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EFFECTS OF FIBER AND LITHIUM ON MECHANICAL PROPERTIES OF CONCRETE MADE FROMRECYCLED CONCRETE AGGREGATE
Title
EFFECTS OF FIBER AND LITHIUM ON MECHANICAL PROPERTIES OF CONCRETE MADE FROMRECYCLED CONCRETE AGGREGATE.
Creator
Eskander, Ashraf, Kuo, Shiou-San, University of Central Florida
Abstract / Description
The growing demand of construction aggregates has raised concern about the availability of natural aggregates. Over two billion tons of natural aggregate are produced each year in the United States and that number is expected to increase to 2.5 billion tons by 2020. This has raised concern about the availability of natural aggregate. Discarding demolished concrete into landfills is a costly solution from an economical and environmental point of view. Many U.S. highway agencies are re-using...
Show moreThe growing demand of construction aggregates has raised concern about the availability of natural aggregates. Over two billion tons of natural aggregate are produced each year in the United States and that number is expected to increase to 2.5 billion tons by 2020. This has raised concern about the availability of natural aggregate. Discarding demolished concrete into landfills is a costly solution from an economical and environmental point of view. Many U.S. highway agencies are re-using Recycled Concrete Aggregates (RCA) as construction material. The use of fiber reinforcement in Portland Cement Concrete (PCC) has recently become a popular option in concrete construction because of its influence on preventing segregation, reducing early shrinkage cracks and increasing residual load capacity. Alkali-Silica Reaction (ASR) is a major problem in concrete, especially when using RCA, causing concrete expansion and cracks. Recently lithium has been found to reduce expansion due to ASR. This thesis will investigate the effect, of fibers soaked in lithium nitrate on the mechanical properties of RCA.
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Date Issued
2006
Identifier
CFE0001296, ucf:46878
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0001296
The Formation and Characterization of Mesoscopic J- and H-aggregates with Controlled Morphologies by the Co- and Templated Assembly of Cyanine Dyes
Title
The Formation and Characterization of Mesoscopic J- and H-aggregates with Controlled Morphologies by the Co- and Templated Assembly of Cyanine Dyes.
Creator
Rhodes, Samuel, Fang, Jiyu, Jiang, Tengfei, Dong, Yajie, Florczyk, Stephen, Pang, Sean, University of Central Florida
Abstract / Description
The supramolecular aggregates of ?-conjugated molecules have become an area of great interest to the scientific community in recent years for their promise in biosensors and optoelectronic devices. Among various supramolecular aggregates, J- and H-aggregates of ?-conjugated dye molecules are particularly interesting because of their unique optical and excitonic properties that are not given by individual molecules. H-aggregates are composed of dye molecules in a face-to-face stacking, giving...
Show moreThe supramolecular aggregates of ?-conjugated molecules have become an area of great interest to the scientific community in recent years for their promise in biosensors and optoelectronic devices. Among various supramolecular aggregates, J- and H-aggregates of ?-conjugated dye molecules are particularly interesting because of their unique optical and excitonic properties that are not given by individual molecules. H-aggregates are composed of dye molecules in a face-to-face stacking, giving rise to a blue-shifted absorption band compared with the monomer band and a strong emission quenching. In contrast, J-aggregates represent an edge-to-edge stacking of dye molecules, showing a red-shifted absorption band with respect to the monomer band and a strong fluorescence emission. However, the use of J- and H-aggregates in biosensors and optoelectronic devices remains a challenge because of the difficulty of controlling their sizes and morphologies. In this dissertation, we develop two different paths for controlling the size and morphology of J- and H-aggregates. First, we show that the co-assembly of cyanine dyes and lithocholic acid (LCA) in ammonia solution can lead to the formation of mesoscopic J- and H-aggregate fibers, depending on the condition under which the co-assembly occurs. Second, we report the formation of mesoscopic J-aggregate tubes by using the preformed LCA tubes as a template. The structure, optical, and electronic properties of these J- and H-aggregate fiber and tubes are studied as a function of temperature. Finally, we exploit their applications as photo-induced electron transfer supramolecular probes for the detection of dopamine, an important neurotransmitter in central and peripheral nervous systems.
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Date Issued
2018
Identifier
CFE0007412, ucf:52718
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007412
Pyroglutamylated amyloid beta peptides enhance non-fibrillogenic aggregation of the unmodified peptide
Title
Pyroglutamylated amyloid beta peptides enhance non-fibrillogenic aggregation of the unmodified peptide.
Creator
Goldblatt, Gregory, Tatulian, Suren, Chen, Bo, Teter, Kenneth, King, Stephen, University of Central Florida
Abstract / Description
Alzheimer's disease (AD) is accompanied by abnormal extracellular deposition of amyloid b (Ab) peptide. This has led to the amyloid cascade hypothesis, causatively relating Ab with AD. While Ab deposits assume a fibrillar cross-b structure, prefibrillar oligomers of Ab have been identified as the main cytotoxic agents in AD. Pyroglutamylated amyloid beta (AbpE) peptides are N-terminally truncated and pyroglutamylated (at Glu3 or Glu11) Ab molecules that display enhanced cytotoxicity and...
