View All Items
(61 - 72 of 72)
Pages
- 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.
Show less - Date Issued
- 2011
- Identifier
- CFE0003640, ucf:48891
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003640
- Title
- INTEGRATED INP PHOTONIC SWITCHES.
- Creator
-
May-Arrioja, Daniel, LiKamWa, Patrick, University of Central Florida
- Abstract / Description
-
Photonic switches are becoming key components in advanced optical networks because of the large variety of applications that they can perform. One of the key advantages of photonic switches is that they redirect or convert light without having to make any optical to electronic conversions and vice versa, thus allowing networking functions to be lowered into the optical layer. InP-based switches are particularly attractive because of their small size, low electrical power consumption, and...
Show morePhotonic switches are becoming key components in advanced optical networks because of the large variety of applications that they can perform. One of the key advantages of photonic switches is that they redirect or convert light without having to make any optical to electronic conversions and vice versa, thus allowing networking functions to be lowered into the optical layer. InP-based switches are particularly attractive because of their small size, low electrical power consumption, and compatibility with integration of laser sources, photo-detectors, and electronic components. In this dissertation the development of integrated InP photonic switches using an area-selective zinc diffusion process has been investigated. The zinc diffusion process is implemented using a semi-sealed open-tube diffusion technique. The process has proven to be highly controllable and reproducible by carefully monitoring of the diffusion parameters. Using this technique, isolated p-n junctions exhibiting good I-V characteristics and breakdown voltages greater than 10 V can be selectively defined across a semiconductor wafer. A series of Mach-Zehnder interferometric (MZI) switches/modulators have been designed and fabricated. Monolithic integration of 1x2 and 2x2 MZI switches has been demonstrated. The diffusion process circumvents the need for isolation trenches, and hence optical losses can be significantly reduced. An efficient optical beam steering device based on InGaAsP multiple quantum wells is also demonstrated. The degree of lateral current spreading is easily regulated by controlling the zinc depth, allowing optimization of the injected currents. Beam steering over a 21 microns lateral distance with electrical current values as low as 12.5 mA are demonstrated. Using this principle, a reconfigurable 1x3 switch has been implemented with crosstalk levels better than -17 dB over a 50 nm wavelength range. At these low electrical current levels, uncooled and d.c. bias operation is made feasible. The use of multimode interference (MMI) structures as active devices have also been investigated. These devices operate by selective refractive index perturbation on very specific areas within the MMI structure, and this is again realized using zinc diffusion. Several variants such as a compact MMI modulator that is as short as 350 µm, a robust 2x2 photonic switch and a tunable MMI coupler have been demonstrated.
Show less - Date Issued
- 2006
- Identifier
- CFE0001368, ucf:47007
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001368
- Title
- DESIGN AND ASSESSMENT OF COMPACT OPTICAL SYSTEMS TOWARDS SPECIAL EFFECTS IMAGING.
- Creator
-
Chaoulov, Vesselin, Rolland, Jannick, University of Central Florida
- Abstract / Description
-
A main challenge in the field of special effects is to create special effects in real time in a way that the user can preview the effect before taking the actual picture or movie sequence. There are many techniques currently used to create computer-simulated special effects, however current techniques in computer graphics do not provide the option for the creation of real-time texture synthesis. Thus, while computer graphics is a powerful tool in the field of special effects, it is neither...
Show moreA main challenge in the field of special effects is to create special effects in real time in a way that the user can preview the effect before taking the actual picture or movie sequence. There are many techniques currently used to create computer-simulated special effects, however current techniques in computer graphics do not provide the option for the creation of real-time texture synthesis. Thus, while computer graphics is a powerful tool in the field of special effects, it is neither portable nor does it provide work in real-time capabilities. Real-time special effects may, however, be created optically. Such approach will provide not only real-time image processing at the speed of light but also a preview option allowing the user or the artist to preview the effect on various parts of the object in order to optimize the outcome. The work presented in this dissertation was inspired by the idea of optically created special effects, such as painterly effects, encoded in images captured by photographic or motion picture cameras. As part of the presented work, compact relay optics was assessed, developed, and a working prototype was built. It was concluded that even though compact relay optics can be achieved, further push for compactness and cost-effectiveness was impossible in the paradigm of bulk macro-optics systems. Thus, a paradigm for imaging with multi-aperture micro-optics was proposed and demonstrated for the first time, which constitutes one of the key contributions of this work. This new paradigm was further extended to the most general case of magnifying multi-aperture micro-optical systems. Such paradigm allows an extreme reduction in size of the imaging optics by a factor of about 10 and a reduction in weight by a factor of about 500. Furthermore, an experimental quantification of the feasibility of optically created special effects was completed, and consequently raytracing software was developed, which was later commercialized by SmARTLens(TM). While the art forms created via raytracing were powerful, they did not predict all effects acquired experimentally. Thus, finally, as key contribution of this work, the principles of scalar diffraction theory were applied to optical imaging of extended objects under quasi-monochromatic incoherent illumination in order to provide a path to more accurately model the proposed optical imaging process for special effects obtained in the hardware. The existing theoretical framework was generalized to non-paraxial in- and out-of-focus imaging and results were obtained to verify the generalized framework. In the generalized non-paraxial framework, even the most complex linear systems, without any assumptions for shift invariance, can be modeled and analyzed.
