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- Title
- RAMAN SPECTROSCOPY OF GLASSESWITH HIGH AND BROAD RAMAN GAIN IN THE BOSON PEAK REGION.
- Creator
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Guo, Yu, Schulte, Alfons, University of Central Florida
- Abstract / Description
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This thesis investigates Raman spectra of novel glasses and their correlation with structure for Raman gain applications. Raman gain for all-optical amplification by fibers depends significantly on the cross section for spontaneous Raman scattering allowing to compare signal strength and spectral coverage. We also investigate the relationship between glass structure and the Boson peak (enhancement of the low-frequency vibrational density of states) and report new inelastic neutron scattering...
Show moreThis thesis investigates Raman spectra of novel glasses and their correlation with structure for Raman gain applications. Raman gain for all-optical amplification by fibers depends significantly on the cross section for spontaneous Raman scattering allowing to compare signal strength and spectral coverage. We also investigate the relationship between glass structure and the Boson peak (enhancement of the low-frequency vibrational density of states) and report new inelastic neutron scattering spectra for niobium-phosphate glasses. Polarization resolved Raman spectra of glasses based on tellurite and phosphate formers have been measured from 6 1500 cm-1 using an excitation wavelength of 514 nm. The Tellurite glasses exhibit Raman Spectra at least 10 times more intense, are more spectrally uniform and possess spectral bandwidths more than a factor of two wider than fused silica. Assignments of the vibrational bands are presented and the compositional dependence of the spectra is discussed with respect to the molecular structure. Significantly high Boson peaks were found in the frequency range from 30-100 cm-1. The Raman gain curves were calculated from the polarized spontaneous Raman spectra. In particular, they show broad and flat band in the low frequency region (50-400 cm-1) suggesting that these glasses may be useful for Raman gain applications extending to very low frequencies. The inelastic neutron scattering spectra of the niobium-phosphate glasses display a pronounced low-frequency enhancement of the vibrational density of states. By averaging over the full accessible wavevector range we obtain an approximate spectral distribution of the vibrational modes. Through direct comparison with the Raman spectra we determine the Raman coupling function which shows a linear behavior near the Boson peak maximum. Possible mechanisms contributing to the low frequency Raman band such as disorder-induced irregular vibrational states are discussed.
Show less - Date Issued
- 2006
- Identifier
- CFE0001322, ucf:47021
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001322
- Title
- A NOVEL SETUP FOR HIGH-PRESSURE RAMAN SPECTROSCOPY UNDER A MICROSCOPE.
- Creator
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Oakeson, Thomas, Schulte, Alfons, University of Central Florida
- Abstract / Description
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Functional properties of biological molecules and cells are affected by environmental parameters such as temperature and pressure. While Raman spectroscopy provides an intrinsic probe of molecular structural changes, the incorporation of a microscope enables studies of minuscule amounts of biological compounds with spatial resolution on a micron scale. We have developed a novel setup which combines a Raman microscope and a high pressure cell. A micro-capillary made out of fused silica...
Show moreFunctional properties of biological molecules and cells are affected by environmental parameters such as temperature and pressure. While Raman spectroscopy provides an intrinsic probe of molecular structural changes, the incorporation of a microscope enables studies of minuscule amounts of biological compounds with spatial resolution on a micron scale. We have developed a novel setup which combines a Raman microscope and a high pressure cell. A micro-capillary made out of fused silica simultaneously serves as the supporting body and the optical window of the pressure cell. The cell has been tested over the pressure range from 0.1 to 4 kbar. Raman spectra of less than 100 nanoliter amount of amino acid and protein solutions have been measured in the micro-capillary high pressure cell. It is also demonstrated that the setup is well suited for spectrally resolved fluorescence measurements at variable pressure.
Show less - Date Issued
- 2007
- Identifier
- CFE0001683, ucf:47208
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001683
- Title
- RAMAN SPECTROSCOPIC STUDY OF SINGLE RED BLOOD CELLS INFECTED BY THE MALARIA PARASITE PLASMODIUM FALCIPARUM.
- Creator
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Carter, William, Schulte, Alfons, University of Central Florida
- Abstract / Description
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Raman micro-spectroscopy provides a non-destructive probe with potential applications as a diagnostic tool for cellular disorders. This study presents micro-Raman spectra of live erythrocytes infected with a malaria parasite and investigates the potential of this probe to monitor molecular changes which occur during differentiation of the parasite inside the cell. At an excitation wavelength of 633 nm the spectral bands are dominated by hemoglobin vibrations yielding information the on...
Show moreRaman micro-spectroscopy provides a non-destructive probe with potential applications as a diagnostic tool for cellular disorders. This study presents micro-Raman spectra of live erythrocytes infected with a malaria parasite and investigates the potential of this probe to monitor molecular changes which occur during differentiation of the parasite inside the cell. At an excitation wavelength of 633 nm the spectral bands are dominated by hemoglobin vibrations yielding information the on structure and spin state of the heme moiety. It also demonstrates the novel use of silica capillaries as a viable method for studying the erythrocytes in an environment that is much closer to their native state, thus opening the possibility of maintaining the cell in vivo for long periods to study the dynamics of the parasite's growth.
Show less - Date Issued
- 2007
- Identifier
- CFE0001780, ucf:47254
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001780
- Title
- MICRO-RAMAN SPECTROSCOPY OF CARBONACEOUS CHONDRITE METEORITES.
- Creator
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Habach, Asmail, Schulte, Alfons, University of Central Florida
- Abstract / Description
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Analyzing the constituents of meteorites has played an important role in forming the contemporary theories of solar system evolution, planets formation, and stellar evolution. Meteorites are often a complex mixture of common rock forming silicates, such as olivines and pyroxenes, with a range of exotic species including hydrated silicates, and in some cases organic compounds. We used Micro-Raman spectroscopy to analyze the compositions of three carbonaceous chondrites: NWA852, Murchison and...
