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Description
This work demonstrated a novel microfluidic device based on direct current (DC) insulator based dielectrophoresis (iDEP) for trapping individual mammalian cells in a microfluidic device. The novel device is also applicable for selective trapping of weakly metastatic mammalian breast cancer cells (MCF-7) from mixtures with mammalian Peripheral Blood Mononuclear Cells (PBMC) and highly metastatic mammalian breast cancer cells, MDA-MB-231. The advantage of this approach is the ease of integration of iDEP structures in microfliudic channels using soft lithography, the use of DC electric fields, the addressability of the single cell traps for downstream analysis and the straightforward multiplexing for single cell trapping. These microfluidic devices are targeted for capturing of single cells based on their DEP behavior. The numerical simulations point out the trapping regions in which single cell DEP trapping occurs. This work also demonstrates the cell conductivity values of different cell types, calculated using the single-shell model. Low conductivity buffers are used for trapping experiments. These low conductivity buffers help reduce the Joule heating. Viability of the cells in the buffer system was studied in detail with a population size of approximately 100 cells for each study. The work also demonstrates the development of the parallelized single cell trap device with optimized traps. This device is also capable of being coupled detection of target protein using MALDI-MS.
ContributorsBhattacharya, Sanchari (Author) / Ros, Alexandra (Committee member) / Ros, Robert (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2013
Description
Creative design lies at the intersection of novelty and technical feasibility. These objectives can be achieved through cycles of divergence (idea generation) and convergence (idea evaluation) in conceptual design. The focus of this thesis is on the latter aspect. The evaluation may involve any aspect of technical feasibility and may be desired at component, sub-system or full system level. Two issues that are considered in this work are: 1. Information about design ideas is incomplete, informal and sketchy 2. Designers often work at multiple levels; different aspects or subsystems may be at different levels of abstraction Thus, high fidelity analysis and simulation tools are not appropriate for this purpose. This thesis looks at the requirements for a simulation tool and how it could facilitate concept evaluation. The specific tasks reported in this thesis are: 1. The typical types of information available after an ideation session 2. The typical types of technical evaluations done in early stages 3. How to conduct low fidelity design evaluation given a well-defined feasibility question A computational tool for supporting idea evaluation was designed and implemented. It was assumed that the results of the ideation session are represented as a morphological chart and each entry is expressed as some combination of a sketch, text and references to physical effects and machine components. Approximately 110 physical effects were identified and represented in terms of algebraic equations, physical variables and a textual description. A common ontology of physical variables was created so that physical effects could be networked together when variables are shared. This allows users to synthesize complex behaviors from simple ones, without assuming any solution sequence. A library of 16 machine elements was also created and users were given instructions about incorporating them. To support quick analysis, differential equations are transformed to algebraic equations by replacing differential terms with steady state differences), only steady state behavior is considered and interval arithmetic was used for modeling. The tool implementation is done by MATLAB; and a number of case studies are also done to show how the tool works. textual description. A common ontology of physical variables was created so that physical effects could be networked together when variables are shared. This allows users to synthesize complex behaviors from simple ones, without assuming any solution sequence. A library of 15 machine elements was also created and users were given instructions about incorporating them. To support quick analysis, differential equations are transformed to algebraic equations by replacing differential terms with steady state differences), only steady state behavior is considered and interval arithmetic was used for modeling. The tool implementation is done by MATLAB; and a number of case studies are also done to show how the tool works.
ContributorsKhorshidi, Maryam (Author) / Shah, Jami J. (Thesis advisor) / Wu, Teresa (Committee member) / Gel, Esma (Committee member) / Arizona State University (Publisher)
Created2014
Description
This thesis contains the applications of the ASU mathematical model (Tolerance Maps, T-Maps) to the construction of T-Maps for patterns of line profiles. Previously, Tolerance Maps were developed for patterns of features such as holes, pins, slots and tabs to control their position. The T-Maps that are developed in this thesis are fully compatible with the ASME Y14.5 Standard. A pattern of square profiles, both linear and 2D, is used throughout this thesis to illustrate the idea of constructing the T-Maps for line profiles. The Standard defines two ways of tolerancing a pattern of profiles - Composite Tolerancing and Multiple Single Segment Tolerancing. Further, in the composite tolerancing scheme, there are two different ways to control the entire pattern - repeating a single datum or two datums in the secondary datum reference frame. T-Maps are constructed for all the different specifications. The Standard also describes a way to control the coplanarity of discontinuous surfaces using a profile tolerance and T-Maps have been developed. Since verification of manufactured parts relative to the tolerance specifications is crucial, a least squares fit approach, which was developed earlier for line profiles, has been extended to patterns of line profiles. For a pattern, two tolerances are specified, and the manufactured profile needs to lie within the tolerance zones established by both of these tolerances. An i-Map representation of the manufactured variation, located within the T-Map is also presented in this thesis.
