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Title: Synthesis of Fluorescent Molecules and their Applications as Viscosity Sensors, Metal Ion Indicators, and Near-Infrared Probes.
Creator: Wang, Mengyuan, Belfield, Kevin, Campiglia, Andres, Miles, Delbert, Frazer, Andrew, Cheng, Zixi, University of Central Florida
Abstract / Description: The primary focus of this dissertation is the development of novel fluorescent near-infrared molecules for various applications. In Chapter 1, a compound dU-BZ synthesized via Sonogashira coupling reaction methodology is described. A deoxyuridine building block was introduced to enhance hydrophilic properties and reduce toxicity, while an alkynylated benzothiazolium dye was incorporated for near-IR emission and reduce photodamage and phototoxicity that is characteristic of common fluorphores...
Show moreThe primary focus of this dissertation is the development of novel fluorescent near-infrared molecules for various applications. In Chapter 1, a compound dU-BZ synthesized via Sonogashira coupling reaction methodology is described. A deoxyuridine building block was introduced to enhance hydrophilic properties and reduce toxicity, while an alkynylated benzothiazolium dye was incorporated for near-IR emission and reduce photodamage and phototoxicity that is characteristic of common fluorphores that are excited by UV or visible light. A 30-fold enhancement of fluorescence intensity of dU-BZ was achieved in a viscous environment. Values of fluorescence quantum yields in 99% glycerol/1% methanol (v/v) of varying temperature from 293 K to 343 K, together with fluorescence quantum yields, radiative and nonradiative rate constants and fluorescence lifetimes in glycerol/methanol solutions of varying viscosities from 4.8 to 950 cP were determined. It was found that both fluorescence quantum yields and fluorescence lifetimes increased with increasing viscosity, which is consistent with results predicted by theory. This suggests that the newly designed compound dU-BZ is capable of functioning as a probe of local microviscosity, and was later confirmed by in vitro bioimaging experiments.In Chapter 2, a new BAPTA (O,O'-bis(2-aminophenyl)ethyleneglycol-N,N,N',N'-tetra acetic acid) and BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)-based calcium indicator, BAPBO-3, is reported. A new synthetic route was employed to simplify both synthesis and purification, which tend to be low yielding and cumbersome for BAPTA derivatives. Upon excitation, a 1.5-fold increase in fluorescence intensity in buffer containing 39 ?? Ca2+ and a 3-fold increase in fluorescence intensity in buffer containing 1 M Ca2+ was observed; modest but promising fluorescence turn-on enhancements.In Chapter 3, a newly-designed unsymmetrical squaraine dye, SQ3, was synthesized. A one-pot synthesis was employed resulting in a 10% yield, a result that is generally quite favorable for the creation of unsymmetrical squaraines Photophysical and photochemical characterization was conducted in various solvents, and a 678 nm absorption maximum and a 692 nm emission maximum were recorded in DMSO solution with a fluorescence quantum yield of 0.32. In vitro cell studies demonstrated that SQ3 can be used as a near-IR probe for bioimaging.
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Date Issued: 2014
Identifier: CFE0005900, ucf:50863
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005900

Title: Folate conjugated hyperbranched polyester nanoparticles for prostate tumor-targeted delivery of a cytotoxic peptide via prostate specific membrane antigen.
Creator: Flores-Fernandez, Orielyz, Perez Figueroa, J. Manuel, Campiglia, Andres, Yestrebsky, Cherie, Harper, James, Khaled, Annette, University of Central Florida
Abstract / Description: Prostate Cancer is the second most deadly cancer in men, after lung cancer. The need for new and effective therapeutics that can constrain prostate cancer progression are challenged by the lack of suitable delivery strategies that target prostate cancer tissue. To study CT20p as potential chemotherapeutic agent in the treatment of prostate cancer we proposed the use of targetable hyperbranched polyester (HBPE) based nanoparticles as delivery system. Folic acid was conjugated to the...
Show moreProstate Cancer is the second most deadly cancer in men, after lung cancer. The need for new and effective therapeutics that can constrain prostate cancer progression are challenged by the lack of suitable delivery strategies that target prostate cancer tissue. To study CT20p as potential chemotherapeutic agent in the treatment of prostate cancer we proposed the use of targetable hyperbranched polyester (HBPE) based nanoparticles as delivery system. Folic acid was conjugated to the nanocarrier to improve the selectivity of the nanoparticle towards specific cell surface targets in prostate cancer cell lines. Specifically we evaluated LNCaP that up-regulated the PSMA receptor. The synthesis of folate conjugated hyperbranched polyester nanoparticles was accomplished using an aliphatic and biodegradable hyperbranched polyester (HBPE). HBPE was prepared from commercially available diethyl malonate and 4-bromobutyl acetate. Our AB2 type monomer displays a three-bond connectivity that grows three-dimensionally under specific polymerization conditions. The product, HBPE, is a polymer with globular configuration that contains surface carboxylic acid groups and holds hydrophobic cavities. Carboxylated HBPE nanoparticles were synthesized via solvent diffusion method. A variety of hydrophobic cargos including: dyes (DiR and DiI) and the cytotoxic peptide CT20p were successfully encapsulated. DLS along with STEM imaging reveal nanoparticle preparations with ~100 nm size. Using water-soluble carbodiimide chemistry, surface modifications were accomplished. Available carboxylic acid groups were conjugated to aminated folic acid to yield folate functionalized nanoparticles.We explore the targeting capability of the Folate-HBPE nanoparticles and demonstrated that the cell internalization of Folate-HBPE into prostate cancer cell lines (LNCaP and PSMA (+) PC-3) was attained via a PSMA-mediated targeting mechanism. Furthermore, when CT20p was delivered to PSMA expressing PCa cells, detachment and death was observed; together with a reduction in the levels of ?1 integrin (CD29) expression, an integrin implicate in cell communication and cell adhesion. CT20p inhibits cell proliferation within 24 h and produce significant cell death after 48 h post treatment. The IC50 of CT20p was calculated at ~7 nM. Additionally, we investigated the capability of Folate-HBPE(CT20p) to perform as a therapeutic agent, in an in vivo setup, using a murine prostate tumor model. The Folate-PEG-HBPE NPs protected CT20p while in circulation and allowed effective uptake by PSMA-mediated targeting. Treatment with Folate-HBPE(CT20p) display localize tumor targeting and significant tumor growth inhibition in PSMA(+) PCa cell lines within days. Together these results suggest the potential of Folate-HBPE(CT20p) nanoparticles in the treatment of prostate cancer.
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Date Issued: 2015
Identifier: CFE0006216, ucf:51112
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006216