Show moreAnalyzing the constituents of meteorites has played an important role in forming the contemporary theories of solar system evolution, planets formation, and stellar evolution. Meteorites are often a complex mixture of common rock forming silicates, such as olivines and pyroxenes, with a range of exotic species including hydrated silicates, and in some cases organic compounds. We used Micro-Raman spectroscopy to analyze the compositions of three carbonaceous chondrites: NWA852, Murchison and Allende. Raman spectra were measured using laser sources with different excitation wavelengths: HeNe 633 nm and Nd:YAG 532 nm. We were able to detect 9 minerals in NWA852, 3 minerals in Murchison and 4 minerals in Allende. Some of these minerals like pyrite in NWA852 and magnetite in NWA852 and Murchison provide evidence for potential previous organic life. Other minerals like ringwoodite in Allende and lizardite in NWA852 reveal information about previous astrophysical and geological events experienced by the meteorites. The detection of graphite in the Murchison and Allende reveals information about the microstructure of these meteorites.
Show less - Date Issued
- 2014
- Identifier
- CFH0004710, ucf:45396
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFH0004710
- Title
- PRESSURE AND TEMPERATURE RESPONSE OF A STIMULI-RESPONSIVE POLYMER PROBED WITH RAMAN MICROSCOPY.
- Creator
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Cariker, Coleman, Schulte, Alfons, University of Central Florida
- Abstract / Description
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Poly(N-isopropylacrylamide) (PNIPAM) is a thermo-responsive hydrogel; that is, it is a macromolecule which exists in a hydrated state beneath its lower critical solution temperature (LCST). Polymers such as PNIPAM undergo a phase transition in response to changes in temperature, pressure, pH, salt concentration, and the addition of co-solvents. Previously, visible-light microscopic measurements of the pressure-induced phase transition have been hindered by the lack of a pressurization...
Show morePoly(N-isopropylacrylamide) (PNIPAM) is a thermo-responsive hydrogel; that is, it is a macromolecule which exists in a hydrated state beneath its lower critical solution temperature (LCST). Polymers such as PNIPAM undergo a phase transition in response to changes in temperature, pressure, pH, salt concentration, and the addition of co-solvents. Previously, visible-light microscopic measurements of the pressure-induced phase transition have been hindered by the lack of a pressurization apparatus with the short working distance and optical transmission properties necessary for high resolution microscopy. We employ a high pressure setup which uses a fused silica micro-capillary to contain the sample. Our experiment reveals differences in the spatial evolution of the phase change across the temperature and pressure thresholds, and Raman measurements allude to conformational differences in the evolution of the phase transitions. The Raman peaks positions are in agreement with previous FTIR measurements, and due to a difference in selection rules additional vibrational bands are observed in the Raman spectra.
Show less - Date Issued
- 2014
- Identifier
- CFH0004694, ucf:45246
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFH0004694
- Title
- HIGH PRESSURE AND MICRO-SPECTROSCOPIC STUDIES OF SINGLE LIVING ERYTHROCYTES AND THE INTRAERYTHROCYTIC MULTPLICATION CYCLE OF PLASMODIUM FALCIPARUM.
- Creator
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ARORA, SILKI, SCHULTE, ALFONS, University of Central Florida
- Abstract / Description
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A novel experimental approach for micro-absorption spectroscopy and high-pressure microscopy of single cells is developed and applied to the investigation of morphological, volume, and spectroscopic changes in healthy red blood cells (RBCs) and erythrocytes infected with the malaria parasite Plasmodium falciparum. Through real-time optical imaging of individual erythrocytes (size ~ 7 microns) we determine the change in volume over the pressure range from 0.1 to 210 MPa. The lateral diameter...
Show moreA novel experimental approach for micro-absorption spectroscopy and high-pressure microscopy of single cells is developed and applied to the investigation of morphological, volume, and spectroscopic changes in healthy red blood cells (RBCs) and erythrocytes infected with the malaria parasite Plasmodium falciparum. Through real-time optical imaging of individual erythrocytes (size ~ 7 microns) we determine the change in volume over the pressure range from 0.1 to 210 MPa. The lateral diameter of healthy RBCs decreases reversibly with pressure with an approximate slope of 0.015 microns / MPa. In infected cells, clear differences in the deformability and between the compression and decompression curves are observed. The results are discussed with respect to the elasticity of the phospholipid membrane and the spectrin molecular network. Employing micro-absorption spectroscopy with spatial resolution of 1.4 microns in the lateral and 3.6 microns in the axial direction the visible absorption spectrum of hemoglobin in a single red blood cell is measured under physiological conditions. The spectra of cells infected with the malaria parasite show changes in peak positions and relative intensities in the Soret and the alpha- and beta-bands. These indicate hemoglobin degradation that can be correlated with the stages of the parasite multiplication cycle and can be used as a potential diagnostic marker. The research is further extended towards the understanding of pressure effects on the ligand binding kinetics to heme proteins. For a well characterized reaction at ambient pressure, CO binding to myoglobin in solution, we investigate the transient absorption following laser flash photolysis over eight decades in time at variable pressure and temperature. The data demonstrate that pressure significantly affects the amplitudes (not just the rates) of the component processes. The amplitude of the geminate process increases with pressure corresponding to a smaller escape fraction of ligands into the solvent and a smaller inner barrier.
Show less - Date Issued
- 2011
- Identifier
- CFE0004039, ucf:49157
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004039
- Title
- MICRO-SPECTROSCOPY OF BIO-ASSEMBLIES AT THE SINGLE CELL LEVEL.
- Creator
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Kera, Jeslin, Chakrabarti, Debopam, Schulte, Alfons, University of Central Florida
- Abstract / Description
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In this thesis, we investigate biological molecules on a micron scale in the ultraviolet spectral region through the non-destructive confocal absorption microscopy. The setup involves a combination of confocal microscope with a UV light excitation beam to measure the optical absorption spectra with spatial resolution of 1.4 ?m in the lateral and 3.6 ?m in the axial direction. Confocal absorption microscopy has the benefits of requiring no labels and only low light intensity for excitation...
Show moreIn this thesis, we investigate biological molecules on a micron scale in the ultraviolet spectral region through the non-destructive confocal absorption microscopy. The setup involves a combination of confocal microscope with a UV light excitation beam to measure the optical absorption spectra with spatial resolution of 1.4 ?m in the lateral and 3.6 ?m in the axial direction. Confocal absorption microscopy has the benefits of requiring no labels and only low light intensity for excitation while providing a strong signal from the contrast generated by the attenuation of propagating light due to absorption. This enables spatially resolved measurements of single live cells and bio-molecules with less than 10^9 molecules in the probe volume. Employing a multichannel detection system, the absorption spectrum of hemoglobin in a single red blood cell is measured on the timescale of seconds. We also extend the spectral range from the visible range to the experimentally more challenging ultra-violet region where characteristic absorption bands of bio-molecules are observed. Exploiting the ultra-violet range, amino acids, nucleic acids solutions, and plant cells are investigated. We measure the spatially resolved absorption spectra at the nucleus of an onion cell and cytoplasm to probe DNA base-pair absorption. Small variations in our micro-absorption data are seen around 260 nm, possibly due to the abundance of DNA in the nucleus. This thesis contributes to the goal of spectroscopic identification of spatial heterogeneities at the single cell level and the label-free detection of proteins and nucleic acids.