ContributorsRao, Shyam Subramanya (Author) / Davidson, Joseph K. (Thesis advisor) / Arizona State University (Publisher)
Created2014
Description
A clean and sustainable alternative to fossil fuels is solar energy. For efficient use of solar energy to be realized, artificial systems that can effectively capture and convert sunlight into a usable form of energy have to be developed. In natural photosynthesis, antenna chlorophylls and carotenoids capture sunlight and transfer the resulting excitation energy to the photosynthetic reaction center (PRC). Small reorganization energy, λ and well-balanced electronic coupling between donors and acceptors in the PRC favor formation of a highly efficient charge-separated (CS) state. By covalently linking electron/energy donors to acceptors, organic molecular dyads and triads that mimic natural photosynthesis were synthesized and studied. Peripherally linked free base phthalocyanine (Pc)-fullerene (C60) and a zinc (Zn) phthalocyanine-C60 dyads were synthesized. Photoexcitation of the Pc moiety resulted in singlet-singlet energy transfer to the attached C60, followed by electron transfer. The lifetime of the CS state was 94 ps. Linking C60 axially to silicon (Si) Pc, a lifetime of the CS state of 4.5 ns was realized. The exceptionally long-lived CS state of the SiPc-C60 dyad qualifies it for applications in solar energy conversion devices. A secondary electron donor was linked to the dyad to obtain a carotenoid (Car)-SiPc-C60 triad and ferrocene (Fc)-SiPc-C60 triad. Excitation of the SiPc moiety resulted in fast electron transfer from the Car or Fc secondary electron donors to the C60. The lifetime of the CS state was 17 ps and 1.2 ps in Car-SiPc-C60 and Fc-SiPc-C60, respectively. In Chapter 3, an efficient synthetic route that yielded regioselective oxidative porphyrin dimerization is presented. Using Cu2+ as the oxidant, meso-β doubly-connected fused porphyrin dimers were obtained in very high yields. Removal of the copper from the macrocycle affords a free base porphyrin dimer. This allows for exchange of metals and provides a route to a wider range of metallporphyrin dimers. In Chapter 4, the development of an efficient and an expedient route to bacteriopurpurin synthesis is discussed. Meso-10,20- diformylation of porphyrin was achieved and one-pot porphyrin diacrylate synthesis and cyclization to afford bacteriopurpurin was realized. The bacteriopurpurin had a reduction potential of - 0.85 V vs SCE and λmax, 845 nm.
ContributorsArero, Jaro (Author) / Gust, Devens (Thesis advisor) / Moore, Ana (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2014
Description
Conformance of a manufactured feature to the applied geometric tolerances is done by analyzing the point cloud that is measured on the feature. To that end, a geometric feature is fitted to the point cloud and the results are assessed to see whether the fitted feature lies within the specified tolerance limits or not. Coordinate Measuring Machines (CMMs) use feature fitting algorithms that incorporate least square estimates as a basis for obtaining minimum, maximum, and zone fits. However, a comprehensive set of algorithms addressing the fitting procedure (all datums, targets) for every tolerance class is not available. Therefore, a Library of algorithms is developed to aid the process of feature fitting, and tolerance verification. This paper addresses linear, planar, circular, and cylindrical features only. This set of algorithms described conforms to the international Standards for GD&T.; In order to reduce the number of points to be analyzed, and to identify the possible candidate points for linear, circular and planar features, 2D and 3D convex hulls are used. For minimum, maximum, and Chebyshev cylinders, geometric search algorithms are used. Algorithms are divided into three major categories: least square, unconstrained, and constrained fits. Primary datums require one sided unconstrained fits for their verification. Secondary datums require one sided constrained fits for their verification. For size and other tolerance verifications, we require both unconstrained and constrained fits
ContributorsMohan, Prashant (Author) / Shah, Jami (Thesis advisor) / Davidson, Joseph K. (Committee member) / Farin, Gerald (Committee member) / Arizona State University (Publisher)
Created2014
Description
Solar energy is a promising alternative for addressing the world's current and future energy requirements in a sustainable way. Because solar irradiation is intermittent, it is necessary to store this energy in the form of a fuel so it can be used when required. The light-driven splitting of water into oxygen and hydrogen (a useful chemical fuel) is a fascinating theoretical and experimental challenge that is worth pursuing because the advance of the knowledge that it implies and the availability of water and sunlight. Inspired by natural photosynthesis and building on previous work from our laboratory, this dissertation focuses on the development of water-splitting dye-sensitized photoelectrochemical tandem cells (WSDSPETCs). The design, synthesis, and characterization of high-potential porphyrins and metal-free phthalocyanines with phosphonic anchoring groups are reported. Photocurrents measured for WSDSPETCs made with some of these dyes co-adsorbed with molecular or colloidal catalysts on TiO2 electrodes are reported as well. To guide in the design of new molecules we have used computational quantum chemistry extensively. Linear correlations between calculated frontier molecular orbital energies and redox potentials were built and tested at multiple levels of theory (from semi-empirical methods to density functional theory). Strong correlations (with r2 values > 0.99) with very good predictive abilities (rmsd < 50 mV) were found when using density functional theory (DFT) combined with a continuum solvent model. DFT was also used to aid in the elucidation of the mechanism of the thermal relaxation observed for the charge-separated state of a molecular triad that mimics the photo-induced proton coupled electron transfer of the tyrosine-histidine redox relay in the reaction center of Photosystem II. It was found that the inclusion of explicit solvent molecules, hydrogen bonded to specific sites within the molecular triad, was essential to explain the observed thermal relaxation. These results are relevant for both advancing the knowledge about natural photosynthesis and for the future design of new molecules for WSDSPETCs.
