRYSTAL LASER MATERIALS
Title
OPTICAL AND PHYSICAL PROPERTIES OF CERAMIC CRYSTAL LASER MATERIALS.
Creator
Simmons, Jed, Bass, Michael, University of Central Florida
Abstract / Description
Historically ceramic crystal laser material has had disadvantages compared to single crystal laser material. However, progress has been made in the last decade and a half to overcome the disadvantages associated with ceramic crystal. Today, because of the promise of ceramic crystal as a high power laser material, investigation into its properties, both physical and optical, is warranted and important. Thermal expansion was measured in this thesis for Nd:YAG (yttrium aluminum garnet) ceramic...
Show moreHistorically ceramic crystal laser material has had disadvantages compared to single crystal laser material. However, progress has been made in the last decade and a half to overcome the disadvantages associated with ceramic crystal. Today, because of the promise of ceramic crystal as a high power laser material, investigation into its properties, both physical and optical, is warranted and important. Thermal expansion was measured in this thesis for Nd:YAG (yttrium aluminum garnet) ceramic crystal using an interferometric method. The interferometer employed a spatially filtered HeNe at 633 nm wavelength. Thermal expansion coefficients measured for the ceramic crystal samples were near the reported values for single crystal Nd:YAG. With a similar experimental setup as that for the thermal expansion measurements, dn/dT for ceramic crystal Nd:YAG was measured and found to be slightly higher than the reported value for single crystal. Depolarization loss due to thermal gradient induced stresses can limit laser performance. As a result this phenomenon was modeled for ceramic crystal materials and compared to single crystals for slab and rod shaped gain media. This was accomplished using COMSOL Multiphysics, and MATLAB. Results indicate a dependence of the depolarization loss on the grain size where the loss decreases with decreased grain size even to the point where lower loss may be expected in ceramic crystals than in single crystal samples when the grain sizes in the ceramic crystal are sufficiently small. Deformation-induced thermal lensing was modeled for a single crystal slab and its relevance to ceramic crystal is discussed. Data indicates the most notable cause of deformation-induced thermal lensing is a consequence of the deformation of the top and bottom surfaces. Also, the strength of the lensing along the thickness is greater than the width and greater than that due to other causes of lensing along the thickness of the slab. Emission spectra, absorption spectra, and fluorescence lifetime were measured for Nd:YAG ceramic crystal and Yb:Lu2O3 ceramic crystal. No apparent inhomogeneous broadening appears to exist in the Nd:YAG ceramic at low concentrations. Concentration and temperature dependence effects on emission spectra were measured and are presented. Laser action in a thin disk of Yb:Y2O3 ceramic crystal was achieved. Pumping was accomplished with a fiber coupled diode laser stack at 938 nm. A slope efficiency of 34% was achieved with maximum output energy of 28.8 mJ/pulse.
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Date Issued
2007
Identifier
CFE0001764, ucf:47273
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0001764
DEVELOPMENT OF LUMINESCENT RUTHENIUM COMPLEXES FOR IN-VITRO FLUORESCENCE IMAGING OF ANGIOGENESIS WITH THE RGD PEPTIDE.
Title
DEVELOPMENT OF LUMINESCENT RUTHENIUM COMPLEXES FOR IN-VITRO FLUORESCENCE IMAGING OF ANGIOGENESIS WITH THE RGD PEPTIDE.
Creator
Victoria, Rosmery, Hinkle, Charles R., University of Central Florida
Abstract / Description
Herein we report the synthesis of an RGD-ruthenium bipyridine 2+ complex aimed at the detection of angiogenesis. Angiogenesis plays a critical role in many pathophysiological processes, such as tumor growth. The alpha v-integrins (alpha v beta 3, alpha v beta 5) are currently used as molecular targeting sites for anti-angiogenic therapies. The 2+ complex is an organometallic luminescent probe, which enables noninvasive, in vitro imaging of alpha v beta 3 expression. Peptides containing the...
Show moreHerein we report the synthesis of an RGD-ruthenium bipyridine 2+ complex aimed at the detection of angiogenesis. Angiogenesis plays a critical role in many pathophysiological processes, such as tumor growth. The alpha v-integrins (alpha v beta 3, alpha v beta 5) are currently used as molecular targeting sites for anti-angiogenic therapies. The 2+ complex is an organometallic luminescent probe, which enables noninvasive, in vitro imaging of alpha v beta 3 expression. Peptides containing the arginine-glycine-aspartic acid (RGD) sequence have been shown to bind strongly to the alpha v beta 3 integrin. The RuBpy probes are soluble in water, display long lifetimes, and are photochemically stable. These properties enable the Ru(tris-bpy) complexes to be useful in numerous applications in biophysical and cell biology. The 2+ complex was synthesized by combining the succinimidyl ester on the RuBpy complex with the lysine of the c(RGDfK) peptide. The results of the one-photon fluorescence bioimaging showed selective binding of the cyclic RGD to alpha v beta 3 integrin, which supports previous literature. The high luminescence intensity, long lifetimes, and low cell toxicity levels of dye 2+, illustrates the potential usage of this probe for future biological applications.
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Date Issued
2012
Identifier
CFH0004234, ucf:44898
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFH0004234
THE APPLICATION OF TWO-PHOTON ABSORBING PROBES IN LYSOSOMAL, ZINC ION SENSING AND FOLATE RECEPTOR-TARGETED BIOIMAGING
Title
THE APPLICATION OF TWO-PHOTON ABSORBING PROBES IN LYSOSOMAL, ZINC ION SENSING AND FOLATE RECEPTOR-TARGETED BIOIMAGING.