Show less - Date Issued
- 2005
- Identifier
- CFE0000513, ucf:46447
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000513
- Title
- DESIGN, SYNTHESIS, AND CHARACTERIZATION OF NOVEL HYDROPHILIC FLUORENE-BASED DERIVATIVES FOR BIOIMAGING APPLICATIONS.
- Creator
-
Nguyen, Dao, Belfield, Kevin, University of Central Florida
- Abstract / Description
-
In this work, hydrophilic fluorene-based derivatives that contain ethylene oxide substituents, have been synthesized and characterized for potential use as new fluorophores for bioimaging applications and for fluorescence sensing of heavy metals. Symmetrical and unsymmetrical fluorene derivatives based on structural types of acceptor-pi-acceptor, acceptor-pi-donor, and donor-pi-donor were characterized by TGA, UV-vis absorption, fluorescence emission, lifetime, anisotropy, and two-photon...
Show moreIn this work, hydrophilic fluorene-based derivatives that contain ethylene oxide substituents, have been synthesized and characterized for potential use as new fluorophores for bioimaging applications and for fluorescence sensing of heavy metals. Symmetrical and unsymmetrical fluorene derivatives based on structural types of acceptor-pi-acceptor, acceptor-pi-donor, and donor-pi-donor were characterized by TGA, UV-vis absorption, fluorescence emission, lifetime, anisotropy, and two-photon absorption (2PA) cross section. They were found to possess high thermal stability, high photostability, high fluorescence quantum yields, and generally large two-photon absorption cross sections, making them quite suitable for new probes in single-photon absorption and two-photon absorption fluorescence microscopy imaging. Novel hydrophilic fluorene derivatives were synthesized from fluorene in multiple steps employing the metal-catalyzed Heck coupling reaction, the Stille reaction, the Sonogashira reaction, the Ullmann condensation reaction, and "click" chemistry. To increase the hydrophilicity of the new compounds, ethylene oxide substituents were utilized for to impart water solubility. An alternative alkylation methodology using ethyleneoxy tosylates was introduced for the synthesis of ethylene oxide-containing fluorene derivatives. Several of these hydrophilic derivatives were incubated into various cell lines as new probes for both conventional and two-photon absorption fluorescence bioimaging. These compounds were biocompatible, exhibiting low cytotoxicity as determined by cell viability studies, and displayed colocalization for selected cellular organelles. In addition, hydrophilic bis(1,2,3-triazolyl)fluorene derivatives were found to exhibit sensitive fluorescence responses in the presence of certain heavy metal, and were selective for sensing zinc and mercury over other a number of other metal ions relevant to living cells or other biological environments. The UV-vis absorption and fluorescence emission spectra of the complexes exhibited a blue-shifted absorption and emission for selective metal chelation upon binding to zinc and mercury(II) ions, resulting in an approximately two-fold enhanced fluorescence response. Fluorescence titration studies revealed that the complexes of 1:2 and 1:3 ligand to metal formed with binding constant values of 108 and 1014 for zinc and mercury ions, respectively. Finally, preliminary experiments were performed to explore the possibility of employing select hydrophilic fluorene-based derivatives in the synthesis of hydrophilic fluorescent gold nanoparticles. Although results are very preliminary, the aim is to use such materials for other biomedical applications, such as surface enhanced scattering resonance and noninvasive photothermal therapy to diagnose and to treat cancers. Thus, this research had led to the discovery of alternative methodologies for synthesis of hydrophilic fluorene derivatives by alkylation with alkyl tosylates and synthesis of hydrophilic fluorescent molecule capped gold nanoparticles. Furthermore, several novel hydrophilic fluorene-based derivatives were synthesized and characterized for their linear and nonlinear photophysical properties, and are now available for further examination of their bioimaging and sensing applications.
Show less - Date Issued
- 2009
- Identifier
- CFE0002930, ucf:48002
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0002930
- Title
- Hybrid integration of second- and third-order highly nonlinear waveguides on silicon substrates.
- Creator
-
Camacho Gonzalez, Guillermo Fernando, Fathpour, Sasan, Likamwa, Patrick, Amezcua Correa, Rodrigo, Peale, Robert, University of Central Florida
- Abstract / Description
-
In order to extend the capabilities and applications of silicon photonics, other materials and compatible technologies have been developed and integrated on silicon substrates. A particular class of integrable materials are those with high second- and third-order nonlinear optical properties. This work presents contributions made to nonlinear integrated photonics on silicon substrates, including chalcogenide waveguides for over an octave supercontinuum generation, and rib-loaded thin-film...
