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- Title
- Multimaterial Fibers and Tapers A Platform for Nonlinear Photonics and Nanotechnology.
- Creator
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Shabahang, Soroush, Abouraddy, Ayman, Vanstryland, Eric, Dogariu, Aristide, Belfield, Kevin, University of Central Florida
- Abstract / Description
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The development of optical sources and components suitable for the mid-infrared is crucial for applications in this spectral range to reach the maturity level of their counterparts in the visible and near-infrared spectral regimes. The recent commercialization of quantum cascade lasers is leading to further interest in this spectral range. Wideband mid-infrared coherent sources, such as supercontinuum generation, have yet to be fully developed. A mid-infrared supercontinuum source would allow...
Show moreThe development of optical sources and components suitable for the mid-infrared is crucial for applications in this spectral range to reach the maturity level of their counterparts in the visible and near-infrared spectral regimes. The recent commercialization of quantum cascade lasers is leading to further interest in this spectral range. Wideband mid-infrared coherent sources, such as supercontinuum generation, have yet to be fully developed. A mid-infrared supercontinuum source would allow for unique applications in spectroscopy and sensing.Over the last decade, it has been shown that high-index confinement in highly nonlinear fibers pumped with high-peak-power pulses is an excellent approach to supercontinuum generation in the visible and near-infrared. Nonlinear waveguides such as fibers offer an obvious advantage in increasing the nonlinear interaction length maintained with a small cross section. In addition, fiber systems do not require optical alignment and are mechanically stable and robust with respect to the environmental changes. These properties have made fiber systems unique in applications where they are implemented in a harsh and unstable environment.In extending this approach into the mid-infrared, I have used chalcogenide glass fibers. Chalcogenide glasses have several attractive features for this application: they have high refractive indices for high optical-confinement, have a wide transparency window in the mid-infrared, and have a few orders-of-magnitude higher nonlinearity than silica glass and other mid-IR glasses. Producing chalcogenide glass fiber tapers offer, furthermore, the possibility of dispersion control and stronger field confinement and hence higher nonlinearity, desired for supercontinuum generation.
Show less - Date Issued
- 2014
- Identifier
- CFE0005252, ucf:50594
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005252
- Title
- Chemometric Applications to a Complex Classification Problem: Forensic Fire Debris Analysis.
- Creator
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Waddell, Erin, Sigman, Michael, Belfield, Kevin, Campiglia, Andres, Yestrebsky, Cherie, Ni, Liqiang, University of Central Florida
- Abstract / Description
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Fire debris analysis currently relies on visual pattern recognition of the total ion chromatograms, extracted ion profiles, and target compound chromatograms to identify the presence of an ignitable liquid according to the ASTM International E1618-10 standard method. For large data sets, this methodology can be time consuming and is a subjective method, the accuracy of which is dependent upon the skill and experience of the analyst. This research aimed to develop an automated classification...
Show moreFire debris analysis currently relies on visual pattern recognition of the total ion chromatograms, extracted ion profiles, and target compound chromatograms to identify the presence of an ignitable liquid according to the ASTM International E1618-10 standard method. For large data sets, this methodology can be time consuming and is a subjective method, the accuracy of which is dependent upon the skill and experience of the analyst. This research aimed to develop an automated classification method for large data sets and investigated the use of the total ion spectrum (TIS). The TIS is calculated by taking an average mass spectrum across the entire chromatographic range and has been shown to contain sufficient information content for the identification of ignitable liquids. The TIS of ignitable liquids and substrates, defined as common building materials and household furnishings, were compiled into model data sets. Cross-validation (CV) and fire debris samples, obtained from laboratory-scale and large-scale burns, were used to test the models. An automated classification method was developed using computational software, written in-house, that considers a multi-step classification scheme to detect ignitable liquid residues in fire debris samples and assign these to the classes defined in ASTM E1618-10. Classifications were made using linear discriminant analysis, quadratic discriminant analysis (QDA), and soft independent modeling of class analogy (SIMCA). Overall, the highest correct classification rates were achieved using QDA for the first step of the scheme and SIMCA for the remaining steps. In the first step of the classification scheme, correct classification rates of 95.3% and 89.2% were obtained for the CV test set and fire debris samples, respectively. Correct classifications rates of 100% were achieved for both data sets in the majority of the remaining steps which used SIMCA for classification. In this research, the first statistically valid error rates for fire debris analysis have been developed through cross-validation of large data sets. The error rates reduce the subjectivity associated with the current methods and provide a level of confidence in sample classification that does not currently exist in forensic fire debris analysis.