Show moreAlzheimer's disease (AD) is accompanied by abnormal extracellular deposition of amyloid b (Ab) peptide. This has led to the amyloid cascade hypothesis, causatively relating Ab with AD. While Ab deposits assume a fibrillar cross-b structure, prefibrillar oligomers of Ab have been identified as the main cytotoxic agents in AD. Pyroglutamylated amyloid beta (AbpE) peptides are N-terminally truncated and pyroglutamylated (at Glu3 or Glu11) Ab molecules that display enhanced cytotoxicity and represent up to 50% of total Ab in AD brains. AbpE significantly enhances the toxicity of unmodified Ab by an unknown mechanism. Although in situ Ab populations are heterogeneous, the majority of studies have been conducted on single Ab species. Here, we examined the structural and morphological changes that occur in mixed Ab/AbpE samples. Circular dichroism and transmission electron microscopy data indicate that AbpE3-42 forms b-sheet structure and undergoes delayed fibrillogenesis compared to unmodified Ab1-42. Further, AbpE3-42 decelerates b-sheet formation in mixed Ab1-42/AbpE3-42 samples. FTIR measurements, using 13C-labeled Ab1-42 and unlabeled AbpE3-42, indicate that AbpE3-42 inhibits cross-b-sheet formation by Ab1-42, which explains the retardation of fibrillogenesis. FTIR on peptides 13C-labeled at specific segments provided site specific structural information. Based on these data, the monomeric Ab structure has been modeled as a b-hairpin stabilized by intramolecular H-bonding with an N-terminal a-helix. These hairpins likely form higher order aggregates through ionic and hydrophobic interactions between the C-terminus of one hairpin and the N-terminus of another. Utilizing a novel technique, hydration from gas phase, we examined the a-helix to b-sheet transitions of these peptides. When combined, AbpE3-42 and Ab1-42 mutually inhibit intermolecular b-sheet formation, instead promoting formation of AbpE3-42/Ab1-42 hetero-oligomers of intramolecular H-bonding. These hetero-oligomers displayed enhanced toxicity to PC12 cells compared to individual peptides and induced greater calcium release from lipid vesicles than unmodified Ab. These results indicate that Ab and AbpE mutually inhibit fibrillogenesis and stabilize hetero-oligomers of enhanced cytotoxicity, possibly through a membrane permeabilization mechanism. Collectively, our findings lead to a new concept that Ab/AbpE hetero-oligomers, not just Ab or AbpE oligomers, are the main cytotoxic species in AD
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Date Issued
2016
Identifier
CFE0006108, ucf:51195
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006108
SELF-ASSEMBLY OF SQUARAINE DYES
Title
SELF-ASSEMBLY OF SQUARAINE DYES.
Creator
Qaddoura, Maher, Belfield, Kevin, University of Central Florida
Abstract / Description
Squaraine dyes have been a subject of extensive investigations lately due to their wide applications in important technological fields such as bioimaging probes, bioconjucation, second generation photosensitizers for photodynamic therapy, second harmonic generating organic dyes, two-photon absorbing materials with large cross section values, and, finally, photoconducting materials in photovoltaic cells. While a large number of patents and papers has been produced regarding their applications...
Show moreSquaraine dyes have been a subject of extensive investigations lately due to their wide applications in important technological fields such as bioimaging probes, bioconjucation, second generation photosensitizers for photodynamic therapy, second harmonic generating organic dyes, two-photon absorbing materials with large cross section values, and, finally, photoconducting materials in photovoltaic cells. While a large number of patents and papers has been produced regarding their applications limited work has been done concerning their thermotropic behavior, including their liquid crystalline properties, or correlation of the crystalline structure to both the solid state aggregation and their photophysical properties. In the first chapter of this dissertation, a series of squaraine dyes, based on 2, 4-bis squaraine including ethyl, propyl, butyl, pentyl, hexyl, and heptyl derivatives, were synthesized by condensation of the corresponding 4-(N,N-di-n-alkylamino)-2-hydroxyphenol with squaric acid. The thermal behavior of the series was recorded using both thermogravemetic analysis (TGA) and differential scanning calorimetry (DSC) while their crystalline structures were elucidated via single crystal X-ray diffraction. The length of the alkyl chain proved to have a significant effect on both the thermotropic behavior and the crystalline structure of the squaraine series. Two derivatives, butyl and heptyl, revealed the presence of liquid crystalline mesophases, smectic and nematic, respectively, that were confirmed and characterized via polarized light microscopy (PLM) and X-ray diffraction. In the second chapter, J- and H- aggregates were investigated in thin films by UV-vis spectroscopy; several of the derivatives formed H- and/or J-aggregates upon thin film formation via spin coating before and after thermal annealing, as indicated by UV-vis spectroscopy. The molecular structure, crystal structure, aggregation, and thermal behavior provide insight into the supramolecular assembly of this important class of materials. Photophysical measurements revealed large molar absorptivity, reasonably high fluorescence quantum yields, and significant fluorescence anisotropy, making these derivatives suitable candidates for a number of electro-optic and photonics applications. The third chapter was devoted to investigate liquid crystal-directed supramolecular assembly of a squaraine dye. Thus, The squaraine (SQ) dye, 2, 4-bis squaraine was used to prepare a series of SQ dye/cholesteryl pelargonate mixtures with varying dye concentrations (1%, 3%, 7.5%, 10.8%, 15%, and 20% w/w). Their phase transitions were investigated using differential scanning calorimetry, polarized light microscopy and X-ray diffraction. The squaraine dye itself exhibits no liquid crystalline behavior. The concentration of the dye in the cholesteric compound proved to have a significant effect on the dye aggregation behavior and phase transitions in cholesteryl pelargonate manifested by the appearance of new mesophases and formation of J- and H- aggregates. The texture morphology, X-ray diffraction analyses, and UV-vis absorbance spectra provide compelling evidence of the viability of the self-assembly of squaraines in the liquid crystalline mesophase. In the last chapter we will discuss possible modifications that can improve the aggregation systems.
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Date Issued
2011
Identifier
CFE0003717, ucf:48773
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003717
Evaluating the Use of Recycled Concrete Aggregate in French Drain Applications
Title
Evaluating the Use of Recycled Concrete Aggregate in French Drain Applications.