Show moreIn order to extend the capabilities and applications of silicon photonics, other materials and compatible technologies have been developed and integrated on silicon substrates. A particular class of integrable materials are those with high second- and third-order nonlinear optical properties. This work presents contributions made to nonlinear integrated photonics on silicon substrates, including chalcogenide waveguides for over an octave supercontinuum generation, and rib-loaded thin-film lithium niobate waveguides for highly efficient second-harmonic generation. Through the pursuit of hybrid integration of the two types of waveguides for applications such as on-chip self-referenced optical frequency combs, we have experimentally demonstrated fabrication integrability of chalcogenide and thin-film lithium niobate waveguides in a single chip and a pathway for both second- and third-order nonlinearities occurring therein. Accordingly, design specifications for an efficient nonlinear integrated waveguide are reported, showing over an octave supercontinuum generation and frequency selectivity for second-harmonic generation, enabling potentials of on-chip interferometry techniques for carrier-envelope offset detection, and hence stabilized optical combs.
Show less - Date Issued
- 2019
- Identifier
- CFE0007607, ucf:52560
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007607
- Title
- Investigating New Guaiazulenes and Diketopyrropyrroles for Photonic Applications.
- Creator
-
Ghazvini Zadeh, Ebrahim, Belfield, Kevin, Campiglia, Andres, Yuan, Yu, Zou, Shengli, Cheng, Zixi, University of Central Florida
- Abstract / Description
-
?-Conjugated systems have been the focus of study in recent years in order to understand their charge transport and optical properties for use in organic electronic devices, fluorescence bioimaging, sensors, and 3D optical data storage (ODS), among others. As a result, several molecular building blocks have been designed, allowing new frontiers to be realized. While various successful building blocks have been fine-tuned at both the electronic and molecular structure level to provide advanced...
Show more?-Conjugated systems have been the focus of study in recent years in order to understand their charge transport and optical properties for use in organic electronic devices, fluorescence bioimaging, sensors, and 3D optical data storage (ODS), among others. As a result, several molecular building blocks have been designed, allowing new frontiers to be realized. While various successful building blocks have been fine-tuned at both the electronic and molecular structure level to provide advanced photophysical and optoelectronic characteristics, the azulene framework has been under-appreciated despite its unique electronic and optical properties. Among several attributes, azulenes are vibrant blue naturally occurring hydrocarbons that exhibit large dipolar character, coupled with stimuli-responsive behavior in acidic environments. Additionally, the non-toxic nature and the accompanying eco-friendly feature of some azulenes, namely guaiazulene, may set the stage to further explore a more (")green(") route towards photonic and conductive materials.The first part of this dissertation focuses on exploiting guaiazulene as a natural building block for the synthesis of chromophores with varying stimuli-responsiveness. Results described in Chapter 1 show that extending the conjugation of guaiazulene through its seven-membered ring methyl group with aromatic substituents dramatically impacts the optical properties of the guaiazulenium carbocation. Study of these ?(-)stabilized tropilium ions enabled establishing photophysical structure-property trends for guaiazulene-terminated ?-conjugated analogs under acidic conditions, including absorption, emission, quantum yield, and optical band gap patterns. These results were exploited in the design of a photosensitive polymeric system with potential application in the field of three dimensional (3D) optical data storage (ODS).Chapter 2 describes the use of guaiazulene reactive sites (C-3 and C-4 methyl group) to generate a series of cyclopenta[ef]heptalenes that exhibit strong stimuli-responsive behavior. The approach presents a versatile route that allows for various substrates to be incorporated into the resulting cyclopenta[ef]heptalenes, especially after optimization that led to devising a one-pot reaction toward such tricyclic systems. Examining the UV-vis absorption profiles in neutral and acidic media showed that the extension of conjugation at C(4) of the cyclopenta[ef]heptalene skeleton results in longer absorption maxima and smaller optical energy gaps. Additionally, it was concluded that these systems act as sensitizers of a UV-activated ((<) 300 nm) photoacid generator (PAG), via intermolecular photoinduced electron transfer (PeT), upon which the PAG undergoes photodecomposition resulting in the generation of acid.In a related study, the guaiazulene methyl group at C-4 was employed to study the linear and nonlinear optical properties of 4-styrylguaiazulenes, having the same ?(-)donor with varying ?-spacer. It was realized that the conjugation length correlates with the extent of bathochromic shift of the protonated species. On the other hand, a trend of decreasing quantum yield was established for this set of 4-styrylguaiazulenes, which can be explained by the increasingly higher degree of flexibility.The second part of this dissertation presents a comprehensive investigation of the linear photophysical, photochemical, and nonlinear optical properties of diketopyrrolopyrrole (DPP)-based derivatives, including two-photon absorption (2PA), femtosecond transient absorption, stimulated emission spectroscopy, and superfluorescence phenomena. The synthetic feasibility, ease of modification, outstanding robustness, and attractive spectroscopic properties of DPPs have motivated their study for fluorescence microscopy applications, concluding that the prepared DPP's are potentially suitable chromophores for high resolution stimulated emission depletion (STED) microscopy.
Show less - Date Issued
- 2015
- Identifier
- CFE0006034, ucf:50986
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006034
- Title
- Quantum Chemical Studies for the Engineering of Metal Organic Materials.