Show less - Date Issued
- 2013
- Identifier
- CFE0004954, ucf:49586
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004954
- Title
- Synthesis of Fluorescent Molecules and their Applications as Viscosity Sensors, Metal Ion Indicators, and Near-Infrared Probes.
- Creator
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Wang, Mengyuan, Belfield, Kevin, Campiglia, Andres, Miles, Delbert, Frazer, Andrew, Cheng, Zixi, University of Central Florida
- Abstract / Description
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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.
Show less - Date Issued
- 2014
- Identifier
- CFE0005900, ucf:50863
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005900
- Title
- Investigating New Guaiazulenes and Diketopyrropyrroles for Photonic Applications.
- Creator
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Ghazvini Zadeh, Ebrahim, Belfield, Kevin, Campiglia, Andres, Yuan, Yu, Zou, Shengli, Cheng, Zixi, University of Central Florida
- Abstract / Description
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?-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.
Show less - 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
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Tang, Simon, Belfield, Kevin, Miles, Delbert, Campiglia, Andres, Zou, Shengli, Cheng, Zixi, University of Central Florida
- Abstract / Description
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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.
Show less - 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
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Kim, Bosung, Belfield, Kevin, Zou, Shengli, Campiglia, Andres, Frazer, Andrew, Ali, Gul Shad, University of Central Florida
- Abstract / Description
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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.
Show less - Date Issued
- 2015
- Identifier
- CFE0006041, ucf:50977
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006041
- Title
- Fluorescence Off-On Sensors for F-, K+, Fe3+, and Ca2+ Ions.
- Creator
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Sui, Binglin, Belfield, Kevin, Miles, Delbert, Zou, Shengli, Frazer, Andrew, Bhattacharya, Aniket, University of Central Florida
- Abstract / Description
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Fluorescence spectroscopy has been considered to be one of the most important research techniques in modern analytical chemistry, biochemistry, and biophysics. At present, fluorescence is a dominant methodology widely used in a great number of research domains, including biotechnology, medical diagnostics, genetic analysis, DNA sequencing, flow cytometry, and forensic analysis, to name just a few. In the past decade, with the rapid development of fluorescence microscopy, there has been a...
Show moreFluorescence spectroscopy has been considered to be one of the most important research techniques in modern analytical chemistry, biochemistry, and biophysics. At present, fluorescence is a dominant methodology widely used in a great number of research domains, including biotechnology, medical diagnostics, genetic analysis, DNA sequencing, flow cytometry, and forensic analysis, to name just a few. In the past decade, with the rapid development of fluorescence microscopy, there has been a considerable growth in applying fluorescence technique to cellular imaging. The distinguished merits of fluorescence techniques, such as high sensitivity, non-invasiveness, low cytotoxicity, low cost, and convenience, make it a promising tool to replace radioactive tracers for most biochemical measurements, avoiding the high expense and difficulties of handling radioactive tracers.Among the wide range of applications of fluorescence technique, fluorescent sensing of various cations and anions is one of the most important and active areas. This dissertation is all about developing fluorescent sensors for physiologically significant ions, including F-, K+, Fe3+, and Ca2+. All of these sensors demonstrate fluorescence (")turn-on(") response upon interacting with their respective ions, which makes them much more appealing than those based on fluorescence quenching mechanisms.In Chapter II, a novel highly selective fluorescence turn-on F- sensor (FS), comprised of a fluorene platform serving as the chromophore, and two 1,2,3-triazolium groups functioning as the signaling moieties, is described. The function of FS is established on the basis of deprotonation of the C-H bonds of 1,2,3-triazolium groups, which makes FS the first reported anion sensor based on the deprotonation of a C-H bond. Easy-to-prepare test strips were prepared for determining F- in aqueous media, providing an inexpensive and convenient approach to estimate whether the concentration of F- contained in drinking water is at a safe level.Chapter III contains an optimized synthesis of a reported K+-selective group (TAC), and the development of two TAC-based fluorescence turn-on K+ sensors (KS1 and KS2). The synthetic route of TAC is shortened and its overall yield is enhanced from 3.6% to 19.5%. Both KS1 and KS2 exhibited excellent selectivity toward K+ over other physiological metal cations, high sensitivity for K+ sensing, and pH insensitivity in the physiological pH range. Confocal fluorescence microscopy experiments demonstrate that they are capable of sensing K+ within living cells. 