Creator
Behring, Zachary, Nam, Boo Hyun, Chopra, Manoj, Behzadan, Amir, Kim, Jin-Young, University of Central Florida
Abstract / Description
Recycled concrete aggregate (RCA) is often used as a replacement of virgin aggregate in road foundations (base course), embankments, hot-mix asphalt, and Portland cement concrete. However, the use of RCA in exfiltration drainage systems, such as French drains, is currently prohibited in many states of the U.S. The French drain system collects water runoff from the road pavement and transfers to slotted pipes underground and then filters through coarse aggregate and geotextile. The primary...
Show moreRecycled concrete aggregate (RCA) is often used as a replacement of virgin aggregate in road foundations (base course), embankments, hot-mix asphalt, and Portland cement concrete. However, the use of RCA in exfiltration drainage systems, such as French drains, is currently prohibited in many states of the U.S. The French drain system collects water runoff from the road pavement and transfers to slotted pipes underground and then filters through coarse aggregate and geotextile. The primary concerns with using RCA as a drainage media are the fines content and the precipitation of calcium carbonate to cause a reducing in filter fabric permittivity. Additional concerns include the potential for rehydration of RCA fines.The performance of RCA as drainage material has not been evaluated by many researchers and the limited information limits its use. A literature review has been conducted on the available information related to RCA as drainage material. A survey was issued to the Departments of Transportation across the nation in regards to using RCA particularly in French drains. Some state highway agencies have reported the use of RCA as base course; however, no state reports the use of RCA in exfiltration drainage systems. This thesis describes the investigations on the performance of RCA as backfill material in French drains.RCA was tested for its physical properties including, specific gravity, unit weight, percent voids, absorption, and abrasion resistance. RCA cleaning/washing methods were also applied to evaluate the fines removal processes. The potential for RCA rehydration was evaluated by means of heat of hydration, pH, compressive strength, and setting time. The permeability of RCA was tested using the No. 4 gradation. Long term permeability testing was conducted to evaluate the tendency for geotextile clogging from RCA fines. Calcium carbonate precipitation was also evaluated and a procedure to accelerate the precipitation process was developed.The results show that RCA has a high abrasion value, that is, it is very susceptible to break down from abrasion during aggregate handling such as transportation, stockpiling, or placing. The most effective cleaning method was found to be pressure washing with agitation. RCA has not demonstrated the tendency to rehydrate and harden when mixed with water. The permeability test results show that the No. 4 gradation does not restrict the flow of water; the flow rate is highly dependent on the hydraulic system itself, however excessive fines can cause large reductions in permeability over time. It has been determined that No. 4 gradation of RCA can provide a suitable drainage media providing the RCA is properly treated before its use.
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Date Issued
2013
Identifier
CFE0004974, ucf:49595
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0004974
SOCIAL GROUPING BEHAVIORS OF CAPTIVE FEMALE HIPPOPOTAMUS AMPHIBIUS
Title
SOCIAL GROUPING BEHAVIORS OF CAPTIVE FEMALE HIPPOPOTAMUS AMPHIBIUS.
Creator
Blowers, Tracy, Waterman, Jane, University of Central Florida
Abstract / Description
Levels of sociality vary depending on the costs and benefits associated with grouping behavior. Grouping species form either ephemeral aggregations due to resource availability, or structured groups based on familiarity of individuals. Because there are different costs and benefits associated with different types of groups, it is important to understand more about group structure before making predictions about specific behaviors. Female Hippopotamus amphibius are known to aggregate in the...
Show moreLevels of sociality vary depending on the costs and benefits associated with grouping behavior. Grouping species form either ephemeral aggregations due to resource availability, or structured groups based on familiarity of individuals. Because there are different costs and benefits associated with different types of groups, it is important to understand more about group structure before making predictions about specific behaviors. Female Hippopotamus amphibius are known to aggregate in the wild but the true nature of their grouping behavior is still not understood. My objective was to determine if captive female hippos form either ephemeral aggregations or social groups. Behavioral data, using continuous focal animal sampling and scan sampling, were collected on a group of nine captive female hippos housed at Disney's Animal Kingdom® Theme Park. The behavioral data were used to analyze interactions between hippos, association patterns for kin and non-kin as well as familiarity, dominance hierarchy, and habitat preferences. My results support the hypothesis that hippos are forming social groups due to the attraction to particular individuals. There were more associations between kin than non-kin and also between individuals that have been together longer. Captive female hippos were also found to exhibit dominance patterns within the group. The results from this study may aid in the general understanding of hippopotamus behavior and aid in the captive management of hippos. Using my results as a starting point, research can begin looking at grouping patterns and its costs and benefits of sociality in wild hippopotamus populations.
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Date Issued
2008
Identifier
CFE0002239, ucf:47905
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0002239
Use of Accelerated Calcite Precipitation Method to Investigate Calcium Carbonate Precipitation from Recycled Concrete for Drainage System Applications
Title
Use of Accelerated Calcite Precipitation Method to Investigate Calcium Carbonate Precipitation from Recycled Concrete for Drainage System Applications.
Creator
McCulloch, Toni, Nam, Boo Hyun, Chopra, Manoj, Arboleda Monsalve, Luis, An, Jin Woo, Filler, Dennis, University of Central Florida
Abstract / Description
Recycled concrete aggregate (RCA) is a sustainable construction material that is a viable option for use in drainage systems by replacing virgin aggregate. Replacing virgin aggregate with RCA is beneficial from both economic and environmental perspectives. However, the use of RCA as pipe backfill materials may cause a long-term performance issue such as potential clogging due to fines accumulation and calcite precipitation on filter fabric. Previous studies investigated the long-term...