- Creator
-
Rivera Jacquez, Hector, Masunov, Artem, Balaeff, Alexander, Harper, James, Heider, Emily, Zou, Shengli, Kaden, William, University of Central Florida
- Abstract / Description
-
Metal Organic Materials (MOM) are composed of transition metal ions as connectors and organic ligands as linkers. MOMs have been found to have high porosity, catalytic, and optical properties. Here we study the gas adsorption, color change, and non-linear optical properties of MOMs. These properties can be predicted using theoretical methods, and the results may provide experimentalists with guidance for rational design and engineering of novel MOMs. The theory levels used include semi...
Show moreMetal Organic Materials (MOM) are composed of transition metal ions as connectors and organic ligands as linkers. MOMs have been found to have high porosity, catalytic, and optical properties. Here we study the gas adsorption, color change, and non-linear optical properties of MOMs. These properties can be predicted using theoretical methods, and the results may provide experimentalists with guidance for rational design and engineering of novel MOMs. The theory levels used include semi-empirical quantum mechanical calculations with the PM7 Hamiltonian and, Density Functional Theory (DFT) to predict the geometry and electronic structure of the ground state, and Time Dependent DFT (TD-DFT) to predict the excited states and the optical properties.The molecular absorption capacity of aldoxime coordinated Zn(II) based MOMs (previously measured experimentally) is predicted by using PM7 Theory level. The 3D structures were optimized with and without host molecules inside the pores. The absorption capacity of these crystals was predicted to be 8H2 or 3N2 per unit cell. When going beyond this limit, the structural integrity of the bulk material becomes fractured and microcrystals are observed both experimentally and theoretically.The linear absorption properties of Co(II) based complexes are known to change color when the coordination number is altered. In order to understand the mechanism of this color change TD-DFT methods are employed. The chromic behavior of the Co(II) based complexes studied was confirmed to be due to a chain in coordination number that resulted in lower metal to ligand distances. These distances destabilize the occupied metal d orbitals, and as a consequence of this, the metal to ligand transition energy is lowered enough to allow the crystals to absorb light at longer wavelengths.Covalent organic frameworks (COFs) present an extension of MOM principles to the main group elements. The synthesis of ordered COFs is possible by using predesigned structures andcarefully selecting the building blocks and their conditions for assembly. The crystals formed by these systems often possess non-linear optical (NLO) properties. Second Harmonic Generation (SHG) is one of the most used optical processes. Currently, there is a great demand for materials with NLO optical properties to be used for optoelectronic, imaging, sensing, among other applications. DFT calculations can predict the second order hyperpolarizability ?2 and tensor components necessary to estimate NLO. These calculations for the ?2 were done with the use of the Berry's finite field approach. An efficient material with high ?2 was designed and the resulting material was predicted to be nearly fivefold higher than the urea standard.Two-photon absorption (2PA) is another NLO effect. Unlike SHG, it is not limited to acentric material and can be used development of in vivo bio-imaging agents for the brain. Pt(II) complexes with porphyrin derivatives are theoretically studied for that purpose. The mechanism of 2PA enhancement was identified. For the most efficient porphyrin, the large 2PA cross-section was found to be caused by a HOMO-LUMO+2 transition. This transition is strongly coupled to 1PA allowed Q-band HOMO-LUMO states by large transition dipoles. Alkyl carboxyl substituents delocalize the LUMO+2 orbital due to their strong ?-acceptor effect, enhancing transition dipoles and lowering the 2PA transition to the desirable wavelengths range.The mechanism 2PA cross-section enhancement of aminoxime and aldoxime ligands upon metal addition of is studied with TD-DFT methods. This mechanism of enhancement is found to be caused by the polarization of the ligand orbitals by the metal cation. After polarization an increase in ligand to ligand transition dipole moment. This enhancement of dipole moment is related to the increase in 2PA cross-sections.
Show less - Date Issued
- 2015
- Identifier
- CFE0005990, ucf:50777
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005990
- Title
- Fluorescence Lifetime Imaging and Spectroscopy Aided Tracking of ZnO and CdS:Mn/ZnS/ N-acetyl cysteine (NAC) Quantum Dots in Citrus Plants.
- Creator
-
Washington, Torus, Gesquiere, Andre, Rajaraman, Swaminathan, Zhai, Lei, University of Central Florida
- Abstract / Description
-
In this thesis, we present an efficacious way of tracking nanoparticle movement in plant tissue through the use of fluorescence lifetime imaging (FLIM) and spectroscopy as well as a review of nanoparticle uptake in plants and the proposed mechanisms governing them. Given the increasing number of nanomaterials in agriculture and society as a whole, proper imaging tools and proactive measures must be taken to track nanoparticle movement in plant tissues and create infrastructure and products to...