Title: Investigating New Guaiazulenes and Diketopyrropyrroles for Photonic Applications.
Creator: Ghazvini Zadeh, Ebrahim, Belfield, Kevin, Campiglia, Andres, Yuan, Yu, Zou, Shengli, Cheng, Zixi, University of Central Florida
Abstract / Description: ?-Conjugated systems have been the focus of study in recent years in order to understand their charge transport and optical properties for use in organic electronic devices, fluorescence bioimaging, sensors, and 3D optical data storage (ODS), among others. As a result, several molecular building blocks have been designed, allowing new frontiers to be realized. While various successful building blocks have been fine-tuned at both the electronic and molecular structure level to provide advanced...
Show more?-Conjugated systems have been the focus of study in recent years in order to understand their charge transport and optical properties for use in organic electronic devices, fluorescence bioimaging, sensors, and 3D optical data storage (ODS), among others. As a result, several molecular building blocks have been designed, allowing new frontiers to be realized. While various successful building blocks have been fine-tuned at both the electronic and molecular structure level to provide advanced photophysical and optoelectronic characteristics, the azulene framework has been under-appreciated despite its unique electronic and optical properties. Among several attributes, azulenes are vibrant blue naturally occurring hydrocarbons that exhibit large dipolar character, coupled with stimuli-responsive behavior in acidic environments. Additionally, the non-toxic nature and the accompanying eco-friendly feature of some azulenes, namely guaiazulene, may set the stage to further explore a more (")green(") route towards photonic and conductive materials.The first part of this dissertation focuses on exploiting guaiazulene as a natural building block for the synthesis of chromophores with varying stimuli-responsiveness. Results described in Chapter 1 show that extending the conjugation of guaiazulene through its seven-membered ring methyl group with aromatic substituents dramatically impacts the optical properties of the guaiazulenium carbocation. Study of these ?(-)stabilized tropilium ions enabled establishing photophysical structure-property trends for guaiazulene-terminated ?-conjugated analogs under acidic conditions, including absorption, emission, quantum yield, and optical band gap patterns. These results were exploited in the design of a photosensitive polymeric system with potential application in the field of three dimensional (3D) optical data storage (ODS).Chapter 2 describes the use of guaiazulene reactive sites (C-3 and C-4 methyl group) to generate a series of cyclopenta[ef]heptalenes that exhibit strong stimuli-responsive behavior. The approach presents a versatile route that allows for various substrates to be incorporated into the resulting cyclopenta[ef]heptalenes, especially after optimization that led to devising a one-pot reaction toward such tricyclic systems. Examining the UV-vis absorption profiles in neutral and acidic media showed that the extension of conjugation at C(4) of the cyclopenta[ef]heptalene skeleton results in longer absorption maxima and smaller optical energy gaps. Additionally, it was concluded that these systems act as sensitizers of a UV-activated ((<) 300 nm) photoacid generator (PAG), via intermolecular photoinduced electron transfer (PeT), upon which the PAG undergoes photodecomposition resulting in the generation of acid.In a related study, the guaiazulene methyl group at C-4 was employed to study the linear and nonlinear optical properties of 4-styrylguaiazulenes, having the same ?(-)donor with varying ?-spacer. It was realized that the conjugation length correlates with the extent of bathochromic shift of the protonated species. On the other hand, a trend of decreasing quantum yield was established for this set of 4-styrylguaiazulenes, which can be explained by the increasingly higher degree of flexibility.The second part of this dissertation presents a comprehensive investigation of the linear photophysical, photochemical, and nonlinear optical properties of diketopyrrolopyrrole (DPP)-based derivatives, including two-photon absorption (2PA), femtosecond transient absorption, stimulated emission spectroscopy, and superfluorescence phenomena. The synthetic feasibility, ease of modification, outstanding robustness, and attractive spectroscopic properties of DPPs have motivated their study for fluorescence microscopy applications, concluding that the prepared DPP's are potentially suitable chromophores for high resolution stimulated emission depletion (STED) microscopy.
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Date Issued: 2015
Identifier: CFE0006034, ucf:50986
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006034

Title: Synthesis and Characterization of New Probes for use in Fluorescence and X-ray CT Bioimaging.
Creator: Tang, Simon, Belfield, Kevin, Miles, Delbert, Campiglia, Andres, Zou, Shengli, Cheng, Zixi, University of Central Florida
Abstract / Description: The pursuit of more suitable drugs intended for possible biological applications are a continuously growing topic of research within the scientific community. One of these suitable qualities includes the need for hydrophilicity and or some appropriate delivery system for the drug to enter into biological systems. A system of analyzing and following these compounds would then, however, be necessary to conduct any kind of mechanistic or interaction studies for he said drug within the biological...
Show moreThe pursuit of more suitable drugs intended for possible biological applications are a continuously growing topic of research within the scientific community. One of these suitable qualities includes the need for hydrophilicity and or some appropriate delivery system for the drug to enter into biological systems. A system of analyzing and following these compounds would then, however, be necessary to conduct any kind of mechanistic or interaction studies for he said drug within the biological system. Just to name a few, fluorescence and X-ray computed tomography (CT) methods allow for imaging of biological systems but require the need of compounds with specific qualities. Finally, even with a means of entering and following a oaded drug, it would not be complete without a way of targeting its intended location. Herein, the first chapter reports the synthesis and characterization of a fluorene-based pyridil bis-?-diketone compound with suitable one- and two-photon fluorescent properties and its encapsulation into Pluronic F127 micelles for the possible application of tracking lysosomes. Next the synthesis and characterization of a BODIPY-based fluorophore with excellent fluorescence ability is reported. This compound was conjugated to two triphenylphosphine (TPP) groups and is shown as a potential mitochondria probe within HCT-116 cells. Finally, the synthesis and characterization of diatrizoic acid (DA) based derivatives conjugated to silica nanoparticles, as well as unconjugated, are reported as potential CT contrast agents. The derivatives were also functionalized with maleimide moieties facilitating subsequent potential bioconjugation of a targeting protein via a thiol group.
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Date Issued: 2015
Identifier: CFE0006056, ucf:50961
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006056

Title: Photophysics of Organic Probes and their Applications in Bioimaging (&) Photodynamic Therapy.
Creator: Kim, Bosung, Belfield, Kevin, Zou, Shengli, Campiglia, Andres, Frazer, Andrew, Ali, Gul Shad, University of Central Florida
Abstract / Description: Over the past several decades the phenomenon of luminescence (divided into fluorescence and phosphorescence) has received great attention in the field of biological science. This quest has motivated scientists for a variety of applications, including fluorescence imaging. Fluorescence microscopy techniques that provide unique advantages, such as high spatial resolution and superior sensitivity, have been regarded as attractive tools in biophotonics. With the progress of ultrafast laser...
Show moreOver the past several decades the phenomenon of luminescence (divided into fluorescence and phosphorescence) has received great attention in the field of biological science. This quest has motivated scientists for a variety of applications, including fluorescence imaging. Fluorescence microscopy techniques that provide unique advantages, such as high spatial resolution and superior sensitivity, have been regarded as attractive tools in biophotonics. With the progress of ultrafast laser sources, two-photon absorption (2PA), in which a molecule absorbs two photons simultaneously, has opened possibilities of using it for various applications. Two-photon fluorescence microscopy (2PFM), which affords deeper tissue penetration and excellent three-dimensional (3D) images, is now being widely employed for bioimaging. This dissertation focuses on the design, synthesis, and photophysical characterization of new fluorophores, as well as desirable applications. Chapter 1 gives an account of a brief introduction of luminescence and 2PA, as well as their utilities in biological applications. In chapter 2, a series of new BODIPY derivatives are presented along with their comprehensive linear and nonlinear characteristics. They exhibited excellent photophysical properties including large extinction coefficients, high fluorescence quantum yields, good photostability, and reasonable two-photon absorption cross sections. Two promising compounds were further evaluated as NIR fluorescent probes in one-photon and two-photon fluorescence imaging. Chapter 3 provides the design, synthesis, and photophysical characterization of two BODIPY dyes. In order to assess the potential of using the dye as a fluorescent probe, Lysotracker Red, a commercial lysosomal marker, was investigated for comparison purposes. The results indicate that figure of merit of both compounds were three orders of magnitude higher than that of Lysotracker Red. With an eye towards applications, one of the compounds was encapsulated in silica-based nanoparticles for in vitro and ex vivo one-photon and two-photon fluorescence imaging, in which the surface of the nanoparticle was modified with RGD peptides for specific targeting. The nanoprobe exhibited good biocompatibility and highly selective RGD-mediated uptake in ?V?3 integrin-overexpressing cancers, while maintaining efficient fluorescence quantum yield and high photostability. In chapter 4, the synthesis and photophysical properties of a novel photosensitizer with heavy atoms (halogen) were presented. The dye exhibited low fluorescence quantum yield, resulting in high singlet oxygen generation quantum yield. In vitro photodynamic studies demonstrated that photosensitization of the agent can induce cellular damage, subsequently leading to cell death by a necrotic cell death mechanism, supporting the therapeutic potential of using the agent for photodynamic therapy.
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Date Issued: 2015
Identifier: CFE0006041, ucf:50977
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006041