2PA determination reveals that KS2 has a desirable 2PA cross section of 500 GM at 940 nm, which makes it a two-photon red-emitting fluorescent sensor for K+.Chapter IV describes the development of a novel BODIPY-based fluorescence turn-on Fe3+ sensor (FeS). FeS is a conjugate of two moieties, a BODIPY platform serving as the fluorophore and a 1,10-diaza-18-crown-6 based cryptand acting as the Fe3+ recognition moiety. FeS displays good selectivity, high sensitivity, reversibility, and pH insensitivity toward Fe3+ sensing. Based on its excellent performance in determining Fe3+ and very low cytotoxicity, FeS was effectively applied to sensing Fe3+ in living cells.In Chapter V, a new BODIPY-based fluorescence turn-on sensor (CaS) was designed and synthesized for selectively and sensitively determining Ca2+. CaS is comprised of two moieties, a BODIPY fluorophore and a Ca2+ complexing unit. CaS demonstrated selective fluorescence turn-on response towards Ca2+ over other biological metal cations. Moreover, CaS exhibited desirable sensitivity for Ca2+ detection, which makes it more suitable for extracellular Ca2+ determination. In addition, CaS was insensitive to the pH of the physiological environment, especially in the pH range of blood and serum. Therefore, CaS has potential to be applied to sensing Ca2+ ions in extracellular environments.Chapter VI discusses potential future work of KS2 and CaS, following the results achieved in this dissertation. Based on the desirable performances of both sensors in sensing their respective ions, future work could largely be focused on their applications in cellular imaging.
Show less - Date Issued
- 2014
- Identifier
- CFE0005888, ucf:50883
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005888
- 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
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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.
Show less - 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
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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.
Show less - 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
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Knobel, Gaston, Campiglia, Andres, Clausen, Christian, Belfield, Kevin, Liao, Yi, Bhattacharya, Aniket, University of Central Florida
- Abstract / Description
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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.
Show less - Date Issued
- 2013
- Identifier
- CFE0005102, ucf:50761
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005102
- 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
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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.
Show less - Date Issued
- 2016
- Identifier
- CFE0006528, ucf:51384
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006528
- Title
- Non-Destructive Analysis of Trace Textile Fiber Evidence via Room-Temperature Fluorescence Spectrocopy.
- Creator
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Appalaneni, Krishnaveni, Campiglia, Andres, Belfield, Kevin, Sigman, Michael, Yestrebsky, Cherie, Schulte, Alfons, University of Central Florida
- Abstract / Description
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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.
Show less - Date Issued
- 2013
- Identifier
- CFE0004808, ucf:49740
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004808
- Title
- Cascaded plasmon resonances for enhanced nonlinear optical response.
- Creator
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Toroghi, Seyfollah, Kik, Pieter, Vanstryland, Eric, Kuebler, Stephen, Hagan, David, Belfield, Kevin, University of Central Florida
- Abstract / Description
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The continued development of integrated photonic devices requires low-power, small volume all-optical modulators. The weak nonlinear optical response of conventional optical materials requires the use of high intensities and large interaction volumes in order to achieve significant light modulation, hindering the miniaturization of all-optical switches and the development of lightweight transmission optics with nonlinear optical response. These challenges may be addressed using plasmonic...