Show moreIn this thesis, we present an efficacious way of tracking nanoparticle movement in plant tissue through the use of fluorescence lifetime imaging (FLIM) and spectroscopy as well as a review of nanoparticle uptake in plants and the proposed mechanisms governing them. Given the increasing number of nanomaterials in agriculture and society as a whole, proper imaging tools and proactive measures must be taken to track nanoparticle movement in plant tissues and create infrastructure and products to keep things sustainable and safe. Herein we report a ZnO comparable nanoparticle(-) a CdS:Mn/ZnS/ N-acetyl cysteine (NAC) quantum dot(-) which boasts longer lifetimes and suitable fluorescent properties above ZnO to properly delineate from plant tissue fluorescence of chlorophyll and cinnamic acids. In addition to FLIM mapping, quantum dot localization in plant vascular tissue was clearly seen and confirmed via characteristic emission spectra and time correlated single photon counting decay curves (TCSPC). Most quantum dots were seen to reside in the xylem. Plant age and structure was seen to affect uptake. QD size likely restricted extensive translocation. Inhibitive effects of QDs were likely water and mechanical stress. We surmise that travel of the cadmium quantum dots up the leaf and branch plant tissues is likely most governed by diffusion as the quantum dots bound to the cell structures create a diffusion gradient which aids travel up the leaf.
Show less - Date Issued
- 2017
- Identifier
- CFE0006820, ucf:51772
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006820
- Title
- Prediction of Optical Properties of Pi-Conjugated Organic Materials for Technological Innovations.
- Creator
-
Nayyar, Iffat, Masunov, Artem, Saha, Haripada, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
- Abstract / Description
-
Organic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged ...
Show moreOrganic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged (polaronic) excitations. In this work, we investigate the appropriate theoretical methods used for the (a) prediction of 2PA properties for rational design of organic materials with improved NLO properties, and (b) understanding of the essential electronic excitations controlling the energy-transfer and charge-transport properties in organic optoelectronics. Accurate prediction of these electro-optical properties is helpful for structure-activity relationships useful for technological innovations.In Chapter 1 we emphasize on the potential use of the organic materials for these two applications. The 2PA process is advantageous over one-photon absorption for deep-tissue fluorescence microscopy, photodynamic therapy, microfabrication and optical data storage owing to the three-dimensional spatial selectivity and improved penetration depth in the absorbing or scattering media. The design of the NLO materials with large 2PA cross-sections may reduce the optical damage due to the use of the high intensity laser beams for excitation. The organic molecules also possess self-localized excited states which can decay radiatively or nonradiatively to form excitonic states. This suggests the use of these materials in the electroluminescent devices such as light-emitting diodes and photovoltaic cells through the processes of exciton formation or dissociation, respectively. It is therefore necessary to understand ultrafast relaxation processes required in understanding the interplay between the efficient radiative transfer between the excited states and exciton dissociation into polarons for improving the efficiency of these devices. In Chapter 2, we provide the detailed description of the various theoretical methods applied for the prediction as well as the interpretation of the optical properties of a special class of substituted PPV [poly (p-phenylene vinylene)] oligomers. In Chapter 3, we report the accuracy of different second and third order time dependent density functional theory (TD-DFT) formalisms in prediction of the 2PA spectra compared to the experimental measurements for donor-acceptor PPV derivatives. We recommend a posteriori Tamm-Dancoff approximation method for both qualitative and quantitative analysis of 2PA properties. Whereas, Agren's quadratic response methods lack the double excitations and are not suitable for the qualitative analysis of the state-specific contributions distorting the overall quality of the 2PA predictions. We trace the reasons to the artifactual excited states above the ionization threshold. We also study the effect of the basis set, geometrical constraints and the orbital exchange fraction on the 2PA excitation energies and cross-sections. Higher exchange (BMK and M05-2X) and range-separated (CAM-B3LYP) hybrid functionals are found to yield inaccurate predictions both quantitatively and qualitatively. The failure of the exchange-correlation (XC) functionals with correct asymptotic is traced to the inaccurate transition dipoles between the valence states, where functionals with low HF exchange succeed. In Chapter 4, we test the performance of different semiempirical wavefunction theory methods for the prediction of 2PA properties compared to the DFT results for the same set of molecules. The spectroscopic parameterized (ZINDO/S) method is relatively better than the general purpose parameterized (PM6) method but the accuracy is trailing behind the DFT methods. The poor performances of PM6 and ZINDO/S methods are attributed to the incorrect description of excited-to-excited state transition and 2PA energies, respectively. The different semiempirical parameterizations can at best be used for quantitative analysis of the 2PA properties. The ZINDO/S method combined with different orders of multi-reference configuration interactions provide an improved description of 2PA properties. However, the results are observed to be highly dependent on the specific choice for the active space, order of excitation and reference configurations.In Chapter 5, we present a linear response TD-DFT study to benchmark the ability of existing functional models to describe the extent of self-trapped neutral and charged excitations in PPV and its derivative MEH-PPV considered in their trans-isomeric forms. The electronic excitations in question include the lowest singlet (S1) and triplet (T1†) excitons, positive (P+) and negative (P-) polarons and the lowest triplet (T1) states. Use of the long-range-corrected DFT functional, such as LC-wPBE, is found to be crucial in order to predict the physically correct spatial localization of all the electronic excitations in agreement with experiment. The inclusion of polarizable dielectric environment play an important role