Show less - Date Issued
- 2017
- Identifier
- CFH2000356, ucf:45905
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFH2000356
- Title
- Structure of reflectin protein probed by solid-state nuclear magnetic resonance.
- Creator
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Boykin, Tommy, Chen, Bo, Schulte, Alfons, Tatulian, Suren, Teter, Kenneth, University of Central Florida
- Abstract / Description
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An unusual protein found in squids, termed reflectin, possesses the unique ability for optical reflectivity and proton conductivity. Reflectin has the potential to become optically and electronically tunable, however, the molecular structure of reflectin has yet to be determined. Previous literature has considered using reflectin proteins as diffraction gratings, protonic transistors, and substrates for neural stem cell growth. Applying recombinant protein techniques, we purified the...
Show moreAn unusual protein found in squids, termed reflectin, possesses the unique ability for optical reflectivity and proton conductivity. Reflectin has the potential to become optically and electronically tunable, however, the molecular structure of reflectin has yet to be determined. Previous literature has considered using reflectin proteins as diffraction gratings, protonic transistors, and substrates for neural stem cell growth. Applying recombinant protein techniques, we purified the reflectin 4Ax4 protein. We determined the leucine, tryptophan, and threonine amino acids are in an ordered state by solid-state nuclear magnetic resonance (NMR). Knowing these ordered amino acids is possibly the key to understanding reflectin's natural optical and electrical properties. Understanding the link between reflectin's structure and electrical properties is essential to make the next generation of bioelectronic materials based on inexpensive, natural resources.
Show less - Date Issued
- 2019
- Identifier
- CFE0007433, ucf:52712
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007433
- Title
- Spherical self-assembly of rous sarcoma virus CA, probed by solid-state NMR and the structure of prostate acidic phosphatase and reflectin protein.
- Creator
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Qiao, Xin, Chen, Bo, Tatulian, Suren, Schulte, Alfons, Cole, Alexander, University of Central Florida
- Abstract / Description
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In this dissertation, we investigate the morphology of three different protein assemblies, which are formed by prostate acidic phosphatase, residues 248-286 (PAP39), reflectin and rous sarcoma virus capsid (RSV CA). First of all, the main aim of this research is to study the structure of PAP39 which is derived from protease cleavage of Prostate Acidic Phosphatase. The PAP39 can form fibrils of different morphologies in phosphate-buffered saline (PBS) and NaBiCarb (25 mM sodium bicarbonate and...
Show moreIn this dissertation, we investigate the morphology of three different protein assemblies, which are formed by prostate acidic phosphatase, residues 248-286 (PAP39), reflectin and rous sarcoma virus capsid (RSV CA). First of all, the main aim of this research is to study the structure of PAP39 which is derived from protease cleavage of Prostate Acidic Phosphatase. The PAP39 can form fibrils of different morphologies in phosphate-buffered saline (PBS) and NaBiCarb (25 mM sodium bicarbonate and 40 mM sodium phosphate, pH=8.83) buffer conditions, each exhibiting different potentials to enhance the infection of HIV in vitro due to different assemble pathways. In this project, we use solid state nuclear magnetic resonance (ssNMR) and Transmission electron microscopy (TEM) to probe the molecular structure and the fibril morphology in those two buffers. In the second part, we study the optical property of reflectin and also apply ssNMR to evaluate its structure. Reflectin is a protein derived from in flat, structural platelets in reflective tissues of the Hawaiian bobtail squid which obtain unique self-assembling and optical properties. Its self- assembly manifest tunable iridescence and modulate incident light. It can be easily processed into thin films, photonic grating structures and fibrils. SsNMR and TEM are used to determine the structure of reflectin assembly and elucidate the mechanism for the iridescence.In the last part, we study the spherical assembly of RSV CA, which consists of 12 CA pentamers. Therefore, the high resolution structural information of this RSV CA spherical assembly can provide essential information to understand how the same CA protein switches into conformation suitable for pentameric assembly and causes sharp curvature in authentic capsid. We use transmission electron microscopy (TEM) to screen appropriate assembly and obtain spherical assembly sample contains predominantly of T=1 capsid. A series of 2D and 3D spectra were acquired. The ssNMR spectra of the assembly exhibit similar resolution and resonance patterns to those of the RSV CA tubular assembly in our previous work. By referring to the assignments of the tubular assembly, we assign 200 residues of the 237-residue RSV CA in its spherical assembly. The assignments show some regions of RSV CA adopt different chemical shifts, in spite of overall similar resonances, which implies the structural rearrangements upon the spherical assembly and conformation variation of CA to switch between hexameric and pentameric state.
Show less - Date Issued
- 2017
- Identifier
- CFE0006781, ucf:51814
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006781
- Title
- High Pressure Micro-Spectroscopy of Biological Assemblies and Cells.
- Creator
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Park, Sang, Schulte, Alfons, Chow, Lee, Luo, Weili, Phanstiel, Otto, University of Central Florida
- Abstract / Description
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Functional properties of living cells depend on the thermodynamic variables such as temperature and pressure. A unique tool to investigate volume effects on structure and metabolism of the cell and biomolecules is pressure perturbation. We have developed a new setup that enables micro-spectroscopy and optical imaging of individual live cells at variable pressure from 0.1 to 400 MPa. Following characterization of the setup, pressure and temperature effects on the secondary structure of the...