Show moreThe continued development of integrated photonic devices requires low-power, small volume all-optical modulators. The weak nonlinear optical response of conventional optical materials requires the use of high intensities and large interaction volumes in order to achieve significant light modulation, hindering the miniaturization of all-optical switches and the development of lightweight transmission optics with nonlinear optical response. These challenges may be addressed using plasmonic nanostructures due to their unique ability to confine and enhance electric fields in sub-wavelength volumes. The ultrafast nonlinear response of free electrons in such plasmonic structures and the fast thermal nonlinear optical response of metal nanoparticles, as well as the plasmon enhanced nonlinear Kerr-type response of the host material surrounding the nanostructures could allow ultrafast all-optical modulation with low modulation energy. In this thesis, we investigate the linear and nonlinear optical response of engineered effective media containing coupled metallic nanoparticles. The fundamental interactions in systems containing coupled nanoparticles with size, shape, and composition dissimilarity, are evaluated analytically and numerically, and it is demonstrated that under certain conditions the achieved field enhancement factors can exceed the single-particle result by orders of magnitude in a process called cascaded plasmon resonance. It is demonstrated that these conditions can be met in systems containing coupled nanospheres, and in systems containing non-spherical metal nanoparticles that are compatible with common top-down nanofabrication methods such as electron beam lithography and nano-imprint lithography. We show that metamaterials based on such cascaded plasmon resonance structures can produce enhanced nonlinear optical refraction and absorption compared to that of conventional plasmonic nanostructures. Finally, it is demonstrated that the thermal nonlinear optical response of metal nanoparticles can be enhanced in carefully engineered heterogeneous nanoparticle clusters, potentially enabling strong and fast thermal nonlinear optical response in system that can be produced in bulk through chemical synthesis.
Show less - Date Issued
- 2014
- Identifier
- CFE0005556, ucf:50272
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005556
- Title
- Application of Two-Photon Absorbing Fluorene-Containing Compounds in Bioimaging and Photodyanimc Therapy.
- Creator
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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.
Show less - Date Issued
- 2014
- Identifier
- CFE0005565, ucf:50276
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005565
- Title
- Synthesis of Fluorene-based derivatives, Characterization of Optical properties and their Applications in Two-photon Fluorescence Imaging and Photocatalysis.
- Creator
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Githaiga, Grace, Belfield, Kevin, Patino Marin, Pedro, Chumbimuni Torres, Karin, Zou, Shengli, Cheng, Zixi, University of Central Florida
- Abstract / Description
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The two-photon absorption (2PA) phenomenon has attracted attention from various fields ranging from chemistry and biology to optics and engineering. Two of the common NLO applications in which organic materials have been used are three-dimensional (3D) fluorescence imaging and optical power limiting. Two-photon absorbing materials are, therefore, in great demand to meet the needs of emerging technologies. Organic molecules show great promise to meet this need as they can be customized through...
Show moreThe two-photon absorption (2PA) phenomenon has attracted attention from various fields ranging from chemistry and biology to optics and engineering. Two of the common NLO applications in which organic materials have been used are three-dimensional (3D) fluorescence imaging and optical power limiting. Two-photon absorbing materials are, therefore, in great demand to meet the needs of emerging technologies. Organic molecules show great promise to meet this need as they can be customized through molecular engineering, and as the development of two-photon materials that suit practical application intensifies, so does research to meet this need. However, there remains some uncertainty in the particulars of design criteria for molecules with large 2PA cross sections at desired wavelengths, as such research to understand structure-property relationships is matter of significant importance. As a result, the full potential of 2PA materials has not been fully exploited. Several strategies to enhance the magnitude and tune the wavelength of 2PA have been reported for ?-conjugated organic molecules. On this account, we have designed novel fluorophores using the fluorene moiety and modified it to tune the properties of the compounds.Chapter 2 of this dissertation reports the successful application of fluorene-based compounds in photocatalysis; a process that involves the decomposition of organic compounds into environmentally friendly carbon dioxide and water attesting to the photostability of the fluorene moiety. A facile organic nanoparticle preparation method is reported in chapter 3 using the reprecipitation method, whose surface was then modified using a naturally occurring surfactant, Lecithin, and were then successfully used in fluorescence cell imaging. Chapter 4 reports the design and synthesis of a fluorene-based compound using an acceptor, s-indacene-1, 3, 5, 7(2H, 6H)-tetra one, or Janus Dione, a moiety that is relatively new and that has not been fully exploited despite its very attractive features. Owing to the hydrophobicity of this compound, notwithstanding its unprecedented 2PA cross section, it was not applicable in fluorescence cell imaging but provided the tenets for the design of related derivative. This limitation was circumvented in the concluding chapter by tuning the compound's hydrophilicity. The hydrophilic Janus dione probe was then used as envisioned for cell imaging as the dual prerequisites for fluorescence imaging probes; large 2PA cross sections and high fluorescence quantum yields were met.