for the charged states. The particle-hole symmetry is preserved for both the polymers in trans geometries. These studies indicate two distinct origins leading to self-localization of electronic excitations. Firstly, distortion of molecular geometry may create a spatially localized potential energy well where the state wavefunction self-traps. Secondly, even in the absence of geometric and vibrational dynamics, the excitation may become spatially confined due to energy stabilization caused by polarization effects from surrounding dielectric medium.In Chapter 6, we aim to separate these two fundamental sources of spatial localization. We observe the electronic localization of P+ and P- is determined by the polarization effects of the surrounding media and the character of the DFT functional. In contrast, the self-trapping of the electronic wavefunctions of S1 and T1(T1†) mostly follows their lattice distortions. Geometry relaxation plays an important role in the localization of the S1 and T1† excitons owing to the non-variational construction of the excited state wavefunction. While, mean-field calculated P+, P- and T1 states are always spatially localized even in ground state S0 geometry. Polaron P+ and P- formation is signified by the presence of the localized states for the hole or the electron deep inside the HOMO-LUMO gap of the oligomer as a result of the orbital stabilization at the LC-wPBE level. The broadening of the HOMO-LUMO band gap for the T1 exciton compared to the charged states is associated with the inverted bond length alternation observed at this level. The molecular orbital energetics are investigated to identify the relationships between state localization and the corresponding orbital structure.In Chapter 7, we investigate the effect of various conformational defects of trans and cis nature on the energetics and localization of the charged P+ and P- excitations in PPV and MEH-PPV. We observe that the extent of self-trapping for P+ and P- polarons is highly sensitive on molecular and structural conformations, and distribution of atomic charges within the polymers. The particle-hole symmetry is broken with the introduction of trans defects and inclusion of the polarizable environment in consistent with experiment. The differences in the behavior of PPV and MEH-PPV is rationalized based on their orbital energetics and atomic charge distributions. We show these isomeric defects influence the behavior and drift mobilities of the charge carriers in substituted PPVs.
Show less - Date Issued
- 2013
- Identifier
- CFE0005110, ucf:50722
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005110
- Title
- Specialty Fiber Lasers and Novel Fiber Devices.
- Creator
-
Jollivet, Clemence, Schulzgen, Axel, Moharam, Jim, Richardson, Martin, Mafi, Arash, University of Central Florida
- Abstract / Description
-
At the Dawn of the 21st century, the field of specialty optical fibers experienced a scientific revolution with the introduction of the stack-and-draw technique, a multi-steps and advanced fiber fabrication method, which enabled the creation of well-controlled micro-structured designs. Since then, an extremely wide variety of finely tuned fiber structures have been demonstrated including novel materials and novel designs. As the complexity of the fiber design increased, highly-controlled...
Show moreAt the Dawn of the 21st century, the field of specialty optical fibers experienced a scientific revolution with the introduction of the stack-and-draw technique, a multi-steps and advanced fiber fabrication method, which enabled the creation of well-controlled micro-structured designs. Since then, an extremely wide variety of finely tuned fiber structures have been demonstrated including novel materials and novel designs. As the complexity of the fiber design increased, highly-controlled fabrication processes became critical. To determine the ability of a novel fiber design to deliver light with properties tailored according to a specific application, several mode analysis techniques were reported, addressing the recurring needs for in-depth fiber characterization. The first part of this dissertation details a novel experiment that was demonstrated to achieve modal decomposition with extended capabilities, reaching beyond the limits set by the existing mode analysis techniques. As a result, individual transverse modes carrying between ~0.01% and ~30% of the total light were resolved with unmatched accuracy. Furthermore, this approach was employed to decompose the light guided in Large-Mode Area (LMA) fiber, Photonic Crystal Fiber (PCF) and Leakage Channel Fiber (LCF). The single-mode performances were evaluated and compared. As a result, the suitability of each specialty fiber design to be implemented for power-scaling applications of fiber laser systems was experimentally determined.The second part of this dissertation is dedicated to novel specialty fiber laser systems. First, challenges related to the monolithic integration of novel and complex specialty fiber designs in all-fiber systems were addressed. The poor design and size compatibility between specialty fibers and conventional fiber-based components limits their monolithic integration due to high coupling loss and unstable performances. Here, novel all-fiber Mode-Field Adapter (MFA) devices made of selected segments of Graded Index Multimode Fiber (GIMF) were implemented to mitigate the coupling losses between a LMA PCF and a conventional Single-Mode Fiber (SMF), presenting an initial 18-fold mode-field area mismatch. It was experimentally demonstrated that the overall transmission in the mode-matched fiber chain was increased by more than 11 dB (the MFA was a 250 ?m piece of 50 ?m core diameter GIMF). This approach was further employed to assemble monolithic fiber laser cavities combining an active LMA PCF and fiber Bragg gratings (FBG) in conventional SMF. It was demonstrated that intra-cavity mode-matching results in an efficient (60%) and narrow-linewidth (200 pm) laser emission at the FBG wavelength.In the last section of this dissertation, monolithic Multi-Core Fiber (MCF) laser cavities were reported for the first time. Compared to existing MCF lasers, renown for high-brightness beam delivery after selection of the in-phase supermode, the present new generation of 7-coupled-cores Yb-doped fiber laser uses the gain from several supermodes simultaneously. In order to uncover mode competition mechanisms during amplification and the complex dynamics of multi-supermode lasing, novel diagnostic approaches were demonstrated. After characterizing the laser behavior, the first observations of self-mode-locking in linear MCF laser cavities were discovered.