Show moreFunctional properties of living cells depend on the thermodynamic variables such as temperature and pressure. A unique tool to investigate volume effects on structure and metabolism of the cell and biomolecules is pressure perturbation. We have developed a new setup that enables micro-spectroscopy and optical imaging of individual live cells at variable pressure from 0.1 to 400 MPa. Following characterization of the setup, pressure and temperature effects on the secondary structure of the peptide Poly-L-glutamic acid (PGA) in deuterated water buffer solution were investigated. The amide I band of PGA is sensitive to pressure and temperature, and by spectral deconvolution, we determined the relative contributions due to the ?-helix and random coil conformations. The population of ?-helix increases with increasing pressure. Pressure effects on single red blood cells and the intracellular protein hemoglobin were studied by micro-Raman spectroscopy. In particular, we observed a shift in the frequency of the iron-histidine vibrational band in both the intracellular hemoglobin and hemoglobin in solutions. The iron-histidine mode is a sensitive structural marker of the crucial iron-protein linkage in heme proteins. The pressure dependent shift suggests a conformational change of the heme environment. This finding was further supported by micro-absorption measurements at variable pressure.In additional experiments, Raman spectroscopy was employed to probe molecular changes that occurred in hemoglobin in erythrocytes infected with the malaria parasite Plasmodium falciparum. The spectra of infected cells indicated that hemoglobin degradation can be correlated with the stages of the parasite multiplication cycle. The research was further extended towards probing size and shape changes of individual cells with pressure. The lateral diameter in yeast cells was observed to decrease with pressure in a reversible way. These results suggest that transport of the intra-cellular water may play a significant role for volume changes.In summary, pressure changes were shown to induce conformational changes in proteins and shape changes in yeast cells. A Raman technique was developed to monitor the states of Plasmodium falciparum multiplication cycle within a red blood cell.
Show less - Date Issued
- 2012
- Identifier
- CFE0004637, ucf:49909
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004637
- Title
- The Schr(&)#246;dinger Equation with Coulomb Potential Admits no Exact Solutions.
- Creator
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Toli, Ilia, Zou, Shengli, Harper, James, Heider, Emily, Chen, Gang, Schulte, Alfons, University of Central Florida
- Abstract / Description
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We prove that the Schr(&)#246;dinger equation with the electrostatic potential energy expressed by the Coulomb potential does not admit exact solutions for three or more bodies. It follows that the exact solutions proposed by Fock are flawed. The Coulomb potential is the problem. Based on the classical (non-quantum) principle of superposition, the Coulomb potential of a system of many particles is assumed to be the sum of all the pairwise Coulomb potentials. We prove that this is not accurate...
Show moreWe prove that the Schr(&)#246;dinger equation with the electrostatic potential energy expressed by the Coulomb potential does not admit exact solutions for three or more bodies. It follows that the exact solutions proposed by Fock are flawed. The Coulomb potential is the problem. Based on the classical (non-quantum) principle of superposition, the Coulomb potential of a system of many particles is assumed to be the sum of all the pairwise Coulomb potentials. We prove that this is not accurate. The Coulomb potential being a hyperbolic (not linear) function, the superposition principle does not apply.The Schr(&)#246;dinger equation as studied in this PhD dissertation is a linear partial differential equation with variable coefficients. The only exception is the Schr(&)#246;dinger equation for the hydrogen atom, which is a linear ordinary differential equation with variable coefficients. No account is kept of the spin or the effects of the relativity.New electrostatic potentials are proposed for which the exact solutions of the Schr(&)#246;dinger equation exist. These new potentials obviate the need for the three-body force interpretations of the electrostatic potential.Novel methods for finding the exact solutions of the differential equations are proposed. Novel proof techniques are proposed for the nonexistence of the exact solutions of the differential equations, be they ordinary or partial, with constant or variable coefficients. Few novel applications of the established approximate methods of the quantum chemistry are reported. They are simple from the viewpoint of the quantum chemistry, but have some important aerospace engineering applications.
Show less - Date Issued
- 2019
- Identifier
- CFE0007733, ucf:52422
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007733
- Title
- Electronic and Optoelectronic Transport Properties of Carbon Nanotube/Organic Semiconductor Devices.
- Creator
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Sarker, Biddut, Khondaker, Saiful, Schulte, Alfons, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
- Abstract / Description
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Organic field effect transistors (OFETs) are of significant research interest due to their promising applications in large area, low-cost electronic devices such as flexible displays, sensor arrays, and radio-frequency identification tags. A major bottleneck in fabricating high-performance OFET is the large interfacial barrier between the metal electrodes and organic semiconductors (OSC) which results in an inefficient charge injection. Carbon nanotubes (CNTs) are considered to be a promising...
Show moreOrganic field effect transistors (OFETs) are of significant research interest due to their promising applications in large area, low-cost electronic devices such as flexible displays, sensor arrays, and radio-frequency identification tags. A major bottleneck in fabricating high-performance OFET is the large interfacial barrier between the metal electrodes and organic semiconductors (OSC) which results in an inefficient charge injection. Carbon nanotubes (CNTs) are considered to be a promising electrode material which can address this challenge.In this dissertation, we demonstrate fabrication of high-performance OFETs using aligned array CNT electrodes and investigate the detailed electronic transport properties of the fabricated devices. The OFETs with CNT electrodes show a remarkable enhancement in the device performance such as high mobility, high current on-off ratio, higher cutoff frequency, absence of short channel effect and better charge carrier injection than those OFETs with metal electrodes. From the low temperature transport measurements, we show that the charge injection barrier at CNT/OSC interface is smaller than that of the metal/OSC interface. A transition from direct tunneling to Fowler-Nordheim tunneling observed in CNT/OSC system shows further evidence of low injection barrier. A lower activation energy measured for the OFETs with CNT electrodes gives evidence of lower interfacial trap states. Finally, OFETs are demonstrated by directly growing crystalline organic nanowires on aligned array CNT electrodes.In addition to investigating the interfacial barrier at CNT/OSC interface, we also studied photoconduction mechanism of the CNT and CNT/OSC nanocomposite thin film devices. We found that the photoconduction is due to the exciton dissociations and charge carrier separation caused by a Schottky barrier at the metallic electrode/CNT interface and diffusion of the charge carrier through percolating CNT networks. In addition, it is found that photoresponse of the CNT/organic semiconductor can be tuned by changing the weight percentage of CNT into the organic semiconductors.
Show less - Date Issued
- 2012
- Identifier
- CFE0004596, ucf:49217
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004596
- Title
- Self-assembly of Amyloid Aggregates Simulated with Molecular Dynamics.