Title: Improvements on Instrumentation to Explore the Multidimensionality of Luminescence Spectroscopy.
Creator: Moore, Anthony, Campiglia, Andres, Chumbimuni Torres, Karin, Harper, James, Rex, Matthew, Lee, Woo Hyoung, University of Central Florida
Abstract / Description: This dissertation presents experimental and instrumentation developments that take full advantage of the multidimensional nature of line narrowing spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. The inconvenience of sample freezing procedures is eliminated with the aid of cryogenic fiber optic probes. Rapid collection of multidimensional data formats such as wavelength time matrices, excitation emission matrices, time-resolved excitation emission matrices and...
Show moreThis dissertation presents experimental and instrumentation developments that take full advantage of the multidimensional nature of line narrowing spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. The inconvenience of sample freezing procedures is eliminated with the aid of cryogenic fiber optic probes. Rapid collection of multidimensional data formats such as wavelength time matrices, excitation emission matrices, time-resolved excitation emission matrices and time resolved excitation emission cubes is made possible with the combination of a pulsed tunable dye laser, a spectrograph and an intensifier-charged coupled device. These data formats provide unique opportunities for processing vibrational luminescence data with second order multivariate calibration algorithms. The use of cryogenic fiber optic probes is extended to commercial instrumentation. An attractive feature of spectrofluorimeters with excitation and emission monochromators is the possibility to record synchronous spectra. The advantages of this approach, which include narrowing of spectral bandwidth and simplification of emission spectra, were demonstrated with the direct analysis of highly toxic dibenzopyrene isomers. The same is true for the collection of steady-state fluorescence excitation-emission matrices. These approaches provide a general solution to unpredictable spectral interference, a ubiquitous problem for the analysis of organic pollutants in environmental samples of unknown composition. Since commercial spectrofluorimeters are readily available in most academic institutions, industrial settings and research institutes, the developments presented here should facilitate the widespread application of line-narrowing spectroscopic techniques to the direct determination, no chromatographic separation, of highly toxic compounds in complex environmental matrixes of unknown composition.
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Date Issued: 2015
Identifier: CFE0005847, ucf:50934
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005847

Title: In Actu Et In Silicio: Linear and Nonlinear Photophysical Characterization of a Novel Europium Complex, and Incorporating Computational Calculations in the Analysis of Novel Organic Compounds.
Creator: Woodward, Adam, Belfield, Kevin, Campiglia, Andres, Harper, James, Frazer, Andrew, Cheng, Zixi, University of Central Florida
Abstract / Description: Despite not being a tangible substance, light is becoming an increasingly valuable tool in numerous areas of science and technology: the use of laser excitation of a fluorescent probe can generate incredibly detailed images of cellular structures without the need for large amounts of dissection; new types of solar cells are being produced using organic dyes to harvest light; computer data can be stored by inducing a chemical change in a compound through irradiation with light. However, before...
Show moreDespite not being a tangible substance, light is becoming an increasingly valuable tool in numerous areas of science and technology: the use of laser excitation of a fluorescent probe can generate incredibly detailed images of cellular structures without the need for large amounts of dissection; new types of solar cells are being produced using organic dyes to harvest light; computer data can be stored by inducing a chemical change in a compound through irradiation with light. However, before any of these materials can be applied in such a way, their properties must first be analyzed for them to be deemed viable.The focus of this dissertation is the photophysical characterization, linear and nonlinear, of a several novel organic compounds, and a europium complex, as well as using quantum chemical calculation techniques to understand some of the phenomena that are witnessed and begin to develop predictive capability. The nonlinear characterization of compounds utilizes wavelengths outside of their linear absorption range, where a focused beam can achieve the same excitation as one at half the wavelength, though this effect has a quadratic dependence on power.The potential for nonlinear excitation, or two-photon absorption (2PA), is becoming of increasing interest and importance for organic chromophores. Exciting only a small volume of material at a focal point makes it possible to nondestructively image samples in 3-dimensions, record data in multiple layers, and fabricate intricate structures through photopolymerization reactions.Lanthanides such as europium are known to exhibit sharp emission bands when excited, typically through an antenna effect due to the low probability of achieving direct excitation. This emission is long-lived, and through gating systems can readily be separated from background noise and autofluorescence (often observed in biological samples) that have much shorter lifetimes. Thus, one of the foci of this dissertation is the photophysical investigation of a series of novel lanthanide complexes, with particular attention to a europium complex.
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Date Issued: 2014
Identifier: CFE0005908, ucf:50891
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005908

Title: Solid Phase Extraction Room Temperature Fluorescence Spectroscopy for the Direct Quantification of Monohydroxy Metabolites of Polycyclic Aromatic Hydrocarbons in Urine Samples.
Creator: Calimag, Korina Jesusa, Campiglia, Andres, Belfield, Kevin, Yestrebsky, Cherie, Chumbimuni Torres, Karin, Schulte, Alfons, University of Central Florida
Abstract / Description: Polycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation pre-concentrates PAH, simplifies matrix composition, and...
Show morePolycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation pre-concentrates PAH, simplifies matrix composition, and facilitates analytical resolution in the chromatographic column. Among the several approaches that exist to pre-concentrate PAH from water samples, the Environmental Protection Agency (EPA) recommends the use of solid-phase extraction (SPE). High-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) are the basis for standard PAH identification and determination. Ultraviolet (UV) absorption and room temperature fluorescence detection are both widely used in HPLC, but the specificity of these detectors is modest. Since PAH identifi(&)#172;cation is solely based on retention times, unambiguous PAH identification requires complete chromatographic resolution of sample components. When HPLC is applied to (")unfamiliar(") samples, the EPA recommends that a supporting analytical technique such as GC-MS be applied to verify compound identification and to check peak-purity HPLC fractions. Independent of the volume of extracted water, the approximate time required to separate and determine the sixteen (")priority pollutants(") (EPA-PAH) via HPLC is approximately 60min. If additional GC-MS analysis is required for unambiguous PAH determination, the total analysis time will reach 2-3 hours per sample. If the concentrations of target species are found to lie outside the detector's response range, the sample must be diluted and the process repeated. These are important considerations when routine analysis of numerous samples is contemplated. Parent PAH are relatively inert and need metabolic activation to express their carcinogenicity. By virtue of the rich heterogeneous distribution of metabolic products they produce, PAH provide a full spectrum of the complexity associated with understanding the initial phase of carcinogenesis. PAH metabolites include a variety of products such as expoxides, hydroxyl aromatics, quinines, dihydrodiols, dioepoxides, tetrols and water soluble conjugates. During the past decades tremendous efforts have been made to develop bio-analytical techniques that possess the selectivity and sensitivity for the problem at hand. Depending on the complexity of the sample and the relative concentrations of the targeted metabolites, a combination of sample preparation techniques is often necessary to reach the limits of detection of the instrumental method of analysis. The numerous preparation steps open ample opportunity to metabolite loss and collection of inaccurate data. Separation of metabolites has been accomplished via HPLC, capillary electrophoresis (CE) and GC-MS. Unfortunately, the existence of chemically related metabolic products with virtually identical fragmentation patterns often challenges the specificity of these techniques. This dissertation presents significant improvements in various fronts. Its first original component (-) which we have named solid-phase nano-extraction (SPNE) - deals with the use of gold nanoparticles (Au NPs) as extracting material for PAH. The advantages of SPNE are demonstrated for the analysis of PAH in water samples via both HPLC1 and Laser-Excited Time-Resolved Shpol'skii Spectroscopy (LETRSS).2 The same concept is then extended to the analysis of monohydroxy-PAH in urine samples via SPE- HPLC3 and In-Capillary SPNE-CE.4 The second original component of this dissertation describes the application of Shpol'skii Spectroscopy to the analysis of polar PAH metabolites. The outstanding selectivity and sensitivity for the direct analysis of PAH at trace concentration levels has made Shpol'skii spectroscopy a leading technique in environmental analysis.5 Unfortunately, the requirement of a specific guest-host combination - typically a non-polar PAH dissolved in an n-alkane - has hindered its widespread application to the field of analytical chemistry. This dissertation takes the first steps in removing this limitation demonstrating its feasibility for the analysis of polar benzo[a]pyrene metabolites in alcohol matrixes.
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Date Issued: 2013
Identifier: CFE0005141, ucf:50693
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005141