Show moreRecycled concrete aggregate (RCA) is a sustainable construction material that is a viable option for use in drainage systems by replacing virgin aggregate. Replacing virgin aggregate with RCA is beneficial from both economic and environmental perspectives. However, the use of RCA as pipe backfill materials may cause a long-term performance issue such as potential clogging due to fines accumulation and calcite precipitation on filter fabric. Previous studies investigated the long-term performance of RCA regarding flow rate. Therefore, this study investigated calcite precipitation potential of RCA. The Accelerated Calcite Precipitation (ACP) procedure was devised and used to estimate (")life-time(") calcite precipitation of RCA for French Drains. The ACP procedure was studied further and improved to optimize the calcite precipitation procedure. The enhanced method was used to compare the calcite precipitation of limestone and RCA samples - sources with varying chemistry and history. Key findings are (1) the clogging due to calcite precipitation of RCA is not as significant as clogging due to the existing and/or accumulated fines, (2) the calcite precipitation can be increased with a temperature of 75(&)deg;C and 17-hour heating time, and (3) the potential for calcite precipitation from RCA is not as significant as limestone for Type I underdrain gradation.
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Date Issued
2018
Identifier
CFE0007321, ucf:52132
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007321
Development of an MRM federation system using COTS simulations
Title
Development of an MRM federation system using COTS simulations.
Creator
Kim, Jaeho, Lee, Gene, Elshennawy, Ahmad, Rabelo, Luis, University of Central Florida
Abstract / Description
The goal of this research is to build an experimental environment for the Simulation Interoperability Laboratory (SIL) of the University of Central Florida (UCF). The Simulation Interoperability Laboratory (SIL) is researching about multi-resolution modeling(MRM), with a focus on military field uses. This thesis proposes steps to develop an MRM federation system and build two different MRM systems using COTS simulations (SIMBox, VR-Forces, and MASA Sword). This report is written to provide...
Show moreThe goal of this research is to build an experimental environment for the Simulation Interoperability Laboratory (SIL) of the University of Central Florida (UCF). The Simulation Interoperability Laboratory (SIL) is researching about multi-resolution modeling(MRM), with a focus on military field uses. This thesis proposes steps to develop an MRM federation system and build two different MRM systems using COTS simulations (SIMBox, VR-Forces, and MASA Sword). This report is written to provide the basis for a time-based MRM federation study in the Simulation Interoperability Laboratory. The report describes many definitions and notions related to Multi-Resolution Modeling(MRM) and discusses examples to make better understanding for further research. MRM is relatively new research, and there are high demands for integrating simulators running in military field purposes. Most military-related research is based on simulators currently being used in the military; this poses a problem for research because the data is classified, resulting in many limitations for outside researchers to see the military's process for building an MRM system or the results of the research. Therefore, development of the MRM federation using COTS simulations can provide many examples of MRM issues for future research.Keywords: Multi-Resolution Modeling, MRM, aggregation, disaggregation, MRE, MRM approach.
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Date Issued
2018
Identifier
CFE0007576, ucf:52565
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007576
SELF-ASSEMBLY AND PHOTOPHYSICS OF SELECTED ORGANIC MATERIALS AND TWO-PHOTON BIOIMAGING WITH PROFLUORESCENT NITROXIDES, POLYELECTROLYTE NANOPARTICLES, AND SQUARAINE PROBES
Title
SELF-ASSEMBLY AND PHOTOPHYSICS OF SELECTED ORGANIC MATERIALS AND TWO-PHOTON BIOIMAGING WITH PROFLUORESCENT NITROXIDES, POLYELECTROLYTE NANOPARTICLES, AND SQUARAINE PROBES.
Creator
Ahn, Hyo-Yang, Belfield, Kevin, University of Central Florida
Abstract / Description
Two-photon absorption and upconverted fluorescence has been utilized in a variety of applications in pure science and engineering. Multiphoton-based techniques were used in this research in order to understand photophysical and chemical characteristics of several fluorescent dyes and to demonstrate some of their key applications. Two-photon fluorescence microscopy (2PFM) has become a powerful technique in bio-photonics for non-invasive imaging in the near-infrared (NIR) region (700~1000 nm)...
Show moreTwo-photon absorption and upconverted fluorescence has been utilized in a variety of applications in pure science and engineering. Multiphoton-based techniques were used in this research in order to understand photophysical and chemical characteristics of several fluorescent dyes and to demonstrate some of their key applications. Two-photon fluorescence microscopy (2PFM) has become a powerful technique in bio-photonics for non-invasive imaging in the near-infrared (NIR) region (700~1000 nm) that often results in less photobleaching. In Chapter 1, there is a brief introduction to fluorescence, examples of fluorescence materials, and a discussion of the advantages of two-photon absorption. 2PFM imaging was utilized in Chapters 2 to 4 for various applications. In Chapter 2, a new squaraine dye is introduced and its linear and nonlinear photophysical properties are characterized. This compound has very high two-photon absorption (2PA) cross sections and high photostability both in an organic solvent and when encapsulated in micelles. Based on these properties, this dye was demonstrated as a near-infrared (NIR) probe in in vitro 2PFM imaging with excitation over 800 nm wavelength. In Chapter 3, new profluorescent nitroxides are introduced. Nitroxide radicals are utilized for electron paramagnetic resonance (EPR) spectroscopy and in biological systems as some are known, in some manner, to mimic the behavior of superoxide dismutase (SOD) that detoxifies or mitigates oxidative stress by trapping free radicals. Here, two profluorescent nitroxides investigated for use as a two-photon fluorescent oxidative stress indicator in in vitro two-photon fluorescence microscopy (2PFM) imaging. In Chapter 4, two-photon excited (2PE) fluorescence of a conjugated polyelectrolyte (CPE), PPESO3, was studied in methanol and in water. The results of CPE quenching studies were comparable under both one-photon excitation conditions and two-photon excitation. CPE coated silica nanoparticles were incubated in HeLa cells and 2PFM imaging was demonstrated for this new class of fluorescent probe. Supramolecular structures based on organized assemblies/aggregation of chromophores have attracted widespread interest as molecular devices with potential applications in molecular electronics, artificial light harvesting, and pharmacology. In Chapter 5, J-aggregate formation was investigated for two porphyrin-based dyes, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS, 4) and an amino tris-sulfonate analog (5) in water via UV-vis, fluorescence, and lifetime decay studies. The effect of aggregation on two-photon absorption properties was also investigated. A functionalized norbornene-based homopolymer, synthesized by the ring opening metathesis polymerization technique was used as a J-aggregation enhancement template and had a role of polymer-templating to facilitate porphyrin aggregation and modulate 2PA. In Chapter 6, squaraine dye aggregates templated with single wall carbon nanotubes (SWCNTs) that were atomically clean were studied by using optical absorption spectroscopy, atomic force microscopy (AFM), and photoconductivity measurements. SWCNTs selectively promote the formation of squaraine dye aggregates with a head-to-head stacking arrangement, and these dye aggregates effectively photosensitize SWCNTs, demonstrating that this novel approach can yield highly photosensitized devices.
