<p> This thesis is part of current research at Center for Intelligence Systems Research (CISR) at The George Washington University for developing new in-vehicle warning systems via Brain-Computer Interfaces (BCIs). The purpose of conducting this research is to contribute to the current gap between BCI and in-vehicle safety studies. It is based on the premise that accurate and timely monitoring of human (driver) brain's signal to external stimuli could significantly aide in detection of driver's intentions and development of effective warning systems. The thesis starts with introducing the concept of BCI and its development history while it provides a literature review on the nature of brain signals. The current advancement and increasing demand for commercial and non-medical BCI products are described. In addition, the recent research attempts in transportation safety to study drivers' behavior or responses through brain signals are reviewed. The safety studies, which are focused on employing a reliable and practical BCI system as an in-vehicle assistive device, are also introduced. A major focus of this thesis research has been on the evaluation and development of the signal processing algorithms which can effectively filter and process brain signals when the human subject is subjected to Visual LED (Light Emitting Diodes) stimuli at different frequencies. The stimulated brain generates a voltage potential, referred to as Steady-State Visual Evoked Potential (SSVEP). Therefore, a newly modified analysis algorithm for detecting the brain visual signals is proposed. These algorithms are designed to reach a satisfactory accuracy rate without preliminary trainings, hence focusing on eliminating the need for lengthy training of human subjects. Another important concern is the ability of the algorithms to find correlation of brain signals with external visual stimuli in real-time. The developed analysis models are based on algorithms which are capable of generating results for real-time processing of BCI devices. All of these methods are evaluated through two sets of recorded brain signals which were recorded by g.TEC CO. as an external source and recorded brain signals during our car driving simulator experiments. The final discussion is about how the presence of an SSVEP based warning system could affect drivers' performances which is defined by their reaction distance and Time to Collision (TTC). Three different scenarios with and without warning LEDs were planned to measure the subjects' normal driving behavior and their performance while they use a warning system during their driving task. Finally, warning scenarios are divided into short and long warning periods without and with informing the subjects, respectively. The long warning period scenario attempts to determine the level of drivers' distraction or vigilance during driving. The good outcome of warning scenarios can bridge between vehicle safety studies and online BCI system design research. The preliminary results show some promise of the developed methods for in-vehicle safety systems. However, for any decisive conclusion that considers using a BCI system as a helpful in-vehicle assistive device requires far deeper scrutinizing.</p>

<p> Glutathione-capped gold nanoparticles of size 1, 3, and 10 nm, CTAB-stabilized gold nanorods, as well as ro-carboxylate-functionalized palladium nanoparticles were synthesized and self-assembled onto graphene oxide to study their coarsening or reshaping behaviors upon heating at different temperatures ranging from 50 &deg;C to 300 &deg;C. These engineered nanoparticle- or nanorod-graphene oxide hybrid materials were studied by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR) spectroscopy, and UV-Vis spectroscopy.</p><p> The spherical nanoparticles would undergo coalescence to become larger particles and the nanorods would undergo reshaping to spherical particles. UV-Vis results show that the plasmonic band of gold nanoparticles at 520 nm would shift to higher wavelength indicating the coarsening into larger particles upon heating. Transmission electron microscopy results were generally in good agreements with the UV-Vis results and would be used as a direct tool to observe the structural changes of gold nanoparticles upon heat treatments.</p><p> Without the presence of graphene oxide, the nanoparticle coalescence began at the temperature between 150 and 200 &deg;C for all three nanoparticles with different core sizes. But with the presence of graphene oxide, nanoparticles start to coalesce at the temperature below 150 &deg;C. The gold nanorods have two plasmonic bands at &sim;780 and &sim;520 nm. The bands at &sim;780 nm for gold nanorods would disappear when the gold nanorods-graphene oxide is heated at 50 &deg;C indicating the complete reshaping of nanorods even at such a low temperature. Gold nanorods themselves are more stable and do not undergo the reshaping completely until the sample is heated above 150 &deg;C. Since graphene oxide is an excellent thermal conductor, we propose that graphene oxide could transfer heat to the nanoparticles and nanorods efficiently, disrupt the interaction of stabilizing ligands, and make them to either coalesce or undergo reshaping at a lower temperature.</p><p> Nanoparticle- and nanorod-graphene oxide hybrid materials were also used to study the effect of covalent and non-covalent interactions between gold nanoparticles or nanorods and graphene oxide during coarsening or reshaping, respectively. Non-covalent interactions were studied by directly adding graphene oxide to aqueous solutions containing water-soluble metal nanoparticles or nanorods, and covalent interactions were achieved by the self-assembly of the same nanoparticles onto thiolated graphene oxide that was prepared by coupling L-cystine using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS). When nanoparticles and nanorods are attached to graphene oxide through additional -covalent bonds, they are more strongly immobilized and therefore would undergo less coalescence and slower reshaping upon heating.</p>