Title: On the Capillary Electrophoresis of Monohydroxy Metabolites of Polycyclic Aromatic Hydrocarbons and its Application to the Analysis of Biological Matrices.
Creator: Knobel, Gaston, Campiglia, Andres, Clausen, Christian, Belfield, Kevin, Liao, Yi, Bhattacharya, Aniket, University of Central Florida
Abstract / Description: Polycyclic aromatic hydrocarbons (PAH) are a class of environmental pollutants consisting of a minimum of two fused aromatics rings originating from the incomplete combustion of organic matter and/or anthropogenic sources. Numerous possible anthropogenic and natural sources make the presence of PAH ubiquitous in the environment. The carcinogenic nature of some PAH and their ubiquitous presence makes their chemical analysis a topic of environmental and toxicological importance. Although...
Show morePolycyclic aromatic hydrocarbons (PAH) are a class of environmental pollutants consisting of a minimum of two fused aromatics rings originating from the incomplete combustion of organic matter and/or anthropogenic sources. Numerous possible anthropogenic and natural sources make the presence of PAH ubiquitous in the environment. The carcinogenic nature of some PAH and their ubiquitous presence makes their chemical analysis a topic of environmental and toxicological importance. Although environmental monitoring of PAH is an important step to prevent exposure to contaminated sites, it provides little information on the actual uptake and subsequent risks. Parent PAH are relatively inert and need metabolic activation to express their carcinogenicity. Covalent binding to DNA appears to be the first critical step in the initiation of the tumor formation process.To this end, the determination of short term biomarkers (-) such as monohydroxy-PAH metabolites (OH-PAH) - fills an important niche to interpret actual PAH exposure levels, prevent extreme body burdens and minimize cancer risk. One would certainly prefer an early warning parameter over a toxicological endpoint (-) such as DNA-adducts (-) indicating that extensive damage has already been done. Several methods have been developed to determine OH-PAH in specific tissue or excreta and food samples. The general trend for the analysis of OH-PAH follows the pattern of sample collection, sample clean-up and pre-concentration, chromatographic separation and quantification. Popular approaches for sample clean-up and pre-concentration include liquid-liquid extraction (LLE) and solid-phase extraction (SPE). Chromatographic separation and quantification has been based on high-performance liquid chromatography-room temperature fluorescence detection (HPLC) and gas chromatography-mass spectrometry (GC-MS).Although chromatographic techniques provide reliable results in the analysis of OH-PAH, their experimental procedures are time consuming and expensive. Elution times of 30-60 minutes are typical and standards must be run periodically to verify retention times. If the concentrations of target species are found to lie outside the detector's response range, the sample must be diluted and the process repeated. On the other end of the concentration range, many samples are (")zeroes,(") i.e. the concentrations are below detection limits. Additional problems arise when laboratory procedures are scaled up to handle thousands of samples under mass screening conditions. Under the prospective of a sustainable environment, the large usage of organic solvents is one of the main limitations of the current chromatographic methodology.This dissertation focuses on the development of a screening methodology for the analysis of OH-PAH in urine and milk samples. Screening techniques capable of providing a (")yes or no(") answer to OH-PAH contamination prevent unnecessary scrutiny of un-contaminated samples via conventional methods, reduce analysis cost and expedite the turnaround time for decision making purposes. The proposed methodology is based on capillary zone electrophoresis (CZE) and synchronous fluorescence spectroscopy (SFS). Metabolites extraction and pre-concentration is achieved with optimized SPE, LLE and/or QuEChERS (quick, easy, cheap, effective, rugged and safe) procedures. The small sample and extracting solvent volumes facilitate the simultaneous extraction of numerous samples via an environmentally friendly procedure, which is well-suited for routine monitoring of numerous samples. Sample stacking is successfully implemented to improve CZE limits of detection by two orders of magnitude. The unique electrophoretic pattern of positional isomers of OH-PAH demonstrates the potential of CZE for the unambiguous determination of metabolites with similar chromatographic behaviors and virtually similar fragmentation patterns. The direct determination of OH-PAH without chromatographic separation is demonstrated via SFS. The non-destructive nature of SFS provides ample opportunity for further metabolite confirmation via chromatographic techniques.
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Date Issued: 2013
Identifier: CFE0005102, ucf:50761
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005102