Show less - Date Issued
- 2015
- Identifier
- CFE0005620, ucf:50207
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005620
- Title
- Enhanced Two-Photon Absorption in a Squaraine-Fluorene-Squaraine Dye: Design, Synthesis, Photophysical Properties, and Solvatochromic Behavior.
- Creator
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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.
Show less - Date Issued
- 2013
- Identifier
- CFE0005384, ucf:50450
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005384
- Title
- Aggregation of Squaraine Dye Derivatives in Solid State Spin-coated Thin Films.
- Creator
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Daoudi, Mohammed, Belfield, Kevin, Miles, Delbert, Campiglia, Andres, Bhattacharya, Aniket, Rex, Matthew, University of Central Florida
- Abstract / Description
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Squaraine dyes have been the subject of intensive studies due their unusual electronic properties that make them good candidates for a wide range of applications in various technological fields. They are particularly promising in nonlinear optics, bioimaging for labeling and sensing of biomolecules, as sensitizers for solar energy harvesting in solar cells and organic photovoltaics, two-photon absorbing materials, near-infrared (NIR) emitting fluorescent probes, second harmonic generation...
Show moreSquaraine dyes have been the subject of intensive studies due their unusual electronic properties that make them good candidates for a wide range of applications in various technological fields. They are particularly promising in nonlinear optics, bioimaging for labeling and sensing of biomolecules, as sensitizers for solar energy harvesting in solar cells and organic photovoltaics, two-photon absorbing materials, near-infrared (NIR) emitting fluorescent probes, second harmonic generation organic dyes, and sensitizers for photodynamic therapy among others. In this dissertation, the aggregation behaviors and features of several squaraine dye derivatives in solid state thin films were studied and reported.In the first chapter of the dissertation, three squaraine dye derivatives with two and four hydroxy groups and with different N-alkyl amino donor substituents were synthesized and used as models to study aggregation behavior. Their UV-vis absorption, thermal properties, and photoluminescence properties were determined. The models with four hydroxy substituents exhibited higher thermal stability and melt at higher temperature compared to the dye with only two hydroxy substituents due to increased hydrogen bonding. The UV-vis absorption and photoluminescence properties in liquid solution at room temperature were found to be similar.In the second chapter, the squaraine dyes, 2,4-bis [4-(N,N-di-n-pentylamino)-2-hydroxyphenyl] squaraine [SQC5(OH)2], 2,4-bis [4-(N,N-di-n-pentylamino)-2,4-hydroxyphenyl] squaraine [SQC5(OH)4 n], and 2,4-bis [4-(N,N-di-isopentylamino)-2,4-hydroxyphenyl] squaraine [SQC5(OH)4 b], where (")n(") and (")b(") stand for normal or linear and branched alkyl groups, respectively, were investigated to study their aggregation in solid state thin film form using UV-vis absorption spectroscopy. The investigation revealed significant differences in aggregation behaviors and features. The dye SQC5(OH)2 mainly exhibited J-type aggregation with an intense absorption band in the NIR region. In contrast, the SQC5(OH)4 n and SQC5(OH)4 b compounds mainly exhibited H-type aggregation, characterized by less intense and blue shifted absorption bands. The third chapter presents the kinetic study conducted on the squaraine dye derivative 2,4-bis [4-(N,N-di-n-pentylamino)-2-hydroxyphenyl] squaraine [SQC5(OH)2] in solid state spin-coated thin films. The study revealed the formation of J-aggregates with bands at 767 nm at room temperature. This aggregate was temperature dependent. It was transformed into H-aggregates as the temperature increased. The activation energy of the decay (transformation) process was found to be 91.2 kJ. The values of ?H and ?S are 88.4 kJ/mol and 48.2 J/K.mol, respectively, indicating the J-aggregate of SQC5(OH)2 was a kinetic product while the H-aggregate was thermondynamically more stable.