- Creator
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Berhanu, Workalemahu, Masunov, Artem, Kolpashchikov, Dmitry, Ye, Jingdong, Zou, Shengli, Schulte, Alfons, University of Central Florida
- Abstract / Description
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ABSTRACTAmyloids are highly ordered cross-? sheet aggregates that are associated with many diseases such as Alzheimer's, type II diabetes and prion diseases. Recently a progress has been made in structure elucidation, environmental effects and thermodynamic properties of amyloid aggregates. However, detailed understanding of how mutation, packing polymorphism and small organic molecules influence amyloid structure and dynamics is still lacking. Atomistic modeling of these phenomena with...
Show moreABSTRACTAmyloids are highly ordered cross-? sheet aggregates that are associated with many diseases such as Alzheimer's, type II diabetes and prion diseases. Recently a progress has been made in structure elucidation, environmental effects and thermodynamic properties of amyloid aggregates. However, detailed understanding of how mutation, packing polymorphism and small organic molecules influence amyloid structure and dynamics is still lacking. Atomistic modeling of these phenomena with molecular dynamics (MD) simulations holds a great promise to bridge this gap. This Thesis describes the results of MD simulations, which provide insight into the effects of mutation, packing polymorphism and molecular inhibitors on amyloid peptides aggregation. Chapter 1 discusses the structure of amyloid peptides, diseases associated with amyloid aggregation, mechanism of aggregation and strategies to treat amyloid diseases. Chapter 2 describes the basic principles of molecular dynamic simulation and methods of trajectory analysis used in the Thesis. Chapter 3 presents the results of the study of several all-atom molecular dynamics simulations with explicit solvent, starting from the crystalline fragments of two to ten monomers each. Three different hexapeptides and their analogs produced with single glycine replacement were investigated to study the structural stability, aggregation behavior and thermodynamics of the amyloid oligomers. Chapter 4 presents multiple molecular dynamics (MD) simulation of a pair polymorphic form of five short segments of amyloid peptide. Chapter 5 describes MD study of single-layer oligomers of the full-length insulin with a goal to identify the structural elements that are important for insulin amyloid stability, and to suggest single glycine mutants that may improve formulation. Chapter 6 presents the investigation of the mechanism of the interaction of polyphenols molecules with the protofibrils formed by an amyloidogenic hexapeptide fragment (VQIVYK) of Tau peptide by molecular dynamics simulations in explicit solvent. We analyzed the trajectories of the large (7(&)#215;4) aggregate with and without the polyphenols.Our MD simulations for both the short and full length amyloids revealed adding strands enhances the internal stability of wildtype aggregates. The degree of structural similarity between the oligomers in simulation and the fibril models constructed based on experimental data may explain why adding oligomers shortens the experimentally observed nucleation lag phase of amyloid aggregation. The MM-PBSA free energy calculation revealed nonpolar components of the free energy is more favorable while electrostatic solvation is unfavorable for the sheet to sheet interaction. This explains the acceleration of aggregation by adding nonpolar co-solvents (methanol, tri?uoroethanol, and hexa?uoroisopropanol). Free energy decomposition shows residues situated at the interface were found to make favorable contribution to the peptide -peptide association.The results from the simulations might provide both the valuable insight for amyloid aggregation as well as assist in inhibitor design efforts. First, the simulation of the single glycine mutants at the steric zipper of the short segments of various pathological peptides indicates the intersheet steric zipper is important for amyloid stability. Mutation of the side chains at the dry steric zipper disrupts the sheet to sheet packing, making the aggregation unstable. Thus, designing new peptidomimetic inhibitors able to prevent the fibril formation based on the steric zipper motif of the oligomers, similar to the ones examined in this study may become a viable therapeutic strategy. The various steric zipper microcrystal structures of short amyloid segments could be used as a template to design aggregation inhibitor that can block growth of the aggregates. Modification of the steric zipper structure (structure based design) with a single amino acid changes, shuffling the sequences, N- methylation of peptide amide bonds to suppress hydrogen bonding ability of NH groups or replacement with D amino acid sequence that interact with the parent steric zipper could be used in computational search for the new inhibitors. Second, the polyphenols were found to interact with performed oligomer through hydrogen bonding and induce conformational change creating an altered aggregate. The conformational change disrupts the intermolecular amyloid contact remodeling the amyloid aggregate. The recently reported microcrystal structure of short segments of amyloid peptides with small organic molecules could serve as a pharamcophore for virtual screening of aggregation inhibitor using combined docking and MD simulation with possible enhancement of lead enrichment. Finally, our MD simulation of short segments of amyloids with steric zipper polymorphism showed the stability depends on both sequence and packing arrangements. The hydrophilic polar GNNQQNY and NNQNTF with interface containing large polar and/or aromatic side chains (Q/N) are more stable than steric zipper interfaces made of small or hydrophobic residues (SSTNVG, VQIVYK, and MVGGVV). The larger sheet to sheet interface of the dry steric zipper through polar Q/N rich side chains was found to holds the sheets together better than non Q/N rich short amyloid segments. The packing polymorphism could influence the structure based design of aggregation inhibitor and a combination of different aggregation inhibitors might be required to bind to various morphologic forms of the amyloid peptides.
Show less - Date Issued
- 2011
- Identifier
- CFE0004088, ucf:49131
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004088
- Title
- Nano-pipette as nanoparticle analyzer and capillary gated ion transistor.
- Creator
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Rudzevich, Yauheni, Chow, Lee, Heinrich, Helge, Schulte, Alfons, Yuan, Jiann-Shiun, University of Central Florida
- Abstract / Description
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The ability to precisely count inorganic and organic nanoparticles and to measure their size distribution plays a major role in various applications such as drug delivery, nanoparticles counting, and many others. In this work I present a simple resistive pulse method that allows translocations, counting, and measuring the size and velocity distribution of silica nanoparticles and liposomes with diameters from 50 nm to 250 nm. This technique is based on the Coulter counter technique, but has...