<p>Transforming growth factor beta (TGF-beta) is an important cytokine responsible for a wide range of different cellular functions including extracellular matrix formation, angiogenesis and epithelial-mesenchymal transition. We have sought to use self-assembling DNA nanostructures to influence TGF-beta signaling.</p><p>The predictable Watson Crick base pairing allows for designing selfassembling nanoscale structures using oligonucleotides. We have used the method of DNA origami to assemble structures functionalized with multiple peptides that bind TGF-beta receptors outside the ligand binding domain. This allows the nanostructures to cluster TGF-beta receptors and lower the energy barrier of ligand binding thus sensitizing the cells to TGF-beta stimulation. To prove efficacy of our nanostructures we have utilized immunofluorescent staining of Smad2/4 in order to monitor TGF-beta mediated translocation of Smad2/4 to the cell nucleus. We have also utilized Smad2/4 responsive luminescence constructs that allows us to quantify TGF-beta stimulation with and without nanostructures.</p><p>To functionalize our nanostructures we relied on biotin-streptavidin linkages. This introduces a multivalency that is not necessarily desirable in all designs. Therefore we have investigated alternative means of functionalization. </p><p>The first approach is based on targeting DNA nanostructure by using zinc finger binding proteins. Efficacy of zinc finger binding proteins was assayed by the use of enzyme-linked immunosorbent (ELISA) assay and atomic force microscopy (AFM). While ELISA indicated a relative specificity of zinc finger proteins for target DNA sequences AFM showed a high degree of non-specific binding and insufficient affinity. </p><p>The second approach is based on using peptide nucleic acid (PNA) incorporated in the nanostructure through base pairing. PNA is a synthetic DNA analog consisting of a backbone of repeating N-(2-aminoethyl)-glycine units to which purine and pyrimidine bases are linked by amide bonds. The solid phase synthesis of PNA allows for convenient extension of the backbone into a peptide segment enabling peptide functionalization of DNA nanostructures. We have investigated how the neutral character of PNA alters the incorporation in DNA based nanostructures compared to a DNA control using biotinylation and AFM.</p><p>Results indicate that PNA can successfully be used as a way of functionalizing DNA nanostructures. Additionally we have shown that functionalized nanostructures are capable of sensitizing cells to TGF-beta stimulation.</p> / Dissertation

Emerging fields such as "Organs on a Chip", disease modeling in vitro, stem cell manufacturing and wearable bioelectronics are demanding rapid development of 3D Microelectrode Arrays (MEAs) for electrical interfacing with biological constructs. The work reported in this thesis focuses on two developmental tracks: "Dynamic 3D MEAs" and metal microfabrication for 3D MEAs. In the first part of the thesis, we explore the capabilities and limitations of 3D printed microserpentines (µserpentines) and utilize these structures to develop dynamic 3D microelectrodes. Analytical modeling of µserpentines flexibility followed by integration into a flexible Kapton® package and PDMS insulation are demonstrated. These 3D MEAs were further characterized in dynamic impedance measurement experiments and with an artificial skin model demonstrating their potential for wearable bioelectronics. In the second part of the thesis, microfabrication of the 3D metal MEAs for in vitro cell constructs is reported. These were fabricated using laser micromachining in 2D and transitioned out-of-plane to the final 3D conformation by a custom fabricated Hypodermic Needle Array (Hypo-Rig). The 3D metal MEAs were packaged on multiple substrates, and a 3D insulation layer was defined to fabricate microelectrodes that were subsequently characterized mechanically and electrically.