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Date Issued
2011
Identifier
CFE0003978, ucf:48665
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003978
Aggregation of Squaraine Dye Derivatives in Solid State Spin-coated Thin Films
Title
Aggregation of Squaraine Dye Derivatives in Solid State Spin-coated Thin Films.
Creator
Daoudi, Mohammed, Belfield, Kevin, Miles, Delbert, Campiglia, Andres, Bhattacharya, Aniket, Rex, Matthew, University of Central Florida
Abstract / Description
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.
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Date Issued
2015
Identifier
CFE0005778, ucf:50064
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005778
SYNTHESIS AND APPLICATIONS OF RING OPENING METATHESIS POLYMERIZATION BASED FUNCTIONAL BLOCK COPOLYMERS
Title
SYNTHESIS AND APPLICATIONS OF RING OPENING METATHESIS POLYMERIZATION BASED FUNCTIONAL BLOCK COPOLYMERS.
Creator
Biswas, Sanchita, Belfield, Kevin, University of Central Florida
Abstract / Description
Ring opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the...
Show moreRing opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the superparamagnetic polymeric nanocomposites. The J-aggregation properties of the porphyrin dyes were improved via self-assembly with a customized norbornene polymer. Novel multimodal copolymer probes were synthesized for two-photon fluorescence integrin-targeted bioimaging. In Chapter 1 a brief overview of ROMP along with ruthenium metal catalysts and selected applications of the polymers related to this research is presented. Superparamagnetic maghemite nanoparticles are important in biotechnology fields, such as enhanced magnetic resonance imaging (MRI), magnetically controlled drug delivery, and biomimetics. However, cluster formation and eventual loss of nano-dimensions is a major obstacle for these materials. Chapter 2 presents a solution to this problem through nanoparticles stabiulized in a polymer matrix. The synthesis and chracterization of novel diblock copolymers, consisting of epoxy pendant anchoring groups to chelate maghemite nanoparticles and steric stabilizing groups, as well as generation of nanocomposites and their characterization, including surface morphologies and magnetic properties, is discussed in Chapter 2. In Chapter 3, further improvement of the nanocomposites by ligand modification and the synthesis of pyrazole-templated diblock copolymers and their impact to stabilize the maghemite nanocomposite are presented. Additionally, the organic soluble magnetic nanocomposites with high magnetizations were encapsulated in an amphiphilic copolymer and dispersed in water to assess their water stability by TEM. To gain a preliminary measure of biocopatibility of the micelle-encapsulated polymeric magnetic nanocomposites, cell-viability was determined. In Chapter 4, aggregation behaviors of two porphyrin-based dyes were investigated. A new amphiphilic homopolymer containing secondary amine moieties was synthesized and characterized. In low pH, the polymer became water soluble and initiated the stable J-aggregation of the porphyrin. Spectroscopic data supported the aggregation behavior. Two photon fluorescence microscopy (2PFM) has become a powerful technique in bioimaging for non-invasive imaging and potential diagnosis and treatment of a number of diseases via excitation in the near-infrared (NIR) region. The fluorescence emission upon two-photon absorption (2PA) is quadratically dependent with the intensity of excitation light (compared to the linear dependence in the case of one-photon absoprtion), offering several advantages for biological applications over the conventional one-photon absorption (1PA) due to the high 3D spatial resolution that is confined near the focal point along with less photodamage and interference from the biological tissues at longer wavelength (~700-900 nm). Hence, efficient 2PA absorbing fluorophores conjugated with specific targeting moieties provides an even better bioimaging probe to diagnose desired cellular processes or areas of interest The αVβ3 integrin adhesive protein plays a significant role in regulating angiogenesis and is over-expressed in uncontrolled neovascularization during tumor growth, invasion, and metastasis. Cyclic-RGD peptides are well-known antagonists of αVβ3 integrin which suppress the angiogenesis process, thus preventing tumor growth. In Chapter 5 the synthesis, photophysical studies and bioimaging is reported for a versatile norbornene-based block copolymer multifunctional scaffold containing biocompatible (PEG), two-photon fluorescent (fluorenyl), and targeting (cyclic RGD peptide) moieties. This water-soluble polymeric multi scaffold probe with negligible cytotoxicity exhibited much stronger fluorescence and high localization in U87MG cells (that overexpress integrin) compared to control MCF7 cells. The norbornene-based polymers and copolymers have quite remarkable versatility for the creation of advanced functional magnetic, photonic, and biophotonic materials.