Show moreThe ability to precisely count inorganic and organic nanoparticles and to measure their size distribution plays a major role in various applications such as drug delivery, nanoparticles counting, and many others. In this work I present a simple resistive pulse method that allows translocations, counting, and measuring the size and velocity distribution of silica nanoparticles and liposomes with diameters from 50 nm to 250 nm. This technique is based on the Coulter counter technique, but has nanometer size pores. It was found that ionic current drops when nanoparticles enter the nanopore of a pulled micropipette, producing a clear translocation signal. Pulled borosilicate micropipettes with opening 50 ~ 350 nm were used as the detecting instrument. This method provides a direct, fast and cost-effective way to characterize inorganic and organic nanoparticles in a solution. In this work I also introduce a newly developed Capillary Ionic Transistor (CIT). It is presented as a nanodevice which provides control of ionic transport through nanochannel by gate voltage. CIT is Ionic transistor, which employs pulled capillary as nanochannel with a tip diameter smaller than 100 mm. We observed that the gate voltage applied to gate electrode, deposited on the outer wall of a capillary, affect a conductance of nanochannel, due to change of surface charge at the solution/capillary interface. Negative gate voltage corresponds to lower conductivity and positive gate increases conductance of the channel. This effect strongly depends on the size of the channel. In general, at least one dimension of the channel has to be small enough for electrical double layer to overlap.
Show less - Date Issued
- 2014
- Identifier
- CFE0005880, ucf:50882
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005880
- Title
- Resistive Pulse study of Vesicles and Liposomes.
- Creator
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Lin, Yuqing, Chow, Lee, Schulte, Alfons, Tatulian, Suren, Yuan, Jiann-Shiun, University of Central Florida
- Abstract / Description
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In this work, the properties of the liposomes, the artificially created vesicles by various methods, are explored by a resistive pulse method using micropipettes. The fact that vesicles are fundamental in the wide range of functionalities they fulfill as organelles strengthen the desire of understanding the properties of them. The motivation of this work comes from the significant roles that liposomes play in the development of targeted drug delivery systems. Among other significant variables...
Show moreIn this work, the properties of the liposomes, the artificially created vesicles by various methods, are explored by a resistive pulse method using micropipettes. The fact that vesicles are fundamental in the wide range of functionalities they fulfill as organelles strengthen the desire of understanding the properties of them. The motivation of this work comes from the significant roles that liposomes play in the development of targeted drug delivery systems. Among other significant variables, the size of liposomes is found to be one of the dominating parameters in liposome based drug delivery, and the correlation between liposome size and delivery efficiency is discussed. To help improving the size evaluation ability, a few mainstream methods for liposome size detection and measurements are reviewed. As a reliable and accessible alternative method for liposomes detection, the resistive pulse method is introduced and the measurement on liposomes size change upon pH gradient was performed using this method. With our current liposome composition, we found the size increases as environmental pH increases. Further investigation is performed with vesicular pH=6, 7, and 8, respectively. Lastly, the stability of the small unilamellar vesicles (SUV) was studied via resistive pulse method, by monitoring the size change of 50nm liposomes as function of time. A significant size change in freshly prepared 50nm liposomes is recorded. This information will provide invaluable knowledge for targeting tumor with tight tissues, where small size liposomes are needed.
Show less - Date Issued
- 2015
- Identifier
- CFE0005826, ucf:50933
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005826
- Title
- Solid Phase Extraction Room Temperature Fluorescence Spectroscopy for the Direct Quantification of Monohydroxy Metabolites of Polycyclic Aromatic Hydrocarbons in Urine Samples.
- Creator
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Calimag, Korina Jesusa, Campiglia, Andres, Belfield, Kevin, Yestrebsky, Cherie, Chumbimuni Torres, Karin, Schulte, Alfons, University of Central Florida
- Abstract / Description
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Polycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation pre-concentrates PAH, simplifies matrix composition, and...
Show morePolycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation pre-concentrates PAH, simplifies matrix composition, and facilitates analytical resolution in the chromatographic column. Among the several approaches that exist to pre-concentrate PAH from water samples, the Environmental Protection Agency (EPA) recommends the use of solid-phase extraction (SPE). High-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) are the basis for standard PAH identification and determination. Ultraviolet (UV) absorption and room temperature fluorescence detection are both widely used in HPLC, but the specificity of these detectors is modest. Since PAH identifi(&)#172;cation is solely based on retention times, unambiguous PAH identification requires complete chromatographic resolution of sample components. When HPLC is applied to (")unfamiliar(") samples, the EPA recommends that a supporting analytical technique such as GC-MS be applied to verify compound identification and to check peak-purity HPLC fractions. Independent of the volume of extracted water, the approximate time required to separate and determine the sixteen (")priority pollutants(") (EPA-PAH) via HPLC is approximately 60min. If additional GC-MS analysis is required for unambiguous PAH determination, the total analysis time will reach 2-3 hours per sample. If the concentrations of target species are found to lie outside the detector's response range, the sample must be diluted and the process repeated. These are important considerations when routine analysis of numerous samples is contemplated. Parent PAH are relatively inert and need metabolic activation to express their carcinogenicity. By virtue of the rich heterogeneous distribution of metabolic products they produce, PAH provide a full spectrum of the complexity associated with understanding the initial phase of carcinogenesis. PAH metabolites include a variety of products such as expoxides, hydroxyl aromatics, quinines, dihydrodiols, dioepoxides, tetrols and water soluble conjugates. During the past decades tremendous efforts have been made to develop bio-analytical techniques that possess the selectivity and sensitivity for the problem at hand. Depending on the complexity of the sample and the relative concentrations of the targeted metabolites, a combination of sample preparation techniques is often necessary to reach the limits of detection of the instrumental method of analysis. The numerous preparation steps open ample opportunity to metabolite loss and collection of inaccurate data. Separation of metabolites has been accomplished via HPLC, capillary electrophoresis (CE) and GC-MS. Unfortunately, the existence of chemically related metabolic products with virtually identical fragmentation patterns often challenges the specificity of these techniques. This dissertation presents significant improvements in various fronts. Its first original component (-) which we have named solid-phase nano-extraction (SPNE) - deals with the use of gold nanoparticles (Au NPs) as extracting material for PAH. The advantages of SPNE are demonstrated for the analysis of PAH in water samples via both HPLC1 and Laser-Excited Time-Resolved Shpol'skii Spectroscopy (LETRSS).2 The same concept is then extended to the analysis of monohydroxy-PAH in urine samples via SPE- HPLC3 and In-Capillary SPNE-CE.4 The second original component of this dissertation describes the application of Shpol'skii Spectroscopy to the analysis of polar PAH metabolites. The outstanding selectivity and sensitivity for the direct analysis of PAH at trace concentration levels has made Shpol'skii spectroscopy a leading technique in environmental analysis.5 Unfortunately, the requirement of a specific guest-host combination - typically a non-polar PAH dissolved in an n-alkane - has hindered its widespread application to the field of analytical chemistry. This dissertation takes the first steps in removing this limitation demonstrating its feasibility for the analysis of polar benzo[a]pyrene metabolites in alcohol matrixes.