Theses (M.S.)--Marshall University, 2006. / Title from document title page. Includes abstract. Document formatted into pages: contains v, 75 pages including illustrations. Bibliography: p. 72-75.

<p> There are many unexplained phenomena that have been observed via atomic force microscopy (AFM) experiments. Understanding the cause of these phenomena is important to perform more accurate quantitative imaging using contact-resonance AFM and other contact-mode AFM techniques at higher scan speeds. This thesis presents evidence to confirm the existence of a scan speed dependent contact-mode AFM phenomenon and applies a squeeze film hydrodynamic lubrication model to explain it. Contact-resonance spectroscopy is used to investigate the phenomenon in which, above a critical scan speed, there is a monotonic decrease in the measured contact-resonance frequency with increasing scan speed. The observed phenomenon was replicated on a mica sample in a randomized set of AFM experiments performed at the National Institute for Standards and Technology (NIST). A literature review revealed that there is a thin water film that exists on mica under certain relative humidity (RH) conditions that has dynamic properties. The squeeze film hydrodynamic lubrication model predicts the general trend observed in the experimental data. However, there exists a higher order model that can be used to investigate the scan speed phenomenon more completely. </p><p>

<p> Characterization of magnetic domain structure is essential to understand and manipulate the magnetic properties of materials. In this thesis, we have utilized Lorentz Transmission Electron Microscopy (LTEM) in combination with image simulations based on micromagnetic models, to investigate the magnetic domain structure of a unique nano-chessboard structure consisting of L1<i> 0</i> and L1₂ phases in a Co₄₀Pt₆₀ alloy. We have shown high-resolution LTEM images of nano-size magnetic features acquired through spherical aberration correction in Lorentz Fresnel mode. Phase reconstructions based on the transport of intensity equation has been carried out to fully understand the magnetic domain structure and to extract quantitative information, including direction of magnetic induction and magnetic domain wall width, from the Lorentz TEM images. The experimental Fresnel images of the nano-chessboard structure show zig-zag shaped magnetic domain walls at the inter-phase boundaries between L1<i>0</i> and L1₂ phases. A circular magnetization distribution with vortex and anti-vortex type arrangement is evident in the phase reconstructed magnetic induction maps as well as simulated maps. The magnetic contrast in experimental LTEM images has been properly interpreted with the help of magnetic induction maps simulated for various relative electron beam-sample orientations inside TEM. Apart from the nano-chessboard structure, this alloy shows other interesting microstructural features such as anti-phase boundaries, tweed structure, coarse L1<i>0</i> plates, and macro-twins all of which have been characterized using conventional bright field/dark field TEM imaging and compared with their respective Lorentz TEM images. The magnetic domain wall widths obtained for each microstructure has been compared and the influence of microstructure and the particle size on wall widths has been discussed.</p><p>