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Date Issued
2010
Identifier
CFE0003065, ucf:48296
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003065
THE STUDY OF THREE DIFFERENT LAYERED STRUCTURES AS MODEL SYSTEMS FOR HYDROGEN STORAGE MATERIALS
Title
THE STUDY OF THREE DIFFERENT LAYERED STRUCTURES AS MODEL SYSTEMS FOR HYDROGEN STORAGE MATERIALS.
Creator
Oztek, Muzaffer, Hampton, Michael, University of Central Florida
Abstract / Description
The strength and success of the hydrogen economy relies heavily on the storage of hydrogen. Storage systems in which hydrogen is sequestered in a solid material have been shown to be advantageous over storage of hydrogen as a liquid or compressed gas. Many different types of materials have been investigated, yet the desired capacity and uptake/release characteristics required for implementation have not been reached. In this work, porphyrin aggregates were investigated as a new type of...
Show moreThe strength and success of the hydrogen economy relies heavily on the storage of hydrogen. Storage systems in which hydrogen is sequestered in a solid material have been shown to be advantageous over storage of hydrogen as a liquid or compressed gas. Many different types of materials have been investigated, yet the desired capacity and uptake/release characteristics required for implementation have not been reached. In this work, porphyrin aggregates were investigated as a new type of material for hydrogen storage. The building blocks of the aggregates are porphyrin molecules that are planar and can assume a face to face arrangement that is also known as H-aggregation. The H-aggregates were formed in solution, upon mixing of aqueous solutions of two different porphyrins, one carrying positively charged and the other one carrying negatively charged functional groups. The cationic porphyrin used was meso-tetra(4-N,N,N-trimethylanilinium) porphine (TAP) and it was combined with four different anionic porphyrins, meso-tetra(4-sulfonatophenyl)porphine (TPPS), meso-tetra(4-carboxyphenyl) porphine (TCPP), Cu(II) meso-tetra(4-carboxyphenyl) porphine, and Fe(III) meso-tetra(4-carboxyphenyl) porphine. The force of attraction that held two oppositely charged porphyrin molecules together was electrostatic attraction between the peripheral groups. Solid state aggregates were successfully isolated either by solvent evaporation or by centrifuging and freeze drying. TCPP-TAP and Cu(II)TCPP-TAP aggregates were shown to interact with hydrogen starting from 150 °C up to 250 °C. The uptake capacity was about 1 weight %. Although this value is very low, this is the first observation of porphyrin aggregates absorbing hydrogen. This opened the way for further research to improve hydrogen absorption properties of these materials, as well as other materials based on this model. Two other materials that are also based on planar building blocks were selected to serve as a comparison to the porphyrin aggregates. The first of those materials was metal intercalated graphite compounds. In such compounds, a metal atom is placed between the layers of graphene that make up the graphite. Lithium, calcium and lanthanum were selected in this study. Theoretical hydrogen capacity was calculated for each material based on the hydriding of the metal atoms only. The fraction of that theoretical hydrogen capacity actually displayed by each material increased from La to Ca to Li containing graphite. The weight % hydrogen observed for these materials varied between 0.60 and 2.0 %. The other material tested for comparison was KxMnO2, a layered structure of MnO2 that contained the K atoms in between oxygen layers. The hydrogen capacity of the KxMnO2 samples was similar to the other materials tested in the study, slightly above 1 weight %. This work has shown that porphyrin aggregates, carbon based and manganese dioxide based materials are excellent model materials for hydrogen storage. All three materials absorb hydrogen. Porphyrin aggregates have the potential to exhibit adjustable hydrogen uptake and release temperatures owing to their structure that could interact with an external electric or magnetic field. In the layered materials, it is possible to alter interlayer spacing and the particular intercalates to potentially produce a material with an exceptionally large hydrogen capacity. As a result, these materials can have significant impact on the use of hydrogen as an energy carrier.
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Date Issued
2011
Identifier
CFE0003752, ucf:48769
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003752
Squaraine dyes, design and synthesis for various functional materials applications
Title
Squaraine dyes, design and synthesis for various functional materials applications.
Creator
Zhang, Yuanwei, Belfield, Kevin, Campiglia, Andres, Zou, Shengli, Frazer, Andrew, Cheng, Zixi, University of Central Florida
Abstract / Description
This dissertation contains the synthesis and characterization of squaraine based new functional materials. In the first part of this thesis work, a water soluble benzothiazolium squaraine dye was synthesized with pyridium pendents, and controlled aggregation properties were achieved. After formation of partially reversible J-aggregation on a polyelectrolyte (poly(acryl acid) sodium salt) template, the nonlinear, two-photon absorption cross section per repeat unit was found to be above 30-fold...
Show moreThis dissertation contains the synthesis and characterization of squaraine based new functional materials. In the first part of this thesis work, a water soluble benzothiazolium squaraine dye was synthesized with pyridium pendents, and controlled aggregation properties were achieved. After formation of partially reversible J-aggregation on a polyelectrolyte (poly(acryl acid) sodium salt) template, the nonlinear, two-photon absorption cross section per repeat unit was found to be above 30-fold enhanced compared with nonaggregate and/or low aggregates. Using a similar strategy, sulfonate anions were introduced into the squaraine structure, and the resulting compounds exhibited good water solubilities. A 'turn on' fluorescence was discovered when these squaraine dyes interacted with bovine serum albumin (BSA), titration studies by BSA site selective reagents show these squaraine dyes can bind to both site I and II of BSA, with a preference of site II. Introduction of these squaraine dyes to BSA nanoparticles generated near-IR protein nano fabricates, and cell images were collected. Metal sensing properties were also studied using the sulfonates containing a benzoindolium squaraine dye, and the linear response of the absorption of the squaraine dye to the concentration of Hg2+ makes it a good heavy metal-selective sensing material that can be carried out in aqueous solution. Later, a squaraine scaffold was attached to deoxyribonucleosides by Sonogashira coupling reactions, in which the reaction conditions were modified. Iodo-deoxyuridine and bromo-deoxyadenosine were used as the deoxyribonucleosides building blocks, and the resulting squaraine dye-modified deoxyribonucleosides exhibited near-IR absorption and emission properties due to the squaraine chromophore. Interestingly, these non-natural deoxyribonucleosdies showed viscosity dependent photophysical properties, which make them nice candidates for fluorescence viscosity sensors at the cellular level. After incubation with cells, these viscosity sensors were readily uptaken by cell, and images were obtained showing regions of high viscosity in cells.