Show less - Date Issued
- 2013
- Identifier
- CFE0005141, ucf:50693
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005141
- Title
- convective heat transfer in quasi-one-dimensional magnetic fluid in horizontal field and temperature gradients.
- Creator
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Huang, Jun, Luo, Weili, Schulte, Alfons, Del Barco, Enrique, Kassab, Alain, University of Central Florida
- Abstract / Description
-
In this work we studied the convective heat transfer in a magnetic fluid in both zero and applied magnetic fields. The natural convection is observed in a quasi-one dimensional magnetic fluid in a horizontal temperature gradient. The horizontal non-homogeneous magnetic fields were applied across the sample cell either parallel or anti-parallel to the temperature gradient. The temperature profile was measured by eight thermocouples and temperature sensitive paint. The flow velocity field and...
Show moreIn this work we studied the convective heat transfer in a magnetic fluid in both zero and applied magnetic fields. The natural convection is observed in a quasi-one dimensional magnetic fluid in a horizontal temperature gradient. The horizontal non-homogeneous magnetic fields were applied across the sample cell either parallel or anti-parallel to the temperature gradient. The temperature profile was measured by eight thermocouples and temperature sensitive paint. The flow velocity field and streamlines were obtained by optical flow method. Calculated Nusselt numbers, Rayleigh number, and Grashof number show that the convective flow is the main heat transfer mechanism in applied fields in our geometry. It was found that when the field gradient is parallel with temperature gradient, the fields enhance the convective heat transfer while the fields inhibit it in anti-parallel configuration by analyzing the temperature difference across the sample, flow patterns, and perturbation Q field in applied fields. Magnetic Rayleigh number and magnetic Grashof number show that the thermomagnetic convections dominate in high magnetic fields. It is shown that the physical nature of the field effect is corresponding to the magnetic body force which is perpendicular to the gravity in our experiments. When the direction of the magnetic body force is same with temperature gradient in parallel configuration, the body force increases the convective heat transfer; while it has opposite effect in anti-parallel configuration.Our study will not only shed light on the fundamental mechanisms for thermomagnetic convection but also help to develop the potential field-controlled heat transfer devices.
Show less - Date Issued
- 2015
- Identifier
- CFE0005957, ucf:50810
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005957
- Title
- Redox-Active Solid State Materials and its Biomedical and Biosensing Applications.
- Creator
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Gupta, Ankur, Seal, Sudipta, Dong, Yajie, Cho, Hyoung Jin, Zhai, Lei, Schulte, Alfons, University of Central Florida
- Abstract / Description
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Reactive oxygen species (ROS) are byproducts of physiological processes in human body, and strengthened production of ROS is known to cause acute conditions such as inflammation, aging, Alzheimer's disease, melanoma and ovarian cancer, fibrosis and multiple sclerosis. Therefore, early detection of ROS at nanomolar concentration (at cellular level) and developing more potent antioxidants is essential for regular health monitoring. As an example, ROS are also responsible for inflammation...
Show moreReactive oxygen species (ROS) are byproducts of physiological processes in human body, and strengthened production of ROS is known to cause acute conditions such as inflammation, aging, Alzheimer's disease, melanoma and ovarian cancer, fibrosis and multiple sclerosis. Therefore, early detection of ROS at nanomolar concentration (at cellular level) and developing more potent antioxidants is essential for regular health monitoring. As an example, ROS are also responsible for inflammation reactions at orthopedic implants-tissue interface triggered by wear debris. Inflammation induced by ROS results in revision surgery. Coatings of redox-active materials exhibiting antioxidant properties on implants have potential to mitigate the inflammation and delay the need of revision surgery. This dissertation focus on developing advanced functional nanomaterials by tailoring the surface chemistry of existing materials. Surface chemistry of materials can be altered by introducing surface and edge defects in the lattice structure Three materials system doped cerium oxide nanoparticles (d-CNPs), cerium oxide thin films (CeOx) and molybdenum disulfide (MoS2) nanoparticles, have been studied for its surface and edge contributions in potential biomedical and biosensing applications. Surface (d-CNPs and CeOx thin films) and edge chemistry (MoS2) have been tailored to understand its role and specific response.Surface Ce3+/Ce4+ oxidation state in CNPs controls the bio-catalytic activity. Higher superoxide dismutase (SOD) is demonstrated by high Ce3+/Ce4+ oxidation state. On the other hand, improved catalase mimetic activity is observed for low Ce3+/Ce4+ CNPs. Different CNPs preparation results in different Ce3+ to Ce4+ ratio, particle size, surface coating, and agglomeration, thus significantly varying the antioxidant properties of CNPs. In the first section of the dissertation, sustainable one-step room temperature synthesis of rare earth element (La, Sm, and Er) d-CNPs have been developed to effectively control the Ce3+ to Ce4+ ratio for specific biological application. Substitution of Ce4+ ions by trivalent dopants from ceria lattice increases the oxygen vacancies and density of catalytic sites. Uniform distribution of trivalent dopant in ceria lattice confirmed by EFTEM is attributed to enhanced SOD mimetic activity, ROS scavenging and tuning surface Ce3+/Ce4+ oxidation state in CNPs. Surface chemistry of redox-active cerium oxide coating on orthopedic implants also plays a vital role in scavenging ROS and mitigating inflammation. Thus, surface chemistry of CeOx thin films deposited by atomic layer deposited (ALD), have also been tailored by controlling the film thickness. CeOx film of 2 nm thickness has high Ce3+/Ce4+ (ratio 1) whereas higher thickness films (6-33 nm) have lower Ce3+/Ce4+ (ratio 0.30-0.37). These films have been further tested for catalase mimetic activity and hydrogen peroxide (H2O2) detection. Sensor selectivity is always a key issue. Most often, ascorbic acid found in the biological system, interfere in the electrochemical detection of H2O2 resulting in selectivity issue, thus protective Nafion layer is required to prevent cerium oxide-ascorbic acid interaction.To improve the selectivity of electrochemical sensors, Sulfur-deficient redox-active MoS2 have been utilized for electrochemical detection of pharmaceutically relevant chemical species. S-deficient MoS2 nanoparticles have been prepared by liquid exfoliation method to increase Mo-edge density and tested as sensing materials for detection of pharmaceutically relevant H2O2, hypochlorous acid (HOCl) and reactive nitrogen (NO*) species. The addition of ascorbic acid and uric acid have shown no interference during H2O2 detection. Change in S to Mo ratio have been studied using x-ray photoelectron spectroscopy. Density functional theory (DFT) have been employed to understand the detection mechanism and size-dependent sensitivity of MoS2. DFT study further reveals the role of S-deficiency and Mo- and S-edges in the higher catalytic activity of 5-7 nm MoS2 particles.Through these studies, the importance of defects in nanomaterials and their exotic properties at the nanoscale have been demonstrated. Understanding developed from these studies have provided the framework to develop more advanced functional nanomaterials for biomedical and biosensing applications.