Show less - Date Issued
- 2014
- Identifier
- CFE0005354, ucf:50491
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005354
- Title
- Broad Bandwidth, All-fiber, Thulium-doped Photonic Crystal Fiber Amplifier for Potential Use in Scaling Ultrashort Pulse Peak Powers.
- Creator
-
Sincore, Alex, Richardson, Martin, Shah, Lawrence, Amezcua Correa, Rodrigo, University of Central Florida
- Abstract / Description
-
Fiber based ultrashort pulse laser sources are desirable for many applications; however generating high peak powers in fiber lasers is primarily limited by the onset of nonlinear effects such as self-phase modulation, stimulated Raman scattering, and self-focusing. Increasing the fiber core diameter mitigates the onset of these nonlinear effects, but also allows unwanted higher-order transverse spatial modes to propagate. Both large core diameters and single-mode propagation can be...
Show moreFiber based ultrashort pulse laser sources are desirable for many applications; however generating high peak powers in fiber lasers is primarily limited by the onset of nonlinear effects such as self-phase modulation, stimulated Raman scattering, and self-focusing. Increasing the fiber core diameter mitigates the onset of these nonlinear effects, but also allows unwanted higher-order transverse spatial modes to propagate. Both large core diameters and single-mode propagation can be simultaneously attained using photonic crystal fibers.Thulium-doped fiber lasers are attractive for high peak power ultrashort pulse systems. They offer a broad gain bandwidth, capable of amplifying sub-100 femtosecond pulses. The longer center wavelength at 2 ?m theoretically enables higher peak powers relative to 1 ?m systems since nonlinear effects inversely scale with wavelength. Also, the 2 ?m emission is desirable to support applications reaching further into the mid-IR.This work evaluates the performance of a novel all-fiber pump combiner that incorporates a thulium-doped photonic crystal fiber. This fully integrated amplifier is characterized and possesses a large gain bandwidth, essentially single-mode propagation, and high degree of polarization. This innovative all-fiber, thulium-doped photonic crystal fiber amplifier has great potential for enabling high peak powers in 2 ?m fiber systems; however the current optical-to-optical efficiency is low relative to similar free-space amplifiers. Further development and device optimization will lead to higher efficiencies and improved performance.
Show less - Date Issued
- 2014
- Identifier
- CFE0005260, ucf:50611
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005260
- Title
- REFRACTIVE INDICES OF LIQUID CRYSTALS AND THEIR APPLICATIONS IN DISPLAY AND PHOTONIC DEVICES.
- Creator
-
Li, Jun, Wu, Shin-Tson, University of Central Florida
- Abstract / Description
-
Liquid crystals (LCs) are important materials for flat panel display and photonic devices. Most LC devices use electrical field-, magnetic field-, or temperature-induced refractive index change to modulate the incident light. Molecular constituents, wavelength, and temperature are the three primary factors determining the liquid crystal refractive indices: ne and no for the extraordinary and ordinary rays, respectively. In this dissertation, we derive several physical models for describing...
Show moreLiquid crystals (LCs) are important materials for flat panel display and photonic devices. Most LC devices use electrical field-, magnetic field-, or temperature-induced refractive index change to modulate the incident light. Molecular constituents, wavelength, and temperature are the three primary factors determining the liquid crystal refractive indices: ne and no for the extraordinary and ordinary rays, respectively. In this dissertation, we derive several physical models for describing the wavelength and temperature effects on liquid crystal refractive indices, average refractive index, and birefringence. Based on these models, we develop some high temperature gradient refractive index LC mixtures for photonic applications, such as thermal tunable liquid crystal photonic crystal fibers and thermal solitons. Liquid crystal refractive indices decrease as the wavelength increase. Both ne and no saturate in the infrared region. Wavelength effect on LC refractive indices is important for the design of direct-view displays. In Chapter 2, we derive the extended Cauchy models for describing the wavelength effect on liquid crystal refractive indices in the visible and infrared spectral regions based on the three-band model. The three-coefficient Cauchy model could be used for describing the refractive indices of liquid crystals with low, medium, and high birefringence, whereas the two-coefficient Cauchy model is more suitable for low birefringence liquid crystals. The critical value of the birefringence is deltan~0.12. Temperature is another important factor affecting the LC refractive indices. The thermal effect originated from the lamp of projection display would affect the performance of the employed liquid crystal. In Chapter 3, we derive the four-parameter and three-parameter parabolic models for describing the temperature effect on the LC refractive indices based on Vuks model and Haller equation. We validate the empirical Haller equation quantitatively. We also validate that the average refractive index of liquid crystal decreases linearly as the temperature increases. Liquid crystals exhibit a large thermal nonlinearity which is attractive for new photonic applications using photonic crystal fibers. We derive the physical models for describing the temperature gradient of the LC refractive indices, ne and no, based