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Date Issued
2013
Identifier
CFE0005451, ucf:50369
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005451
Mechanisms of Alpha-Synuclein-Induced Neurodegenertaion in Parkinson's Disease and Stroke
Title
Mechanisms of Alpha-Synuclein-Induced Neurodegenertaion in Parkinson's Disease and Stroke.
Creator
Belal, Cherine, Chan, Sic, Ebert, Steven, Self, William, Teter, Kenneth, University of Central Florida
Abstract / Description
Parkinson's disease (PD) is a debilitating neurodegenerative disorder affecting one million Americans. Despite its social and economic impact, the pathological cascades that lead to neuron dysfunction and degeneration in PD are poorly understood. Endoplasmic reticulum (ER) stress has been implicated as an initiator or contributing factor in neurodegenerative diseases including PD. The ER is an organelle central to protein folding and intracellular Ca2+ homeostasis. Perturbations of these...
Show moreParkinson's disease (PD) is a debilitating neurodegenerative disorder affecting one million Americans. Despite its social and economic impact, the pathological cascades that lead to neuron dysfunction and degeneration in PD are poorly understood. Endoplasmic reticulum (ER) stress has been implicated as an initiator or contributing factor in neurodegenerative diseases including PD. The ER is an organelle central to protein folding and intracellular Ca2+ homeostasis. Perturbations of these functions result in ER stress and upregulation of ER stress proteins, of which some have been implicated in counteracting ER stress-induced cell death. The mechanisms that lead to ER stress and how ER stress proteins contribute to the degenerative cascades remain unclear but their understanding is critical to devising effective therapies for PD. Both the accumulation of mutant a-synuclein (aSyn), which causes an inherited form of PD, and the inhibition of mitochondrial complex I function by PD-inducing neurotoxin lead to ER stress. The critical involvement of ER stress in experimental models of PD supports its potential relevance to PD pathogenesis and led us to test the hypothesis whether the homocysteine-inducible ER protein (Herp), an ubiquitin-like domain (UBD) containing ER-resident protein, can counteract mutant Alpha Syn- and neurotoxin- induced pathological cascades.
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Date Issued
2011
Identifier
CFE0004470, ucf:49310
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0004470
Harmful Algal Bloom Mitigation using Recycle Concrete Aggregate coated with Fixed-Quat.
Title
Harmful Algal Bloom Mitigation using Recycle Concrete Aggregate coated with Fixed-Quat.
Creator
Ezeodurukwe, Ikenna, Lee, Woo Hyoung, Randall, Andrew, Sadmani, A H M Anwar, University of Central Florida
Abstract / Description
Human activities generate surplus nutrients which may lead to algal bloom events in water resources along with serious ecological problems and thus substantial economic losses. Particularly, harmful algal blooms (HABs) represent toxic cyanobacterial blooms which produce cyanotoxins. The primary concerns of HABs are the exposures to a wide variety of cyanotoxins via ingestion of contaminated drinking water, inhalation during recreational activities, and consumption of contaminated fish and...
Show moreHuman activities generate surplus nutrients which may lead to algal bloom events in water resources along with serious ecological problems and thus substantial economic losses. Particularly, harmful algal blooms (HABs) represent toxic cyanobacterial blooms which produce cyanotoxins. The primary concerns of HABs are the exposures to a wide variety of cyanotoxins via ingestion of contaminated drinking water, inhalation during recreational activities, and consumption of contaminated fish and shellfish. However, conventional physical and chemical methods are not always possible to efficiently handle these HABs events. It is urgent to develop viable and rapid solutions to control HABs in field and mitigate the effects of HABs in fresh water, particularly in those that serve as sources of drinking water supply.(&)nbsp;Quaternary ammonium compounds (Quats) represent a wide range of cationic compounds with different formulation that constitutes products for agriculture, domestic and medical and industry. As organic antimicrobial compounds, Quats can be used as alternatives to existing chemical-based technique for HABs control due to its less toxicity and its affinity to variety of surface. In this study, recycled concrete aggregate (RCA) from a regional construction and demolition (C(&)D) waste recycling facility was used as a sustainable and environmentally friendly substrate and coated with a composite of silica-quaternary ammonium compounds (Fixed-Quat).(&)nbsp;Then, the algistatic capabilities of imparting antimicrobial properties of Quats to the RCA surface, which involve the covalent attachment of the biocides to the surfaces (sol-gel technique), were evaluated with HABs-causing algal species, Microcystis aeruginosa. Chlorophyll-a was measured to determine the efficiency of HABs mitigation using Fixed-Quat coated RCA in terms of photosynthetic inactivation of the selected algae. OD660 and pH were measured as key parameters to monitor algal cell growth and cement hydration. Notably, a 61% reduction of chlorophyll-a within 6 hours and complete removal of chlorophyll-a within 8 hours were achieved, indicating that Fixed-Quat coated RCA would be efficient in growth inhibition of Microcystis aeruginosa. Overall, with an appropriate design for field application and further evaluations like lifetime of Quat coating and potential recovery of treated algae, the Fixed-Quat antimicrobial coated RCA would be a promising and sustainable(&)nbsp;alternative to conventional HABs mitigation methods in various aquatic systems.