Title: Multidimensional Room-Temperature Fluorescence Microscopy for the Nondestructive Analysis of Forensic Trace Textile Fibers.
Creator: Mujumdar, Nirvani, Campiglia, Andres, Sigman, Michael, Harper, James, Rex, Matthew, Peale, Robert, University of Central Florida
Abstract / Description: The purpose of this dissertation is to advance nondestructive methodology for forensic fiber examination. Non-destructive techniques that can either discriminate between similar fibers or match a known to a questioned fiber (-) and still preserve the physical integrity of the fibers for further court examination - are highly valuable in forensic science. A challenging aspect of forensic fiber examinations involves the comparison of fibers colored with visually indistinguishable dyestuffs....
Show moreThe purpose of this dissertation is to advance nondestructive methodology for forensic fiber examination. Non-destructive techniques that can either discriminate between similar fibers or match a known to a questioned fiber (-) and still preserve the physical integrity of the fibers for further court examination - are highly valuable in forensic science. A challenging aspect of forensic fiber examinations involves the comparison of fibers colored with visually indistinguishable dyestuffs. This is not an uncommon situation, as there are numerous indistinguishable fibers pre-dyed with commercial dyes of virtually identical colors. Minimal chemical structural variations are actually encouraged by the dye patent process and commercial competition.The common denominator to forensic methodology is the fact that fiber analysis primarily focuses on the dyes used to color the fibers and do not investigate other potential discriminating components present in the fiber. This dissertation explores a different aspect of fiber analysis as it focuses on the total fluorescence emission of fibers. In addition to the contribution of the textile dye (or dyes) to the fluorescence spectrum of the fiber, we consider the contribution of intrinsic fluorescence impurities (-) i.e. impurities imbedded into the fibers during fabrication of garments - as a reproducible source of fiber comparison. Although fluorescence microscopy is used in forensic labs for single fiber examination, measurements are made with the aid of band-pass filters that provide very limited information on the spectral profiles of fibers. We take the non-destructive nature of fluorescence microscopy to a higher level of selectivity with the collection of room-temperature fluorescence excitation emission matrices (RTF-EEMs). The information contained in the EEMs was first used to select the best excitation wavelength for recording first order data, i.e. two-dimensional fluorescence spectra. Pairwise comparisons involved the following visually indistinguishable fibers: nylon 361 pre-dyed with acid yellow (AY) 17 and AY 23, acrylic 864 pre-dyed with basic green (BG) 1 and BG 4, acetate satin 105B pre-dyed with disperse blue (DB) 3 and DB 14, and polyester 777 pre-dyed with disperse red (DR) 1 and DR 19. With the exception of acrylic 864 fibers dyed with BG1 and BG4, the comparison of two-dimensional spectra via principal component analysis (PCA) provided accurate fiber identification for all the analyzed fibers. The same approach was later applied to the investigation of laundering effects on the comparison of textile fibers. The presence of brighteners and other detergent components adsorbed in the fibers provided spectral fingerprints that enhanced the fiber identification process.The full dimensionality of EEMs was then explored with the aid of parallel factor analysis (PARAFAC), a second order algorithm capable to determine the number of fluorescence components that contribute to an EEM along with their individual excitation and emission profiles. The application of PARAFAC was carried out unsupervised and supervised by linear discrimination analysis (LDA). The classification performances of PARAFAC and LDA-supervised PARAFAC were compared to the one obtained with supervised discriminant unfolded partial least squares (DU-PLS). The best discrimination was obtained with the supervised DU-PLS, which allowed the pairwise differentiation of the four pairs of investigated fibers.DU-PLS was then used to investigate weathering effects on the spectral features of cotton 400 pre-dyed with DB1, nylon 361 pre-dyed with AY17 and acrylic 864 pre-dyed with BG4. The investigated fibers were exposed to humid (Florida) and dry (Arizona) weathering conditions for three, six, nine and twelve months. In all cases, this algorithm was unable to differentiate non-exposed acrylic fibers from exposed acrylic fibers. DU-PLS was able to differentiate non-exposed cotton and nylon fibers from exposed fibers to Florida and Arizona weathering conditions. It was possible to determine the period of exposure to either Florida or Arizona conditions. It was also possible to discriminate between fibers exposed to Florida or Arizona weathering conditions for the same period of time. These results provide the foundation for future studies towards a non-destructive approach capable to provide information on the history of the fiber.
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Date Issued: 2016
Identifier: CFE0006838, ucf:51773
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006838

Title: Novel Photodynamic Cancer Therapy Agent and Biochemical Phosphate Sensor Based on Nanomaterials.
Creator: Fadhel, Alaa, Campiglia, Andres, Belfield, Kevin, Harper, James, Koculi, Eda, Bhattacharya, Aniket, University of Central Florida
Abstract / Description: Biochemical research and clinical studies have revolutionized the field of medicine in both diagnosis and therapy. Researchers in the field of biochemistry and biotechnology are using nanomaterials in different applications to develop devices and materials that offer benefits to both patients and the health care industry. These include biochemical sensors, enzyme encapsulation, biomarkers, and drug delivery improvements for the treatment of cancer. This dissertation focuses on investigating...
Show moreBiochemical research and clinical studies have revolutionized the field of medicine in both diagnosis and therapy. Researchers in the field of biochemistry and biotechnology are using nanomaterials in different applications to develop devices and materials that offer benefits to both patients and the health care industry. These include biochemical sensors, enzyme encapsulation, biomarkers, and drug delivery improvements for the treatment of cancer. This dissertation focuses on investigating two biochemical aspects using nanomaterials; namely therapy and clinical diagnosis.For therapy purposes, Silica nanoparticles were used as drug delivery system to develop a new photodynamic cancer therapy agent photo-acid generator (PAG) that selectively induces necrotic cell death of cancer cells. The developed PAG is oxygen-independent and - when excited at specific wavelengths - drops the pH within the lysosome of cancer cells to produce apoptosis/necrosis. It was specifically designed for in vivo applications and conjugated with synthesized, highly monodispersed silica nanoparticles (Si NPs) functionalized with amine groups via amid links (SiN-NH-PAG). Additional Features include high photo-acid quantum yield, high one-photon (1PA) and two-photon absorption (2PA) with low fluorescence quantum yield. In vivo, confocal microscope studies with HCT-116 (Human colorectal carcinoma) cancer cells showed that photodynamic processes in the presence of PAG were completed under one- photon absorption (1PA) conditions. In these experiments, cells were imaged at 1 min intervals for a total of 4 hours with the aid of Differential Interference Contrast (DIC). Among the photodynamic therapy agents tested via cytotoxicity experiments with the MTS assay, (SiN-NH- PAG) showed the best efficiency to induce cell death. The increased effectiveness of the new agent is probably due to the large number of PAG groups present on the surface of Si NPs.iiLysosome colocalization indicates that PAGs are mainly built in lysosomes. The increase of acidic content inside the lysosome was demonstrated with the aid of the LysoSensor Green probe. The drop in the intralysosomal pH was approximately 0.3 units. This is a desirable outcome as most cells underwent necrosis at pH ? 4.4. For clinical diagnosis purposes, a biochemical sensor was developed for the analysis of phosphate ions in urine samples. Abnormal levels of inorganic phosphate in human urine samples are related to the development of certain types of cancers affecting several organs of the human body, including breast, pancreas, lung and thyroid. The new biochemical sensor is based on the fluorescence energy transfer between a lanthanide luminescent probe [Tb-EDTA]-1 and gold nanoparticles (Au NPs) capped with a Cetyltrimethylammonium bromide (CTAB) micelle. With this approach, it was possible to selectively determine inorganic phosphate (Pi) in urine samples at the micro-molar concentration level. Urine samples collected from healthy, non-smoking individuals showed no interference from concomitants usually found in human urine samples. The simplicity of analysis provides an approach well-suited for (")real-time(") monitoring of phosphate ions. Analysis time is made possible within approximately 10 min per sample.
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Date Issued: 2016
Identifier: CFE0006528, ucf:51384
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006528