Show less - Date Issued
- 2015
- Identifier
- CFE0005778, ucf:50064
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005778
- Title
- Overexpression of human Cu/Zn Superoxide Dismutase in Mice: A Model to Study the Effect of Increased Superoxide Scavenging on the Autonomic Control of the Heart.
- Creator
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Hatcher, Jeffrey, Cheng, Zixi, Bossy-Wetzel, Ella, Fernandez-Valle, Cristina, Belfield, Kevin, University of Central Florida
- Abstract / Description
-
Dysregulation of the autonomic cardiovascular control is a complication of diseases including diabetes, hypertension, sleep apnea, and aging. A common factor in these conditions is an increase in reactive oxygen species (ROS) in neural, cardiac, and endothelial tissues. Cu/Zn superoxide dismutase (SOD1) is an intracellular anti-oxidant enzyme that catalyzes dismutation of the superoxide anion (O2.-) to hydrogen peroxide (H2O2). Expression and function of this enzyme are diminished in...
Show moreDysregulation of the autonomic cardiovascular control is a complication of diseases including diabetes, hypertension, sleep apnea, and aging. A common factor in these conditions is an increase in reactive oxygen species (ROS) in neural, cardiac, and endothelial tissues. Cu/Zn superoxide dismutase (SOD1) is an intracellular anti-oxidant enzyme that catalyzes dismutation of the superoxide anion (O2.-) to hydrogen peroxide (H2O2). Expression and function of this enzyme are diminished in pathologies that impair cardiovascular autonomic control. This study employed mice overexpressing a transgene for human SOD1 (hSOD1) to determine if its overexpression would alter autonomic regulation of BP, HR, and BRS in healthy animals, and if this animal line (C57B6SJL-Tg (SOD1)2 Gur/J) could be used in future studies to determine if hSOD1 overexpression can preserve cardiac autonomic function in disease models. To accomplish this aim, using anesthetized SOD1 and C57 (control) mice, we recorded HR, and aortic depressor nerve (ADN) activity changes in response to pharmacologically-induced BP changes in order to measure baroreflex and baroreceptor sensitivity, respectively. In order to identify any alterations in central, efferent, and cardiac components of the baroreflex arc, we electrically stimulated the left ADN and left cervical vagus and compared the reductions in BP and HR between the C57 and SOD1 mice. Time- and frequency-domain analysis of heart rate variability (HRV) was performed using pulse pressure recordings prior to pharmacologic or surgical procedures. We found that hSOD1 overexpression in the SOD1 mouse line, in comparison to C57 controls did not significantly affect resting HR (C57: 558 (&)#177; 8 vs. SOD1:553 (&)#177; 13 beats-per-minute) or blood pressure (C57: 88.8 (&)#177; 2.9 vs.SOD1: 85.8 (&)#177; 2.1 mmHg). hSOD1 overexpression did not affect the decrease in average mean arterial pressure (MAP) following injection of sodium nitroprusside (SNP) (C57: 38.7 (&)#177; 1.4 vs. SOD1: 39.5 (&)#177; 1.3 mmHg) or increase in average MAP (C57: 135.8 (&)#177; 3.1 vs. SOD1: 136.6 (&)#177; 3.5 mmHg) following injection of phenylephrine (PE). BRS, as measured by the averaged regression lines for ?HR/?MAP for the SNP-induced tachycardic baroreflex (C57: 0.57 (&)#177; 0.06 bpm/mmHg, SOD1: 0.61 (&)#177; 0.08 bpm/mmHg)) and the PE-induced bradycardic baroreflex (C57: -2.9 (&)#177; 0.57 bmp/mmHg, SOD1: -4.3 (&)#177; 0.84 bpm/mmHg) are not significantly different between C57 and SOD1. Baroreceptor activation showed a significant increase in gain (C57: 5.4 (&)#177; 0.3 vs. SOD1: 7.4 (&)#177; 0.5 %/mmHg, P (<) 0.01) in the SOD1 transgenic mice. Heart rate depression in response to electrical stimulation of the left ADN and cervical vagus was comparable between C57 and SOD1, though MAP reduction in response to ADN stimulation is slightly, but significantly increased at 50 Hz in SOD1 animals. Time- domain analysis of HRV did not reveal any significant difference in beat-to-beat variability between SOD1 and C57 (SDNN: C57: 2.78 (&)#177; 0.20, SOD1: 2.89 (&)#177; 0.27), although frequency-domain analysis uncovered a significant reduction in the low-frequency power component of the HRV power spectral distribution (C57: 1.19 (&)#177; 0.11, SOD1: 0.35 (&)#177; 0.06, P (<) 0.001). This study shows that although hSOD1 overexpression does not affect overall baroreflex function, it does potentiate baroreceptor sensitivity and brain stem control of arterial pressure, and reduces low-frequency beat-to-beat variations in HR, without affecting total HRV.