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Date Issued
2018
Identifier
CFE0007400, ucf:52066
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007400
THE APPLICATION OF TWO-PHOTON ABSORBING PROBES IN LYSOSOMAL, ZINC ION SENSING AND FOLATE RECEPTOR-TARGETED BIOIMAGING
Title
THE APPLICATION OF TWO-PHOTON ABSORBING PROBES IN LYSOSOMAL, ZINC ION SENSING AND FOLATE RECEPTOR-TARGETED BIOIMAGING.
Creator
WANG, XUHUA, Belfield, Kevin D., University of Central Florida
Abstract / Description
Two-photon fluorescence microscopy (2PFM) has become a powerful technique for bioimaging in non-invasive cancer diagnosis and also investigating the mechanization and original of a variety of diseases by tracking various biological processes. Because the fluorescence emission by two photon absorbing (2PA) is directly proportional to the square of the intensity of excitation light, this intrinsic property of 2PA provides 2PFM great advantages over traditional one-photon fluorescence microscopy...
Show moreTwo-photon fluorescence microscopy (2PFM) has become a powerful technique for bioimaging in non-invasive cancer diagnosis and also investigating the mechanization and original of a variety of diseases by tracking various biological processes. Because the fluorescence emission by two photon absorbing (2PA) is directly proportional to the square of the intensity of excitation light, this intrinsic property of 2PA provides 2PFM great advantages over traditional one-photon fluorescence microscopy (1PFM), including high 3D spatial localization, less photodamage and interference from biological tissue because of using longer wavelength excitation (700-1300 nm). However, most 2PA probes are hydrophobic and their photostabilities are questionable, severely limiting their biological and medical applications. In addition, probes with significant specificity for certain organelles for tracking cellular processes or metal ions for monitoring neural transmission are somewhat rare. Moreover, it is also very significant to deliver the probes to specific disease sites for early cancer diagnosis. In order to increase the water solubility of probes, polyethylene glycol (PEG) was introduced to a fluorene-based 2PA probe LT1 for lysosomal 2PFM cell imaging. The 2PFM bioimaging application of the novel two-photon absorbing fluorene derivative LT1, selective for the lysosomes of HCT 116 cancer cells is described in Chapter II. Linear and nonlinear photophysical and photochemical properties of the probe were investigated to evaluate the potential of the probe for 2PFM lysosomal imaging. After the investigation of the cytotoxicity of this new probe, colocalization studies of the probe with commercial lysosomal probe Lysotracker Red in HCT 116 cells were conducted. A high colocalization coefficient (0.96) was achieved and demonstrated the specific localization of the probe in lysosomes. A figure of merit, FM, was introduced by which all fluorescent probes for 2PFM can be compared. LT1 was demonstrated to have a number of properties that far exceed those of commercial lysotracker probes, including much higher 2PA cross sections, good fluorescence quantum yield, and, importantly, high photostability, all resulting in a superior figure of merit. Consequently, 2PFM was used to demonstrate lysosomal tracking with LT1. In addition to lysosomes, it is also very significant to investigate the physiological roles of free metal ions in biological processes, especially Zn2+, because Zn2+ normally serves either as the catalytic elements in enzymatic activity centers or as structural elements in enzymes and transcription factors. However, biocompatible and effective Zn2+ probes for 2PFM bioimaging are infrequent. In Chapter III, 2PFM bioimaging with a hydrophilic 2PA Zn2+ sensing fluorescent probe, bis(1,2,3-triazolyl)fluorene derivative, is described. 2PFM bioimaging of the probe in living HeLa cancer cells was demonstrated. The results revealed a significant fluorescence increase upon introduction of Zn2+ into the cancer cells, and a reversible Zn2+ binding to the probe was also demonstrated, providing a robust probe for two-photon fluorescence zinc ion sensing. Early cancer diagnosis is another critical application for 2PFM, but there are still huge challenges for this new technique in clinical areas. Most 2PA probes with large two-photon absorbing cross sections and fluorescence quantum efficiency are synthetically more accessible in hydrophobic forms. In order to increase the efficiency of the probes and minimize the effect of the probe on the human body, delivery of the probe specifically to cancer sites is desired. The synthesis and characterization of narrow dispersity organically modified silica nanoparticles (SiNPs), diameter ~30 nm, entrapping a hydrophobic two-photon absorbing fluorenyl dye, are reported in Chapter IV. The surface of the SiNPs was functionalized with folic acid to specifically deliver the probe to folate receptor (FR) over-expressing HeLa cells, making these folate 2PA dye-doped SiNPs potential candidates as probes for two-photon fluorescence microscopy (2PFM) bioimaging. In vitro studies using FR over-expressing HeLa cells demonstrated specific cellular uptake of the functionalized nanoparticles. However, when the concentration of the dye in SiNPs increased for higher signal output, the fluorescence quantum efficiency of a probe normally decreases because of self-quenching. In Chapter V, a near-infrared (NIR) emitting probe is reported to overcome this limitation through both aggregate-enhanced fluorescence emission and aggregate enhanced two-photon absorption. The dye was encapsulated in SiNPs and the surface of the nanoparticles was functionalized with PEG followed by a folic acid derivative to specifically target folate receptors. NIR emission is important for deep tissue imaging. In vitro studies using HeLa cells that upregulate folate receptors indicated specific cellular uptake of the folic acid functionalized SiNP nanoprobe. Meanwhile, the probe was also investigated for live animal imaging by employing mice bearing HeLa tumors for in vivo studies. Ex vivo 2PFM tumor imaging was then conducted to achieve high quality 3D thick tissue tumor images.
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Date Issued
2011
Identifier
CFE0003640, ucf:48891
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003640