ContributorsMéndez-Hernández, Dalvin D (Author) / Moore, Ana L (Thesis advisor) / Mujica, Vladimiro (Thesis advisor) / Gust, Devens J. (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2014
Description
Increasing computational demands in data centers require facilities to operate at higher ambient temperatures and at higher power densities. Conventionally, data centers are cooled with electrically-driven vapor-compressor equipment. This paper proposes an alternative data center cooling architecture that is heat-driven. The source is heat produced by the computer equipment. This dissertation details experiments investigating the quantity and quality of heat that can be captured from a liquid-cooled microprocessor on a computer server blade from a data center. The experiments involve four liquid-cooling setups and associated heat-extraction, including a radical approach using mineral oil. The trials examine the feasibility of using the thermal energy from a CPU to drive a cooling process. Uniquely, the investigation establishes an interesting and useful relationship simultaneously among CPU temperatures, power, and utilization levels. In response to the system data, this project explores the heat, temperature and power effects of adding insulation, varying water flow, CPU loading, and varying the cold plate-to-CPU clamping pressure. The idea is to provide an optimal and steady range of temperatures necessary for a chiller to operate. Results indicate an increasing relationship among CPU temperature, power and utilization. Since the dissipated heat can be captured and removed from the system for reuse elsewhere, the need for electricity-consuming computer fans is eliminated. Thermocouple readings of CPU temperatures as high as 93°C and a calculated CPU thermal energy up to 67Wth show a sufficiently high temperature and thermal energy to serve as the input temperature and heat medium input to an absorption chiller. This dissertation performs a detailed analysis of the exergy of a processor and determines the maximum amount of energy utilizable for work. Exergy as a source of realizable work is separated into its two contributing constituents: thermal exergy and informational exergy. The informational exergy is that usable form of work contained within the most fundamental unit of information output by a switching device within a CPU. Exergetic thermal, informational and efficiency values are calculated and plotted for our particular CPU, showing how the datasheet standards compare with experimental values. The dissertation concludes with a discussion of the work's significance.
ContributorsHaywood, Anna (Author) / Phelan, Patrick E (Thesis advisor) / Herrmann, Marcus (Committee member) / Gupta, Sandeep (Committee member) / Trimble, Steve (Committee member) / Myhajlenko, Stefan (Committee member) / Arizona State University (Publisher)
Created2014
Description
[FeFe]-hydrogenases are enzymes for the reduction of protons to hydrogen. They rely on only the earth abundant first-row transition metal iron at their active site (H cluster). In recent years, a multitude of diiron mimics of hydrogenases have been synthesized, but none of them catalyzes hydrogen production with the same exquisite combination of high turnover frequency and low activation energy as the enzymes. Generally, model complexes fail to include one or both of two features essential to the natural enzyme: an intricate array of outer coordination sphere contacts that constrain the coordination geometry to attain a catalytically optimal conformation, and the redox non-innocence of accessory [FeS] clusters found at or near the hydrogen-activating site. The work presented herein describes the synthesis and electrocatalytic characterization of iron-dithiolate models designed to incorporate these features. First, synthetic strategies are developed for constructing peptides with artificial metal-binding motifs, such as 1,3-dithiolate and phosphines, which are utilized to append diiron-polycarbonyl clusters onto a peptide. The phosphine-functionalized peptides are shown to be better electrocatalysts for proton reduction in water/acetonitrile mixtures than in neat acetonitrile. Second, we report the impact of redox non-innocent ligands on the electrocatalytic properties of two types of [FeFe]-hydrogenase models: dinuclear and mononuclear iron complexes. The bidentate, redox non-innocent α-diimine ligands (N-N), 2,2'-bipyridine and 2,2' bipyrimidine, are used to create complexes with the general formula (μ-SRS)Fe2(CO)4(N-N), new members of the well known family of asymmetric diiron carbonyls. While the 2,2'-bipyridine derivatives can act as electrocatalysts for proton reduction, surprisingly, the 2,2'-bipyrimidine analogues are found to be inactive towards catalysis. Electrochemical investigation of two related Fe(II) complexes, (bdt)Fe(CO)P2 for bdt = benzene-1,2-dithiolate and P2 = 1,1'-diphenylphosphinoferrocene or methyl-2-{bis(diphenylphosphinomethylamino}acetate, related to the distal iron in [FeFe]-hydrogenase show that these complexes catalyze the reduction of protons under mild conditions. However, their reactivities toward the external ligand CO are distinguished by gross geometrical differences.