Show less - Date Issued
- 2015
- Identifier
- CFE0005803, ucf:50025
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005803
- Title
- Light-Matter Interactions of Plasmonic Nanostructures.
- Creator
-
Reed, Jennifer, Zou, Shengli, Belfield, Kevin, Zhai, Lei, Hernandez, Eloy, Vanstryland, Eric, University of Central Florida
- Abstract / Description
-
Light interaction with matter has long been an area of interest throughout history, spanning many fields of study. In recent decades, the investigation of light-matter interactions with nanostructures has become an intense area of research in the field of photonics. Metallic nanostructures, in particular, are of interest due to the interesting properties that arise when interacting with light. The properties are a result of the excitation of surface plasmons which are the collective...
Show moreLight interaction with matter has long been an area of interest throughout history, spanning many fields of study. In recent decades, the investigation of light-matter interactions with nanostructures has become an intense area of research in the field of photonics. Metallic nanostructures, in particular, are of interest due to the interesting properties that arise when interacting with light. The properties are a result of the excitation of surface plasmons which are the collective oscillation of the conduction electrons in the metal. Since the conduction electrons can be thought of as harmonic oscillators, they are quantized in a similar fashion. Just as a photon is a quantum of oscillations of an electromagnetic field, the plasmon is a quantum of electron oscillations of a metal. There are three types of plasmons:1. Bulk plasmons, also called volume plasmons, are longitudinal density fluctuations which propagate through a bulk metal with an eigenfrequency of ?_p called the plasma frequency.2. Localized surface plasmons are non-propagating excitations of the conduction electrons of a metallic nanoparticle coupled to an electromagnetic field. 3. Surface plasmon polaritons are evanescent, dispersive propagating electromagnetic waves formed by a coupled state between a photon and the excitation of the surface plasmons. They propagate along the surface of a metal-dielectric interface with a broad spectrum of eigenfrequencies from ?=0 to ?= ?_p??2. Plasmonics is a subfield of photonics which focuses on the study of surface plasmons and the optical properties that result from light interacting with metal films and nanostructures on the deep subwavelength scale. In this thesis, plasmonic nanostructures are investigated for optical waveguides and other nanophotonic applications through computational simulations primarily base on electrodynamic theory. The theory was formulated by several key figures and established by James Clerk Maxwell after he published a set of relations which describe all classical electromagnetic phenomena, known as Maxwell's equations. Using methods based on Maxwell's equations, the optical properties of metallic nanostructures utilizing surface plasmons is explored. In Chapter 3, light propagation of bright and dark modes of a partially and fully illuminated silver nanorod is investigated for waveguide applications. Then, the origin of the Fano resonance line shape in the scattering spectra of a silver nanorod is investigated. Next, in Chapter 4, the reflection and transmission of a multilayer silver film is simulated to observe the effects of varying the dielectric media between the layers on light propagation. Building on the multilayer film work, metal-insulator-metal waveguides are explored by perforating holes in the bottom layer of a two layer a silver film to investigate the limits of subwavelength light trapping, confinement, and propagation. Lastly, in Chapter 5, the effect of surface plasmons on the propagation direction of electromagnetic wave around a spherical silver nanoparticle which shows an effective negative index of refraction is examined. In addition, light manipulation using a film of silver prisms with an effective negative index of refraction is also investigated. The silver prisms demonstrate polarization selective propagation for waveguide and optical filter applications. These studies provide insight into plasmonic mechanisms utilized to overcome the diffraction limit of light. Through better understanding of how to manipulating light with plasmonic nanostructures, further advancements in nanophotonic technologies for applications such as extremely subwavelength waveguides, sensitive optical detection, optical filters, polarizers, beam splitters, optical data storage devices, high speed data transmission, and integrated subwavelength photonic circuits can be achieved.