Title: Analysis of Benzopyrenes and Benzopyrene Metabolites by Fluorescence Spectroscopy Techniques.
Creator: Al-Farhani, Bassam, Campiglia, Andres, Harper, James, Zou, Shengli, Frazer, Andrew, Lee, Woo Hyoung, University of Central Florida
Abstract / Description: Polycyclic aromatic hydrocarbons (PAHs) are some of the most common and toxic pollutants encountered worldwide. Presently, monitoring is restricted to sixteen PAHs, but it is well understood that this list omits many toxic PAHs. Among the (")forgotten(") PAHs, isomers with molecular weight 302 are of particular concern due to their high toxicological properties. The chromatographic analysis of PAHs with MW 302 is challenged by similar retention times and virtually identical mass fragmentation...
Show morePolycyclic aromatic hydrocarbons (PAHs) are some of the most common and toxic pollutants encountered worldwide. Presently, monitoring is restricted to sixteen PAHs, but it is well understood that this list omits many toxic PAHs. Among the (")forgotten(") PAHs, isomers with molecular weight 302 are of particular concern due to their high toxicological properties. The chromatographic analysis of PAHs with MW 302 is challenged by similar retention times and virtually identical mass fragmentation patterns.The first original component of this dissertation evolves from a high-resolution spectroscopic approach specifically developed to fulfil this gap. Herein, 4.2 K Laser-Excited Time-Resolved Shpol'skii Spectroscopy (4.2K LETRSS) is applied to the analysis of HMW-PAHs in a complex coal tar standard reference material (SRM 1597a). The spectral and lifetime information obtained with LETRSS provide the required selectivity for the unambiguous determination of PAH isomers in the high-performance liquid chromatography (HPLC) fractions. Complete LETRSS analysis is possible with microliters of HPLC fractions and organic solvent. The excellent analytical figures of merit associated to its non-destructive nature, which provides ample opportunity for further analysis with other instrumental methods, makes this approach a unique alternative for the analysis of isomers of HMW-PAHs in complex environmental samples.The second original component of this dissertation focuses on the development of screening methodology for the routine analysis of PAH metabolites in urine samples. It explores the room-temperature fluorescence (RTF) properties of 3-hydroxy-benzo[a]pyrene, benzo[a]pyrene-trans-9,10-dihydrodiol, benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol and benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol previously extracted with octadecyl-silica membranes. RTF measurements from extraction membranes are carried out with the aid of fiber optic probe that eliminates the need for manual optimization of signal intensities. Relative standard deviations varying from 2.07% (benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol) to 8.55% (3-hydroxy-benzo[a]pyrene) were obtained with a straightforward procedure. Analytical recoveries from human urine samples varied from 87.54 (&)#177; 3.11% (3-hydroxy-benzo[a]pyrene) to 99.77 (&)#177; 2.48% (benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol). The excellent analytical figures of merit and the simplicity of the experimental procedure demonstrate the potential of Solid phase extraction-RTF for screening biomarkers of PAH exposure in numerous urine samples.
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Date Issued: 2016
Identifier: CFE0006520, ucf:51363
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006520

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

Title: Study of Polychlorinated Biphenyl Dechlorination by Zero Valent Magnesium With and Without Activated Carbon in Acidified Ethanol-Ethyl Lactate System.
Creator: Zullo, Fiona, Yestrebsky, Cherie, Clausen, Christian, Campiglia, Andres, Zou, Shengli, Duranceau, Steven, University of Central Florida
Abstract / Description: Polychlorinated biphenyls (PCBs) are synthetic organic chemicals that ca de detected in the environment worldwide. PCBs were banned in the U.S in 1979 owing to their toxicity and persistence in the environment. Today PCBs are classified as human carcinogens and are among the top ten of the U.S Environmental Protection Agency's (EPA) most toxic chemicals. Many researchers have shown soil to be contaminated with PCBs at concentrations as high as 750 ppm. Given the toxicity of PCBs, there is an...
Show morePolychlorinated biphenyls (PCBs) are synthetic organic chemicals that ca de detected in the environment worldwide. PCBs were banned in the U.S in 1979 owing to their toxicity and persistence in the environment. Today PCBs are classified as human carcinogens and are among the top ten of the U.S Environmental Protection Agency's (EPA) most toxic chemicals. Many researchers have shown soil to be contaminated with PCBs at concentrations as high as 750 ppm. Given the toxicity of PCBs, there is an urgent need to extract and degrade such chemicals from contaminated soil in a cost effective way. Prior work revealed a novel method of degradation of PCBs via hydrodehalogenation with zero-valent magnesium in acidified ethanol and ethyl lactate as a solvent system. Even though this degradation method gave satisfactory results for PCB degradation, this system cannot tolerate more than 3% water in order to degrade PCBs, limiting its application to wet soil field samples. In the present work a new system of acidified ethanol and ethyl lactate with ZVMg over activated carbon was developed which shows promising results on the degradation process of PCBs even with water present in the system. A detailed study of the byproducts formed in the dechlorination process and a degradation pathway, along with the activity of the system over time, are presented in this research.Also, a study of the mechanism involved in this reaction was done via computational methods to elucidate a mechanism pathway. It was demonstrated that these reactions are exothermic and involved two transition states, the formation of the first transition state being the limiting step of this reaction.The torsion angle of the PCB congeners was also shown to be an extremely important factor in order to be able to use activated carbon as part of the remediation process. These findings allow a greater understanding of the reductive dechlorination assisted by ZVMg and will help to improve the remediation process in field samples.
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Date Issued: 2016
Identifier: CFE0006205, ucf:51105
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006205

Title: Detection of Inorganic Phosphate in Environmental Water Samples using a Terbium and Gold Nanoparticle-based FRET Chemosensor.
Creator: Johnson, Madeleine, Campiglia, Andres, Zou, Shengli, Harper, James, Frazer, Andrew, Khondaker, Saiful, University of Central Florida
Abstract / Description: A novel chemosensor for the detection of inorganic phosphate (Pi) in environmental water samples is outlined. The sensing solution is comprised of a luminescent lanthanide, terbium (Tb3+), chelated to ethylenediaminetetraacetic acid (EDTA) acid in solution with cetyltrimethylammonium bromide (CTAB)- capped gold nanoparticles (AuNPs). The Tb-EDTA and AuNPs undergo a Fluorescence resonance energy transfer (FRET) mechanism in which the Tb3+ luminescence is quenched. Upon the addition of...
Show moreA novel chemosensor for the detection of inorganic phosphate (Pi) in environmental water samples is outlined. The sensing solution is comprised of a luminescent lanthanide, terbium (Tb3+), chelated to ethylenediaminetetraacetic acid (EDTA) acid in solution with cetyltrimethylammonium bromide (CTAB)- capped gold nanoparticles (AuNPs). The Tb-EDTA and AuNPs undergo a Fluorescence resonance energy transfer (FRET) mechanism in which the Tb3+ luminescence is quenched. Upon the addition of inorganic phosphate (Pi), the AuNPs begin to aggregate and precipitate out of solution. The aggregation of AuNPs results in the restoration of the Tb-EDTA signal which can then be correlated to Pi concentration in the matrix of analysis. The developed sensor has the potential for on-site monitoring of Pi in environmental waters at the sampling location; this would be advantageous for the prevention and understanding of eutrophication events caused by anthropogenic release of nutrients such as Pi. The limit of detection (LOD) of the luminescence sensor (83 ppb-Pi) is within the range of LODs previously reported for on-site monitoring of Pi. Quantitative analysis carried out via the multiple standard additions method provided accurate determination of Pi concentrations in heavily contaminated environmental waters. Additional studies include the synthesis of an organic antenna for the sensitization of the lanthanide ion and further improvement of detection levels.
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Date Issued: 2017
Identifier: CFE0006747, ucf:51874
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006747