on the four-parameter model. We find that LC exhibits a crossover temperature To at which dno/dT is equal to zero. The physical models of the temperature gradient indicate that ne, the extraordinary refractive index, always decreases as the temperature increases since dne/dT is always negative, whereas no, the ordinary refractive index, decreases as the temperature increases when the temperature is lower than the crossover temperature (dno/dT<0 when the temperature is lower than To) and increases as the temperature increases when the temperature is higher than the crossover temperature (dno/dT>0 when the temperature is higher than To ). Measurements of LC refractive indices play an important role for validating the physical models and the device design. Liquid crystal is anisotropic and the incident linearly polarized light encounters two different refractive indices when the polarization is parallel or perpendicular to the optic axis. The measurement is more complicated than that for an isotropic medium. In Chapter 4, we use a multi-wavelength Abbe refractometer to measure the LC refractive indices in the visible light region. We measured the LC refractive indices at six wavelengths, lamda=450, 486, 546, 589, 633 and 656 nm by changing the filters. We use a circulating constant temperature bath to control the temperature of the sample. The temperature range is from 10 to 55 oC. The refractive index data measured include five low-birefringence liquid crystals, MLC-9200-000, MLC-9200-100, MLC-6608 (delta_epsilon=-4.2), MLC-6241-000, and UCF-280 (delta_epsilon=-4); four middle-birefringence liquid crystals, 5CB, 5PCH, E7, E48 and BL003; four high-birefringence liquid crystals, BL006, BL038, E44 and UCF-35, and two liquid crystals with high dno/dT at room temperature, UCF-1 and UCF-2. The refractive indices of E7 at two infrared wavelengths lamda=1.55 and 10.6 um are measured by the wedged-cell refractometer method. The UV absorption spectra of several liquid crystals, MLC-9200-000, MLC-9200-100, MLC-6608 and TL-216 are measured, too. In section 6.5, we also measure the refractive index of cured optical films of NOA65 and NOA81 using the multi-wavelength Abbe refractometer. In Chapter 5, we use the experimental data measured in Chapter 4 to validate the physical models we derived, the extended three-coefficient and two-coefficient Cauchy models, the four-parameter and three-parameter parabolic models. For the first time, we validate the Vuks model using the experimental data of liquid crystals directly. We also validate the empirical Haller equation for the LC birefringence delta_n and the linear equation for the LC average refractive index. The study of the LC refractive indices explores several new photonic applications for liquid crystals such as high temperature gradient liquid crystals, high thermal tunable liquid crystal photonic crystal fibers, the laser induced 2D+1 thermal solitons in nematic crystals, determination for the infrared refractive indices of liquid crystals, comparative study for refractive index between liquid crystals and photopolymers for polymer dispersed liquid crystal (PDLC) applications, and so on. In Chapter 6, we introduce these applications one by one. First, we formulate two novel liquid crystals, UCF-1 and UCF-2, with high dno/dT at room temperature. The dno/dT of UCF-1 is about 4X higher than that of 5CB at room temperature. Second, we infiltrate UCF-1 into the micro holes around the silica core of a section of three-rod core PCF and set up a highly thermal tunable liquid crystal photonic crystal fiber. The guided mode has an effective area of 440 ƒÝm2 with an insertion loss of less than 0.5dB. The loss is mainly attributed to coupling losses between the index-guided section and the bandgap-guided section. The thermal tuning sensitivity of the spectral position of the bandgap was measured to be 27 nm/degree around room temperature, which is 4.6 times higher than that using the commercial E7 LC mixture operated at a temperature above 50 degree C. Third, the novel liquid crystals UCF-1 and UCF-2 are preferred to trigger the laser-induced thermal solitons in nematic liquid crystal confined in a capillary because of the high positive temperature gradient at room temperature. Fourth, we extrapolate the refractive index data measured at the visible light region to the near and far infrared region basing on the extended Cauchy model and four-parameter model. The extrapolation method is validated by the experimental data measured at the visible light and infrared light regions. Knowing the LC refractive indices at the infrared region is important for some photonic devices operated in this light region. Finally, we make a completely comparative study for refractive index between two photocurable polymers (NOA65 and NOA81) and two series of Merck liquid crystals, E-series (E44, E48, and E7) and BL-series (BL038, BL003 and BL006) in order to optimize the performance of polymer dispersed liquid crystals (PDLC). Among the LC materials we studied, BL038 and E48 are good candidates for making PDLC system incorporating NOA65. The BL038 PDLC cell shows a higher contrast ratio than the E48 cell because BL038 has a better matched ordinary refractive index, higher birefringence, and similar miscibility as compared to E48. Liquid crystals having a good miscibility with polymer, matched ordinary refractive index, and higher birefringence help to improve the PDLC contrast ratio for display applications. In Chapter 7, we give a general summary for the dissertation.
Show less - Date Issued
- 2005
- Identifier
- CFE0000808, ucf:46677
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000808