Show less - Date Issued
- 2013
- Identifier
- CFE0005049, ucf:49964
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005049
- Title
- Novel Developments on the Extraction and Analysis of Polycyclic Aromatic Hydrocarbons in Environmental Samples.
- Creator
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Wilson, Walter, Campiglia, Andres, Belfield, Kevin, Rex, Matthew, Harper, James, Hoffman, Jay, University of Central Florida
- Abstract / Description
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This dissertation focuses on the development of analytical methodology for the analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples. Chemical analysis of PAHs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Among the hundreds of PAHs present in the environment, the U.S. Environmental Protection Agency (EPA) lists sixteen as "Consent Decree" priority pollutants. Their routine monitoring in...
Show moreThis dissertation focuses on the development of analytical methodology for the analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples. Chemical analysis of PAHs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Among the hundreds of PAHs present in the environment, the U.S. Environmental Protection Agency (EPA) lists sixteen as "Consent Decree" priority pollutants. Their routine monitoring in environmental samples is recommended to prevent human contamination risks.A primary route of human exposure to PAHs is the ingestion of contaminated water. The rather low PAH concentrations in water samples make the analysis of the sixteen priority pollutants particularly challenging. Current EPA methodology follows the classical pattern of sample extraction and chromatographic analysis. The method of choice for PAHs extraction and pre-concentration is solid-phase extraction (SPE). PAHs determination is carried out via high-performance liquid chromatography (HPLC) or gas chromatography/mass spectrometry (GC/MS). When HPLC is applied to highly complex samples, EPA recommends the use of GC/MS to verify compound identification and to check peak-purity of HPLC fractions. Although EPA methodology provides reliable data, the routine monitoring of numerous samples via fast, cost effective and environmentally friendly methods remains an analytical challenge. Typically, 1 L of water is processed through the SPE device in approximately 1 h. The rather large water volume and long sample processing time are recommended to reach detectable concentrations and quantitative removal of PAHs from water samples. Chromatographic elution times of 30 (-) 60 min are typical and standards must be run periodically to verify retention times. If concentrations of targeted PAHs are found to lie outside the detector's response range, the sample must be diluted (or concentrated), and the process repeated. In order to prevent environmental risks and human contamination, the routine monitoring of the sixteen EPA-PAHs is not sufficient anymore. Recent toxicological studies attribute a significant portion of the biological activity of PAH contaminated samples to the presence of high molecular weight (HMW) PAHs, i.e. PAHs with MW ? 300. Because the carcinogenic properties of HMW-PAHs differ significantly from isomer to isomer, it is of paramount importance to determine the most toxic isomers even if they are present at much lower concentrations than their less toxic isomers. Unfortunately, established methodology cannot always meet the challenge of specifically analyzing HMW-PAHs at the low concentration levels of environmental samples. The main problems that confront classic methodology arise from the relatively low concentration levels and the large number of structural isomers with very similar elution times and similar, possibly even virtually identical, fragmentation patterns. This dissertation summarizes significant improvements on various fronts. Its first original component deals with the unambiguous determination of four HMW-PAHs via laser-excited time-resolved Shpol'skii spectroscopy (LETRSS) without previous chromatographic separation. The second original component is the improvement of a relatively new PAH extraction method - solid-phase nanoextraction (SPNE) - which uses gold nanoparticles as extracting material for PAHs. The advantages of the improved SPNE procedure are demonstrated for the analysis of EPA-PAHs and HMW-PAHs in water samples via GC/MS and LETRSS, respectively.
Show less - Date Issued
- 2014
- Identifier
- CFE0005443, ucf:50384
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005443