Title: Non-Destructive Analysis of Trace Textile Fiber Evidence via Room-Temperature Fluorescence Spectrocopy.
Creator: Appalaneni, Krishnaveni, Campiglia, Andres, Belfield, Kevin, Sigman, Michael, Yestrebsky, Cherie, Schulte, Alfons, University of Central Florida
Abstract / Description: Forensic fiber evidence plays an important role in many criminal investigations. Non-destructive techniques that preserve the physical integrity of the fibers for further court examination are highly valuable in forensic science. Non-destructive techniques that can either discriminate between similar fibers or match a known to a questioned fiber - and still preserve the physical integrity of the fibers for further court examination - are highly valuable in forensic science. When fibers cannot...
Show moreForensic fiber evidence plays an important role in many criminal investigations. Non-destructive techniques that preserve the physical integrity of the fibers for further court examination are highly valuable in forensic science. Non-destructive techniques that can either discriminate between similar fibers or match a known to a questioned fiber - and still preserve the physical integrity of the fibers for further court examination - are highly valuable in forensic science. When fibers cannot be discriminated by non-destructive tests, the next reasonable step is to extract the questioned and known fibers for dye analysis with a more selective technique such as high-performance liquid chromatography (HPLC) and/or gas chromatography-mass spectrometry (GC-MS). The common denominator among chromatographic techniques is to primarily focus on the dyes used to color the fibers and do not investigate other potential discriminating components present on the fiber. Differentiating among commercial dyes with very similar chromatographic behaviors and almost identical absorption spectra and/or fragmentation patterns is a challenging task.This dissertation explores a different aspect of fiber analysis as it focuses on the total fluorescence emission of fibers. In addition to the contribution of the textile dye (or dyes) to the fluorescence spectrum of the fiber, we investigate the contribution of intrinsic fluorescence impurities (-) i.e. impurities imbedded into the fibers during fabrication of garments - as a reproducible source of fiber comparison. Differentiation of visually indistinguishable fibers is achieved by comparing excitation-emission matrices (EEMs) recorded from single textile fibers with the aid of a commercial spectrofluorimeter coupled to an epi-fluorescence microscope. Statistical data comparison was carried out via principal component analysis. An application of this statistical approach is demonstrated using challenging dyes with similarities both in two-dimensional absorbance spectra and in three dimensional EEM data. High accuracy of fiber identification was observed in all the cases and no false positive identifications were observed at 99% confidence levels.
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Date Issued: 2013
Identifier: CFE0004808, ucf:49740
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004808

Title: Selective Multivariate Applications in Forensic Science.
Creator: Rinke, Caitlin, Sigman, Michael, Campiglia, Andres, Yestrebsky, Cherie, Kuebler, Stephen, Richardson, Martin, University of Central Florida
Abstract / Description: A 2009 report published by the National Research Council addressed the need for improvements in the field of forensic science. In the report emphasis was placed on the need for more rigorous scientific analysis within many forensic science disciplines and for established limitations and determination of error rates from statistical analysis. This research focused on multivariate statistical techniques for the analysis of spectral data obtained for multiple forensic applications which include...
Show moreA 2009 report published by the National Research Council addressed the need for improvements in the field of forensic science. In the report emphasis was placed on the need for more rigorous scientific analysis within many forensic science disciplines and for established limitations and determination of error rates from statistical analysis. This research focused on multivariate statistical techniques for the analysis of spectral data obtained for multiple forensic applications which include samples from: automobile float glasses and paints, bones, metal transfers, ignitable liquids and fire debris, and organic compounds including explosives. The statistical techniques were used for two types of data analysis: classification and discrimination. Statistical methods including linear discriminant analysis and a novel soft classification method were used to provide classification of forensic samples based on a compiled library. The novel soft classification method combined three statistical steps: Principal Component Analysis (PCA), Target Factor Analysis (TFA), and Bayesian Decision Theory (BDT) to provide classification based on posterior probabilities of class membership. The posterior probabilities provide a statistical probability of classification which can aid a forensic analyst in reaching a conclusion. The second analytical approach applied nonparametric methods to provide the means for discrimination between samples. Nonparametric methods are performed as hypothesis test and do not assume normal distribution of the analytical figures of merit. The nonparametric permutation test was applied to forensic applications to determine the similarity between two samples and provide discrimination rates. Both the classification method and discrimination method were applied to data acquired from multiple instrumental methods. The instrumental methods included: Laser Induced-Breakdown Spectroscopy (LIBS), Fourier Transform Infrared Spectroscopy (FTIR), Raman spectroscopy, and Gas Chromatography-Mass Spectrometry (GC-MS). Some of these instrumental methods are currently applied to forensic applications, such as GC-MS for the analysis of ignitable liquid and fire debris samples; while others provide new instrumental methods to areas within forensic science which currently lack instrumental analysis techniques, such as LIBS for the analysis of metal transfers. The combination of the instrumental techniques and multivariate statistical techniques is investigated in new approaches to forensic applications in this research to assist in improving the field of forensic science.
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Date Issued: 2012
Identifier: CFE0004628, ucf:49942
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004628

Title: Application of Two-Photon Absorbing Fluorene-Containing Compounds in Bioimaging and Photodyanimc Therapy.
Creator: Yue, Xiling, Belfield, Kevin, Campiglia, Andres, Miles, Delbert, Frazer, Andrew, Cheng, Zixi, University of Central Florida
Abstract / Description: Two-photon absorbing (2PA) materials has been widely studied for their highly localized excitation and nonlinear excitation efficiency. Application of 2PA materials includes fluorescence imaging, microfabrication, 3D data storage, photodynamic therapy, etc. Many materials have good 2PA photophysical properties, among which, the fluorenyl structure and its derivatives have attracted attention with their high 2PA cross-section and high fluorescence quantum yield.Herein, several compounds with...
Show moreTwo-photon absorbing (2PA) materials has been widely studied for their highly localized excitation and nonlinear excitation efficiency. Application of 2PA materials includes fluorescence imaging, microfabrication, 3D data storage, photodynamic therapy, etc. Many materials have good 2PA photophysical properties, among which, the fluorenyl structure and its derivatives have attracted attention with their high 2PA cross-section and high fluorescence quantum yield.Herein, several compounds with 2PA properties are discussed. All of these compounds contain one or two fluorenyl core units as part of the conjugated system. The aim of this dissertation is to discuss the application of these compounds according to their photophysical properties. In chapters 2 to 4, compounds were investigated for cell imaging and tissue imaging. In chapter 5, compounds were evaluated for photodynamic therapy effects on cancer cells. Chapters 2 and 3 detail compounds with quinolizinium and pyran as core structures, respectively. Fluorene was introduced into structures as substituents. Quinolizinium structures exhibited a large increase in fluorescence when binding with Bovine Serum Albumin (BSA). Further experiments in cell imaging demonstrated a fluorescence turn-on effect in cell membranes, indicating the possibility for these novel compounds to be promising membrane probes. Pyran structures were conjugated with arginylglycylaspartic acid peptide (RGD) to recognize integrin and introduced in cells and an animal model with tumors. Both probes showed specific targeting of tumor vasculature. Imaging reached penetration as deep as 350 ?m in solid tumors and exhibited good resolution. These results suggest the RGD-conjugated pyran structure should be a good candidate probe for live tissue imaging. Chapter 4 applied a fluorene core structure conjugated with RGD as well. Application of this fluorenyl probe compound is in wound healing animal models. Fluorescence was collected from vasculature and fibroblasts up to ? 1600 ?m within wound tissue in lesions made on the skin of mice. The resolution of images is also high enough to recognize cell types by immunohistochemical staining. This technology can be applied for reliable quantification and illustration of key biological processes taking place during tissue regeneration in the skin. Chapter 5 describes three fluorenyl core structures with photoacid generation properties. One of the structures showed excellent photo-induced toxicity. Cancer cells underwent necrotic cell death due to pH decrease in lysosomes and endosomes, suggesting a new mechanism for photodynamic therapy.
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Date Issued: 2014
Identifier: CFE0005565, ucf:50276
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005565