<p> Recently, there has been growing interest in using transition metals (TM) for catalytic and electromagnetic applications, due to the ability of TMs to form stable compounds in multiple oxidation states. In this research, the focus has been on the synthesis and characterization of carbon-supported TM nanoparticles (NPs), specifically palladium (Pd) and gold (Au) NPs, for catalytic applications, and transition metal oxides (TMO) NPs, specifically Fe₃O₄ NPs for electromagnetic applications. Carbon supports have several advantages, such as enabling even distribution of particles, offering large specific surface area with excellent electron conductivity, and relative chemical inertness. </p><p> In this dissertation, for catalytic applications, emphasis was on removal of trichloroethylene (TCE) from groundwater. For this application, carbon-supported Pd/Au NP catalysts were developed. Pd was chosen because it is more active, stable and selective for desired end-products, and Au has shown to be a good promotor of Pd&rsquo;s catalytic activity. Often, commercially available Pd-based catalysts are made using harsh chemicals, which can be harmful to the environment. Here, an environmentally friendly process with aspects of green chemistry was developed to produce carbon-supported Pd/Au NP catalysts. This process uses a combination of sonochemistry and solvothermal syntheses. The carefully designed carbon-supported Pd/Au NP catalyst material was systematically characterized, tested against TCE, and optimized for increased rate of removal of TCE. Electron microscopy and spectroscopy techniques were used to study the material including structure, configuration and oxidative state. The Pd/Au NPs were found mainly to form clusters with an aggregate-Pd_ShellAu_Core structure. Using state-of-the-art direct detection with electron energy loss spectroscopy, the Pd NPs were found to have an oxidative state of zero (0). The formation of the catalyst material was studied in detail by varying several synthesis parameters including type of solvent, sonication time, synthesis temperature etc. The most optimized catalyst was found remove TCE at double the rate of corresponding commercial Pd-based catalysts in a hydrogen headspace. This material was found to catalyze the removal of TCE via traditional hydrodehalogenation and shows promise for the removal of other contaminants such as trichloropropane (TCP), carbon tetrachloride (CT). </p><p> This green approach to make and optimize TM materials for specific applications was extended to TMOs, specifically magnetite (Fe₃O₄) and further developed for the application of electromagnetism. As catalysts, Fe₃O₄ is used for removal of <i>p</i>-nitrophenol from water. However, since the carbon-supported Pd/Au material system was developed and optimized for catalysis, here, carbon-supported Fe₃O₄ NPs were developed for electromagnetic applications. There has been growing interest in tuning the magnetic properties of materials at room temperature with the use of external electric fields, for long-term applications in data storage and spintronic devices. While a complete reversible change of material properties has not yet been achieved, some success in partial switching has been achieved using multiferroic spinel structures such as Fe₃O₄. These materials experience a change in magnetic moment at room temperature when exposed to the electric fields generated by electrochemical cells such as lithium ion batteries (LIBs) and supercapacitors (SC). In the past, a 1% reversible change was observed in Fe₃O₄ using LIBs. Here, building on the developments from previous material system, Fe₃O₄ NPs were directly hybridized onto the graphene support in order to increase the observable change in magnetic moment. The material was systematically designed and tested for this application, including a study of the material formation. A simple, environmentally friendly synthesis using the solvothermal process was implemented to make the graphene-supported Fe₃O₄ NPs. This new material was found to produce a reversible change of up to 18% in a LIB. In order to overcome some of the difficulties of testing with a LIB, a corresponding hybrid SC was designed, built and calibrated. The graphene-supported Fe₃O₄ NPs were found to produce a net 2% reversibility in the SC, which has not been reported before. The results from both the LIB and SC were analyzed to better understand the mechanism of switching in a spinel ferrite such as Fe₃O₄, which can help optimize the material for future applications. </p><p> The focus of this dissertation was on the development of a methodology for carbon-supported TM and TMO NPs for specific applications. It is envisioned that this approach and strategy will contribute towards the future optimization of similar material systems for a multitude of applications.</p><p>