ContributorsRoy, Souvik (Author) / Jones, Anne K (Thesis advisor) / Moore, Thomas (Committee member) / Trovitch, Ryan (Committee member) / Arizona State University (Publisher)
Created2013
Description
Natural photosynthesis dedicates specific proteins to achieve the modular division of the essential roles of solar energy harvesting, charge separation and carrier transport within natural photosynthesis. The modern understanding of the fundamental photochemistry by which natural photosynthesis operates is well advanced and solution state mimics of the key photochemical processes have been reported previously. All of the early events in natural photosynthesis responsible for the conversion of solar energy to electric potential energy occur within proteins and phospholipid membranes that act as scaffolds for arranging the active chromophores. Accordingly, for creating artificial photovoltaic (PV) systems, scaffolds are required to imbue structure to the systems. An approach to incorporating modular design into solid-state organic mimics of the natural system is presented together with how conductive scaffolds can be utilized in organic PV systems. To support the chromophore arrays present within this design and to extract separated charges from within the structure, linear pyrazine-containing molecular ribbons were chosen as candidates for forming conductive linear scaffolds that could be functionalized orthogonally to the linear axis. A series of donor-wire-acceptor (D-W-A) compounds employing porphyrins as the donors and a C60 fullerene adduct as the acceptors have been synthesized for studying the ability of the pyrazine-containing hetero-aromatic wires to mediate photoinduced electron transfer between the porphyrin donor and fullerene acceptor. Appropriate substitutions were made and the necessary model compounds useful for dissecting the complex photochemistry that the series is expected to display were also synthesized. A dye was synthesized using a pyrazine-containing heteroaromatic spacer that features two porphyrin chromophores. The dye dramatically outperforms the control dye featuring the same porphyrin and a simple benzoic acid linker. A novel, highly soluble 6+kDa extended phthalocyanine was also synthesized and exhibits absorption out to 900nm. The extensive functionalization of the extended phthalocyanine core with dodecyl groups enabled purification and characterization of an otherwise insoluble entity. Finally, in the interest of incorporating modular design into plastic solar cells, a series of porphyrin-containing monomers have been synthesized that are intended to form dyadic and triadic molecular-heterojunction polymers with dedicated hole and electron transport pathways during electrochemical polymerization.
ContributorsWatson, Brian Lyndon (Author) / Gust, Devens (Thesis advisor) / Gould, Ian (Committee member) / Moore, Ana L (Committee member) / Arizona State University (Publisher)
Created2013
Description
Black carbon (BC) is the product of incomplete combustion of biomass and fossil fuels. It is found ubiquitously in nature and is relevant to studies in atmospheric science, soil science, oceanography, and anthropology. Black carbon is best described using a combustion continuum that sub-classifies BC into slightly charred biomass, char, charcoal and soot. These sub-classifications range in particle size, formation temperature, and relative reactivity. Interest in BC has increased because of its role in the long-term storage of organic matter and the biogeochemistry of urban areas. The global BC budget is unbalanced. Production of BC greatly outweighs decomposition of BC. This suggests that there are unknown or underestimated BC removal processes, and it is likely that some of these processes are occurring in soils. However, little is known about BC reactivity in soil and especially in desert soil. This work focuses on soot BC, which is formed at higher temperatures and has a lower relative reactivity than other forms of BC. Here, I assess the contribution of soot BC to central AZ soils and use the isotopic composition of soot BC to identify sources of soot BC. Soot BC is a significant (31%) fraction of the soil organic matter in central AZ and this work suggests that desert and urban soils may be a storage reservoir for soot BC. I further identify previously unknown removal processes of soot BC found naturally in soil and demonstrate that soil soot BC undergoes abiotic (photo-oxidation) and biotic reactions. Not only is soot BC degraded by these processes, but its chemical composition is altered, suggesting that soot BC contains some chemical moieties that are more reactive than others. Because soot BC demonstrates both refractory and reactive character, it is likely that the structure of soot BC; therefore, its interactions in the environment are complex and it is not simply a recalcitrant material.
ContributorsHamilton, George (Author) / Hartnett, Hilairy E (Thesis advisor) / Herckes, Pierre (Committee member) / Hall, Sharon (Committee member) / Arizona State University (Publisher)
Created2013