Title: Mass Spectral Studies to Investigate Butylbenzene Fragmentation Pathway and Pyrolysis Products.
Creator: Lingam, Balasubramaniam, Sigman, Michael, Clausen, Christian, Campiglia, Andres, Miles, Delbert, Schulte, Alfons, University of Central Florida
Abstract / Description: In this dissertation research, two fundamental studies involving gas chromatography mass spectrometry of n-butylbenzene and pyrolysis products are presented. In the first study, fragmentation pathways of n-butylbenzene in quadrupole ion trap have been investigated. At low energy, product ion corresponding to m/z 92 and m/z 91 are formed via competitive parallel dissociation. Studies have also shown that at higher energy m/z 92 has sufficient internal energy to undergo further fragmentation...
Show moreIn this dissertation research, two fundamental studies involving gas chromatography mass spectrometry of n-butylbenzene and pyrolysis products are presented. In the first study, fragmentation pathways of n-butylbenzene in quadrupole ion trap have been investigated. At low energy, product ion corresponding to m/z 92 and m/z 91 are formed via competitive parallel dissociation. Studies have also shown that at higher energy m/z 92 has sufficient internal energy to undergo further fragmentation yielding m/z 91 via consecutive dissociation. Thus in order to discern the fragmentation pathways of n-butylbenzene, the technique of two-dimensional correlation spectroscopy (2DCOS) was applied to the mass spectral data. Application of 2DCOS resulted in two 2D correlation spectra namely synchronous and asynchronous. A third spectra known as coherence spectra was obtained from the ration of asynchronous to synchronous correlation intensities. For the elucidation of n-butylbenzene fragmentation pathways, all the three spectra were utilized in this study. The second study in this dissertation involves investigation of pyrolysis products to aid in fire debris analysis. One of the major concerns in fire debris analysis is that pyrolysis products can mask the patterns of compounds of interest and make the chromatographic results interpretation extremely difficult. One of the approaches for investigating the formation of pyrolysis products is to subject the commonly found building materials to controlled heating in laboratory. In this study, new heating methodologies for controlled heating of substrates involving furnace, paint-cans and flat steel pans have been developed. The substrates used for investigating pyrolysis products were polystyrene, polyvinylchloride, polybutadiene, yellow-pine, nylon carpet and padding. Experiments were also performed to investigate the influence of hydrocarbons on the formation of pyrolysis.
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Date Issued: 2015
Identifier: CFE0005651, ucf:50167
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005651

Title: Enhanced Two-Photon Absorption in a Squaraine-Fluorene-Squaraine Dye: Design, Synthesis, Photophysical Properties, and Solvatochromic Behavior.
Creator: Moreshead, William, Belfield, Kevin, Campiglia, Andres, Zou, Shengli, Frazer, Andrew, Beiler, Rosalind, University of Central Florida
Abstract / Description: The discovery of any new technology is usually accompanied by a need for new or improved materials which make that technology useful in practical applications. In the case of two-photon absorption (2PA) this has truly been the case. Since its first demonstration in 1961, there has been an ever increasing quest to understand the relationships between two-photon absorption and the structure of two-photon absorbing materials. This quest has been motivated by the many applications for 2PA which...
Show moreThe discovery of any new technology is usually accompanied by a need for new or improved materials which make that technology useful in practical applications. In the case of two-photon absorption (2PA) this has truly been the case. Since its first demonstration in 1961, there has been an ever increasing quest to understand the relationships between two-photon absorption and the structure of two-photon absorbing materials. This quest has been motivated by the many applications for 2PA which have been reported, including fluorescence bioimaging, 3D microfabrication, 3D optical data storage, upconverted lasing, and photodynamic therapy.The work presented in this dissertation represents another step in the effort to better understand the structure/property relationships of 2PA. In this work a new, squaraine-fluorene-squaraine molecule, proposed through a joint effort of quantum and synthetic chemists, was synthesized and its photophysical properties were measured. The measurements included linear and two-photon photophysical properties, as well as solvatochromic behavior. Quantum calculations were done to aid in understanding those photophysical and solvatochromic properties. A single squaraine dye was also synthesized and used as a model compound to assist in understanding this new structure.In Chapter 1 an introduction to 2PA and several of its applications is given. Chapter 2 gives a background of 2PA structure/property relationships that have been reported to date, based on work done with polymethine dyes. Chapter 3 gives a full account of the synthesis, characterization, and detailed quantum chemical analyses of this new squaraine-fluorene-squaraine molecule and the corresponding model compound squaraine dye. Chapter 4 gives some additional work and suggested future directions.
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Date Issued: 2013
Identifier: CFE0005384, ucf:50450
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005384

chemometrics (4)	+ -
Fluorescence (3)	+ -
Two-photon absorption (3)	+ -
forensic science (3)	+ -
photodynamic therapy (3)	+ -

two-photon absorption (3)	+ -
Analytical Chemistry (2)	+ -
BODIPY (2)	+ -
Chemometrics (2)	+ -
Degradation (2)	+ -
J-aggregation (2)	+ -
Polycyclic Aromatic Hydrocarbons (2)	+ -
SSNMR (2)	+ -
Shpol'skii spectroscopy (2)	+ -
Textile Fibers (2)	+ -
benzo[a]pyrene (2)	+ -
fire debris (2)	+ -
fluorescence microscopy (2)	+ -
fluorescence spectroscopy (2)	+ -
multivariate statistics (2)	+ -
polycyclic aromatic hydrocarbons (2)	+ -
spectroscopy (2)	+ -
1JCC (1)	+ -
5-methylmellein (1)	+ -
A549 (1)	+ -
Accelerated durability (1)	+ -
Agglomerative Hierarchical Cluster Analysis (1)	+ -
Aggreagtion in solid state (1)	+ -
Azulene (1)	+ -
BAPTA (1)	+ -

Campiglia, Andres (51)	+ -
University of Central Florida (51)	+ -
Belfield, Kevin (15)	+ -
Harper, James (15)	+ -
Yestrebsky, Cherie (15)	+ -

Sigman, Michael (13)	+ -
Frazer, Andrew (12)	+ -
Zou, Shengli (11)	+ -
Clausen, Christian (7)	+ -
Cheng, Zixi (6)	+ -
Rex, Matthew (6)	+ -
Bhattacharya, Aniket (5)	+ -
Chumbimuni Torres, Karin (5)	+ -
Miles, Delbert (5)	+ -
Bridge, Candice (4)	+ -
Ni, Liqiang (4)	+ -
Coffey, Kevin (3)	+ -
Schulte, Alfons (3)	+ -
Beazley, Melanie (2)	+ -
Blair, Richard (2)	+ -
Duranceau, Steven (2)	+ -
Elsheimer, Seth (2)	+ -
Gesquiere, Andre (2)	+ -
Heider, Emily (2)	+ -
Hernandez, Florencio (2)	+ -
Khondaker, Saiful (2)	+ -
Kolpashchikov, Dmitry (2)	+ -
Lee, Woo Hyoung (2)	+ -
Tetard, Laurene (2)	+ -
Ye, Jingdong (2)	+ -

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