Made available in DSpace on 2016-03-07T19:20:22Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-06-19. Added 1 bitstream(s) on 2016-03-07T19:24:01Z : No. of bitstreams: 1 000859514.pdf: 3483784 bytes, checksum: b547cf28a51eb4183a1ac01ea16452fb (MD5) / Portadores de cadeias macromoleculares flexíveis e interligadas covalentemente, os hidrogéis são polímeros hidrofílicos, e quando sintetizados a partir da junção de polímeros sintéticos e naturais possuem excelente biocompatibilidade, biodegradabilidade e porosidade. O que amplia sua aplicabilidade desde liberação controlada, tanto de medicamentos quanto de nutrientes para o solo, implantes terapêuticos, cultura de células e cartilagens, dentre outros. Nesse trabalho, os hidrogéis nanocompósitos foram sintetizados via polimerização radical livre a partir de poliacrilamida (PAAm), carboximetilcelulose (CMC) e zeólita. A caracterização desses nanocompósitos foi realizada a partir de estudos de grau de intumescimento, no qual foram utilizados 4 meio diferentes (água destilada, NaCl (variando- se a concentração em 0,05; 0,10; 0,15 e 0,20 mol/L), CaCl 2 (a 0,15 mol/L) e AlCl 3 (a 0,15 mol/L)); propriedades cinéticas (n e k); espectroscopia de absorção no infravermelho (FTIR); microscopia eletrônica de varredura (MEV) e análises térmicas (TG, DTG e DSC). Concluímos que os hidrogéis de PAAm, CMC e zeólita apresentaram menor capacidade de absorção quando comparados a hidrogéis de PAAm e CMC. Percebemos que a concentração de catalisador N, N, N', N' -tetrametiletilenodiamina (TEMED) tem forte influência sobre o grau de intumescimento dos hidrogéis, pois age diretamente na velocidade e na formação das reações que originam os hidrogéis nanocompósitos. As soluções salinas contendo cargas iônicas maiores (CaCl 2 e AlCl 3 ) apresentam menor desempenho no grau de intumescimento; enquanto que soluções com carga menor (NaCl) apresentam melhor desempenho, sendo que sua concentração não provocou grandes variações no grau de intumescimento. Como visto nas análises de FTIR, MEV e EDS, pode-se afirmar que houve interação entre os hidrogéis de PAAm e CMC... / Carriers and flexible macromolecular chains covalently linked, hydrogels are highly hydrophilic polymers, and when synthesized from the junction of synthetic and natural polymers have excellent biocompatibility, biodegradability and porosity. What expands its applicability from controlled release of both drugs as nutrients to the soil, therapeutic implants, cell culture and cartilage, and others. In this work, nanocomposite hydrogels formed from polyacrylamide (PAAm), carboxymethylcellulose (CMC) and zeolite were synthesized via free radical polymerization. The characterizations of these nanocomposites were made from swelling degree studies in four different media (distilled water, NaCl (varying the concentration of 0.05; 0.10; 0, 15 and 0.20 mol / L), CaCl 2 (0.15 mol / L) and AlCl 3 (0.15 mol / L); kinetic properties (n and k); fourier transform infrared spectroscopy (FTIR); scanning electron microscopy (SEM) and thermal analysis (TG, DTG and DSC). It was possible to conclude that the PAAm, CMC and zeolite hydrogels had lower absorption capacity when compared to hydrogels without zeolite. Also, the concentration of N, N, N', N' - tetramethylethylenediamine TEMED catalyst has strong influence on the degree of swelling of hydrogels, because it acts directly on the speed and in the polymerization reactions. Saline solutions containing large ionic charges (CaCl 2 and AlCl 3 ) have lower performance in the swelling degree when compared to solutions with small charge (NaCl), being that its variation no provoked significant changes in the swelling degree. As seen in the FTIR, SEM and EDS techniques, there was interaction between hydrogels PAAm and CMC with the zeolite, decreasing the matrix pore sizes which directly influences the degree of swelling and structure of hydrogels. From thermal analysis, it was possible to conclude that the zeolite increased the thermal stability of nanocomposites. Thus ...

abstract: Atomic force microscopy (AFM) has become an important tool to characterize and image surfaces with nanoscale resolution. AFM imaging technique has been utilized to study a wide range of substances such as DNA, proteins, cells, silicon surfaces, nanowires etc. Hence AFM has become extremely important in the field of biochemistry, cell biology and material science. Functionalizing the AFM tip made it possible to detect molecules and their interaction using recognition imaging at single molecule level. Also the unbinding force of two molecules can be investigated based on AFM based single molecule force spectroscopy. In the first study, a new chemical approach to functionalize the AFM tip in a simple and user-friendly way has been described. Copper-free click chemistry and a vinyl sulfone PEG linker have been utilized during the process. Using this technique, human thrombin and integrin were detected in separate experiments. Then a novel tri-arm linker with two recognition molecules on it was designed and two proteins (human thrombin and integrin) were detected simultaneously in the same experiment using recognition imaging. This technique can be applied to understand many multivalent interactions taking place in nature. Using the same tri-arm linker functionalized with two biotin molecules, the interaction of streptavidin with mono-biotin and bis-biotin ligands were investigated. The thermal stability of streptavidin-biotin complex was also studied using SDS-PAGE analysis. In the final study, structure of native chromatin extracted from normal and cancer cell lines were analyzed using AFM imaging and agarose gel electrophoresis. Different salt fractions were used to extract chromatin region depending on their solubility. Mnase sensitivity of the chromatin sample was used to understand the open and closed structures of chromatin from different sources. The amount of chromatin in different salt fractions could act as an indicator of amount of open and condensed chromatin in normal and cancer cells. Eventually this ratio of closed and open structure of chromatin could be an indicator of tumorigenic nature of particular cell lines. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2015