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- Title
- SELF-ASSEMBLY OF SQUARAINE DYES.
- Creator
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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.
Show less - Date Issued
- 2011
- Identifier
- CFE0003717, ucf:48773
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003717
- Title
- SELF-ASSEMBLY AND PHOTOPHYSICS OF SELECTED ORGANIC MATERIALS AND TWO-PHOTON BIOIMAGING WITH PROFLUORESCENT NITROXIDES, POLYELECTROLYTE NANOPARTICLES, AND SQUARAINE PROBES.
- Creator
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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.
Show less - Date Issued
- 2011
- Identifier
- CFE0003978, ucf:48665
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003978
- Title
- Synthesis, linear and nonlinear photophysical characterization of two symmetrical pyrene-terminated squaraine derivatives in solution.
- Creator
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Ballestas Barrientos, Alfonso, Belfield, Kevin, Harper, James, Clausen, Christian, University of Central Florida
- Abstract / Description
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Two indole-based squaraine dyes bonded to two pyrenyl groups through vinyl- and ethynyl- linkers were synthesized with the aim of enhancing the intramolecular charge transfer interaction in addition to improving their optical properties. The absorption and emission properties of these derivatives were determined in order to gain an insight into the intensity of this type of interaction, their aggregation behavior and compare them with results obtained through quantum chemical calculations....
Show moreTwo indole-based squaraine dyes bonded to two pyrenyl groups through vinyl- and ethynyl- linkers were synthesized with the aim of enhancing the intramolecular charge transfer interaction in addition to improving their optical properties. The absorption and emission properties of these derivatives were determined in order to gain an insight into the intensity of this type of interaction, their aggregation behavior and compare them with results obtained through quantum chemical calculations. Both compounds presented high photochemical stability in THF, and the linear spectroscopic characterization revealed high extinction coefficients, large fluorescence quantum yields and relatively low tendency of forming excimers in several solvents. The nonlinear spectroscopic study revealed two-photon absorption cross section maxima greater than 10,000 GM (1 GM = 1 (&)#215; 10-50 cm4 s/photon), which are improved values in comparison with the indole-based squaraine core. The experimental results were compared with time-dependent DFT calculations. These observations propose a new trend in the formulation of highly absorbing organic molecules containing pyrenyl groups for the development of new materials with Organic Light-Emitting Diode (OLED) applications. Moreover, this work contributes to the study of intramolecular charge transfer interaction and its tailoring for the improvement of the linear and nonlinear optical properties.
Show less - Date Issued
- 2015
- Identifier
- CFE0006024, ucf:50999
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006024
- 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
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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
- SQUARAINE DYES FOR TWO-PHOTON FLUORESCENCE BIOIMAGING APPLICATIONS.
- Creator
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Colon Gomez, Maria, Belfield, Kevin, University of Central Florida
- Abstract / Description
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Near-infrared emitting squaraine dyes are promising candidates for bioimaging applications. Two-photon fluorescence microscopy (2PFM) imaging is a powerful tool being used for studying biological function since it produces 3D images with minimal damage to cells and lower fluorophore photobleaching. The fluorescence wavelength of squaraine dyes normally falls in the near infrared region, providing deeper penetration through biological samples such as thick tissue sections. Squaraine dyes that...
Show moreNear-infrared emitting squaraine dyes are promising candidates for bioimaging applications. Two-photon fluorescence microscopy (2PFM) imaging is a powerful tool being used for studying biological function since it produces 3D images with minimal damage to cells and lower fluorophore photobleaching. The fluorescence wavelength of squaraine dyes normally falls in the near infrared region, providing deeper penetration through biological samples such as thick tissue sections. Squaraine dyes that could work for imaging cells and tissues for 2PFM imaging were synthesized and underwent comprehensive photophysical characterization, such as UV-Vis absorption, fluorescence, and anisotropy. The squaraine dyes were tested for cell toxicity to determine the concentration at which the cells should be incubated with the dye for 2PFM. In addition, the squaraine dyes were incubated with cancer cells to evaluate their utility in the bioimaging process. The squaraine dye that is not soluble in water can be incorporated in silica nanoparticles or micelles to facilitate dispersal in water for evaluation of its use as a probe. The prospective squaraine dyes can be used in cells and tissues for imaging that can then be analyzed to ascertain its use as a probe for biomedical applications, such as early cancer detection.
Show less - Date Issued
- 2013
- Identifier
- CFH0004338, ucf:45020
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFH0004338
- Title
- Squaraine dyes, design and synthesis for various functional materials applications.
- Creator
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Zhang, Yuanwei, Belfield, Kevin, Campiglia, Andres, Zou, Shengli, Frazer, Andrew, Cheng, Zixi, University of Central Florida
- Abstract / Description
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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.
Show less - Date Issued
- 2013
- Identifier
- CFE0005451, ucf:50369
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005451
- 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