Creator
WANG, XUHUA, Belfield, Kevin D., University of Central Florida
Abstract / Description
Two-photon fluorescence microscopy (2PFM) has become a powerful technique for bioimaging in non-invasive cancer diagnosis and also investigating the mechanization and original of a variety of diseases by tracking various biological processes. Because the fluorescence emission by two photon absorbing (2PA) is directly proportional to the square of the intensity of excitation light, this intrinsic property of 2PA provides 2PFM great advantages over traditional one-photon fluorescence microscopy...
Show moreTwo-photon fluorescence microscopy (2PFM) has become a powerful technique for bioimaging in non-invasive cancer diagnosis and also investigating the mechanization and original of a variety of diseases by tracking various biological processes. Because the fluorescence emission by two photon absorbing (2PA) is directly proportional to the square of the intensity of excitation light, this intrinsic property of 2PA provides 2PFM great advantages over traditional one-photon fluorescence microscopy (1PFM), including high 3D spatial localization, less photodamage and interference from biological tissue because of using longer wavelength excitation (700-1300 nm). However, most 2PA probes are hydrophobic and their photostabilities are questionable, severely limiting their biological and medical applications. In addition, probes with significant specificity for certain organelles for tracking cellular processes or metal ions for monitoring neural transmission are somewhat rare. Moreover, it is also very significant to deliver the probes to specific disease sites for early cancer diagnosis. In order to increase the water solubility of probes, polyethylene glycol (PEG) was introduced to a fluorene-based 2PA probe LT1 for lysosomal 2PFM cell imaging. The 2PFM bioimaging application of the novel two-photon absorbing fluorene derivative LT1, selective for the lysosomes of HCT 116 cancer cells is described in Chapter II. Linear and nonlinear photophysical and photochemical properties of the probe were investigated to evaluate the potential of the probe for 2PFM lysosomal imaging. After the investigation of the cytotoxicity of this new probe, colocalization studies of the probe with commercial lysosomal probe Lysotracker Red in HCT 116 cells were conducted. A high colocalization coefficient (0.96) was achieved and demonstrated the specific localization of the probe in lysosomes. A figure of merit, FM, was introduced by which all fluorescent probes for 2PFM can be compared. LT1 was demonstrated to have a number of properties that far exceed those of commercial lysotracker probes, including much higher 2PA cross sections, good fluorescence quantum yield, and, importantly, high photostability, all resulting in a superior figure of merit. Consequently, 2PFM was used to demonstrate lysosomal tracking with LT1. In addition to lysosomes, it is also very significant to investigate the physiological roles of free metal ions in biological processes, especially Zn2+, because Zn2+ normally serves either as the catalytic elements in enzymatic activity centers or as structural elements in enzymes and transcription factors. However, biocompatible and effective Zn2+ probes for 2PFM bioimaging are infrequent. In Chapter III, 2PFM bioimaging with a hydrophilic 2PA Zn2+ sensing fluorescent probe, bis(1,2,3-triazolyl)fluorene derivative, is described. 2PFM bioimaging of the probe in living HeLa cancer cells was demonstrated. The results revealed a significant fluorescence increase upon introduction of Zn2+ into the cancer cells, and a reversible Zn2+ binding to the probe was also demonstrated, providing a robust probe for two-photon fluorescence zinc ion sensing. Early cancer diagnosis is another critical application for 2PFM, but there are still huge challenges for this new technique in clinical areas. Most 2PA probes with large two-photon absorbing cross sections and fluorescence quantum efficiency are synthetically more accessible in hydrophobic forms. In order to increase the efficiency of the probes and minimize the effect of the probe on the human body, delivery of the probe specifically to cancer sites is desired. The synthesis and characterization of narrow dispersity organically modified silica nanoparticles (SiNPs), diameter ~30 nm, entrapping a hydrophobic two-photon absorbing fluorenyl dye, are reported in Chapter IV. The surface of the SiNPs was functionalized with folic acid to specifically deliver the probe to folate receptor (FR) over-expressing HeLa cells, making these folate 2PA dye-doped SiNPs potential candidates as probes for two-photon fluorescence microscopy (2PFM) bioimaging. In vitro studies using FR over-expressing HeLa cells demonstrated specific cellular uptake of the functionalized nanoparticles. However, when the concentration of the dye in SiNPs increased for higher signal output, the fluorescence quantum efficiency of a probe normally decreases because of self-quenching. In Chapter V, a near-infrared (NIR) emitting probe is reported to overcome this limitation through both aggregate-enhanced fluorescence emission and aggregate enhanced two-photon absorption. The dye was encapsulated in SiNPs and the surface of the nanoparticles was functionalized with PEG followed by a folic acid derivative to specifically target folate receptors. NIR emission is important for deep tissue imaging. In vitro studies using HeLa cells that upregulate folate receptors indicated specific cellular uptake of the folic acid functionalized SiNP nanoprobe. Meanwhile, the probe was also investigated for live animal imaging by employing mice bearing HeLa tumors for in vivo studies. Ex vivo 2PFM tumor imaging was then conducted to achieve high quality 3D thick tissue tumor images.
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Date Issued
2011
Identifier
CFE0003640, ucf:48891
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003640

Pages