Show less - Date Issued
- 2017
- Identifier
- CFE0006944, ucf:51655
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006944
- Title
- Self-assembly of Rous Sarcoma Virus capsid protein, probed by Solid-state NMR and TEM.
- Creator
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Jeon, Jaekyun, Chen, Bo, Tatulian, Suren, Schulte, Alfons, Cole, Alexander, University of Central Florida
- Abstract / Description
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The retroviral capsid protein (CA) is derived from the cleavage of Gag polyprotein during the maturation process, and self-assembles into a polymorphic fullerene-like shell encasing the viral genome materials. The orthoretroviral CAs, for instance, Human Immunodeficiency Virus (HIV) and Rous Sarcoma Virus (RSV) CA, has little similarity in their sequence composition but a common 3D structure. They form distinct capsid assembly in vivo and a range of similar assemblies in vitro. Due to the...
Show moreThe retroviral capsid protein (CA) is derived from the cleavage of Gag polyprotein during the maturation process, and self-assembles into a polymorphic fullerene-like shell encasing the viral genome materials. The orthoretroviral CAs, for instance, Human Immunodeficiency Virus (HIV) and Rous Sarcoma Virus (RSV) CA, has little similarity in their sequence composition but a common 3D structure. They form distinct capsid assembly in vivo and a range of similar assemblies in vitro. Due to the substantial polymorphism, such assemblies are not amenable for conventional structural biology techniques such as X-ray diffraction crystallography and cryo-electron microscopy (cryo-EM). Solid-state NMR spectroscopy is the optimal platform to study these CA assemblies to attain site-specific structural and dynamic information. However, it is challenging to make signal assignments for such non-crystalline and large biomolecules as retroviral CA assemblies. In this study, we were to elucidate the assembly mechanism of retroviral capsids by applying the state-of-art solid-state NMR techniques on the RSV CA assembly system and establishing an atomistic resolution structural model. The RSV CA is the second most studied protein among the retroviral family after HIV that causes AIDS (acquired immune deficiency syndrome), but there is no atomistic model for RSV CA assemblies available.In this study, we showed that highly uniform tubular RSV CA assembly can be prepared. Screened by TEM, our tubular assembly showed sharp 6-fold symmetry under diffraction, illustrating the quasi-crystalline character. Subsequently we acquired a series of solid-state NMRivspectra for tubular RSV CA assembly, and completed chemical shift signal assignments with samples of various isotope labeling. Then, combining cryo-EM electron density map of tubular assembly of RSV CA with the secondary structures derived from solid-state NMR, we established an atomistic resolution structure model. In this model, we identified the residue-specific assembly interfaces. Interestingly, our model revealed the structural re-arrangements upon the assembly and suggested that the tubular assembly of RSV CA may take a different assembly pathway from that of HIV capsid.
Show less - Date Issued
- 2016
- Identifier
- CFE0006332, ucf:51572
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006332
- Title
- Non-Destructive Analysis of Trace Textile Fiber Evidence via Room-Temperature Fluorescence Spectrocopy.
- Creator
-
Appalaneni, Krishnaveni, Campiglia, Andres, Belfield, Kevin, Sigman, Michael, Yestrebsky, Cherie, Schulte, Alfons, University of Central Florida
- Abstract / Description
-
Forensic fiber evidence plays an important role in many criminal investigations. Non-destructive techniques that preserve the physical integrity of the fibers for further court examination are highly valuable in forensic science. Non-destructive techniques that can either discriminate between similar fibers or match a known to a questioned fiber - and still preserve the physical integrity of the fibers for further court examination - are highly valuable in forensic science. When fibers cannot...
Show moreForensic fiber evidence plays an important role in many criminal investigations. Non-destructive techniques that preserve the physical integrity of the fibers for further court examination are highly valuable in forensic science. Non-destructive techniques that can either discriminate between similar fibers or match a known to a questioned fiber - and still preserve the physical integrity of the fibers for further court examination - are highly valuable in forensic science. When fibers cannot be discriminated by non-destructive tests, the next reasonable step is to extract the questioned and known fibers for dye analysis with a more selective technique such as high-performance liquid chromatography (HPLC) and/or gas chromatography-mass spectrometry (GC-MS). The common denominator among chromatographic techniques is to primarily focus on the dyes used to color the fibers and do not investigate other potential discriminating components present on the fiber. Differentiating among commercial dyes with very similar chromatographic behaviors and almost identical absorption spectra and/or fragmentation patterns is a challenging task.This dissertation explores a different aspect of fiber analysis as it focuses on the total fluorescence emission of fibers. In addition to the contribution of the textile dye (or dyes) to the fluorescence spectrum of the fiber, we investigate the contribution of intrinsic fluorescence impurities (-) i.e. impurities imbedded into the fibers during fabrication of garments - as a reproducible source of fiber comparison. Differentiation of visually indistinguishable fibers is achieved by comparing excitation-emission matrices (EEMs) recorded from single textile fibers with the aid of a commercial spectrofluorimeter coupled to an epi-fluorescence microscope. Statistical data comparison was carried out via principal component analysis. An application of this statistical approach is demonstrated using challenging dyes with similarities both in two-dimensional absorbance spectra and in three dimensional EEM data. High accuracy of fiber identification was observed in all the cases and no false positive identifications were observed at 99% confidence levels.
Show less - Date Issued
- 2013
- Identifier
- CFE0004808, ucf:49740
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004808