6 resultados para Reversible Addition-Fragmentation Chain Transfer

em DRUM (Digital Repository at the University of Maryland)


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The Mongolian gazelle, Procapra gutturosa, resides in the immense and dynamic ecosystem of the Eastern Mongolian Steppe. The Mongolian Steppe ecosystem dynamics, including vegetation availability, change rapidly and dramatically due to unpredictable precipitation patterns. The Mongolian gazelle has adapted to this unpredictable vegetation availability by making long range nomadic movements. However, predicting these movements is challenging and requires a complex model. An accurate model of gazelle movements is needed, as rampant habitat fragmentation due to human development projects - which inhibit gazelles from obtaining essential resources - increasingly threaten this nomadic species. We created a novel model using an Individual-based Neural Network Genetic Algorithm (ING) to predict how habitat fragmentation affects animal movement, using the Mongolian Steppe as a model ecosystem. We used Global Positioning System (GPS) collar data from real gazelles to “train” our model to emulate characteristic patterns of Mongolian gazelle movement behavior. These patterns are: preferred vegetation resources (NDVI), displacement over certain time lags, and proximity to human areas. With this trained model, we then explored how potential scenarios of habitat fragmentation may affect gazelle movement. This model can be used to predict how fragmentation of the Mongolian Steppe may affect the Mongolian gazelle. In addition, this model is novel in that it can be applied to other ecological scenarios, since we designed it in modules that are easily interchanged.

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Spelling is an important literacy skill, and learning to spell is an important component of learning to write. Learners with strong spelling skills also exhibit greater reading, vocabulary, and orthographic knowledge than those with poor spelling skills (Ehri & Rosenthal, 2007; Ehri & Wilce, 1987; Rankin, Bruning, Timme, & Katkanant, 1993). English, being a deep orthography, has inconsistent sound-to-letter correspondences (Seymour, 2005; Ziegler & Goswami, 2005). This poses a great challenge for learners in gaining spelling fluency and accuracy. The purpose of the present study is to examine cross-linguistic transfer of English vowel spellings in Spanish-speaking adult ESL learners. The research participants were 129 Spanish-speaking adult ESL learners and 104 native English-speaking GED students enrolled in a community college located in the South Atlantic region of the United States. The adult ESL participants were in classes at three different levels of English proficiency: advanced, intermediate, and beginning. An experimental English spelling test was administered to both the native English-speaking and ESL participants. In addition, the adult ESL participants took the standardized spelling tests to rank their spelling skills in both English and Spanish. The data were analyzed using robust regression and Poisson regression procedures, Mann-Whitney test, and descriptive statistics. The study found that both Spanish spelling skills and English proficiency are strong predictors of English spelling skills. Spanish spelling is also a strong predictor of level of L1-influenced transfer. More proficient Spanish spellers made significantly fewer L1-influenced spelling errors than less proficient Spanish spellers. L1-influenced transfer of spelling knowledge from Spanish to English likely occurred in three vowel targets (/ɑɪ/ spelled as ae, ai, or ay, /ɑʊ/ spelled as au, and /eɪ/ spelled as e). The ESL participants and the native English-speaking participants produced highly similar error patterns of English vowel spellings when the errors did not indicate L1-influenced transfer, which implies that the two groups might follow similar trajectories of developing English spelling skills. The findings may help guide future researchers or practitioners to modify and develop instructional spelling intervention to meet the needs of adult ESL learners and help them gain English spelling competence.

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Practical application of flow boiling to ground- and space-based thermal management systems hinges on the ability to predict the system’s heat removal capabilities under expected operating conditions. Research in this field has shown that the heat transfer coefficient within two-phase heat exchangers can be largely dependent on the experienced flow regime. This finding has inspired an effort to develop mechanistic heat transfer models for each flow pattern which are likely to outperform traditional empirical correlations. As a contribution to the effort, this work aimed to identify the heat transfer mechanisms for the slug flow regime through analysis of individual Taylor bubbles. An experimental apparatus was developed to inject single vapor Taylor bubbles into co-currently flowing liquid HFE 7100. The heat transfer was measured as the bubble rose through a 6 mm inner diameter heated tube using an infrared thermography technique. High-speed flow visualization was obtained and the bubble film thickness measured in an adiabatic section. Experiments were conducted at various liquid mass fluxes (43-200 kg/m2s) and gravity levels (0.01g-1.8g) to characterize the effect of bubble drift velocity on the heat transfer mechanisms. Variable gravity testing was conducted during a NASA parabolic flight campaign. Results from the experiments showed that the drift velocity strongly affects the hydrodynamics and heat transfer of single elongated bubbles. At low gravity levels, bubbles exhibited shapes characteristic of capillary flows and the heat transfer enhancement due to the bubble was dominated by conduction through the thin film. At moderate to high gravity, traditional Taylor bubbles provided small values of enhancement within the film, but large peaks in the wake heat transfer occurred due to turbulent vortices induced by the film plunging into the trailing liquid slug. Characteristics of the wake heat transfer profiles were analyzed and related to the predicted velocity field. Results were compared and shown to agree with numerical simulations of colleagues from EPFL, Switzerland. In addition, a preliminary study was completed on the effect of a Taylor bubble passing through nucleate flow boiling, showing that the thinning thermal boundary layer within the film suppressed nucleation, thereby decreasing the heat transfer coefficient.

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Over the last decade, rapid development of additive manufacturing techniques has allowed the fabrication of innovative and complex designs. One field that can benefit from such technology is heat exchanger fabrication, as heat exchanger design has become more and more complex due to the demand for higher performance particularly on the air side of the heat exchanger. By employing the additive manufacturing, a heat exchanger design was successfully realized, which otherwise would have been very difficult to fabricate using conventional fabrication technologies. In this dissertation, additive manufacturing technique was implemented to fabricate an advanced design which focused on a combination of heat transfer surface and fluid distribution system. Although the application selected in this dissertation is focused on power plant dry cooling applications, the results of this study can directly and indirectly benefit other sectors as well, as the air-side is often the limiting side for in liquid or single phase cooling applications. Two heat exchanger designs were studied. One was an advanced metallic heat exchanger based on manifold-microchannel technology and the other was a polymer heat exchanger based on utilization of prime surface technology. Polymer heat exchangers offer several advantages over metals such as antifouling, anticorrosion, lightweight and often less expensive than comparable metallic heat exchangers. A numerical modeling and optimization were performed to calculate a design that yield an optimum performance. The optimization results show that significant performance enhancement is noted compared to the conventional heat exchangers like wavy fins and plain plate fins. Thereafter, both heat exchangers were scaled down and fabricated using additive manufacturing and experimentally tested. The manifold-micro channel design demonstrated that despite some fabrication inaccuracies, compared to a conventional wavy-fin surface, 15% - 50% increase in heat transfer coefficient was possible for the same pressure drop value. In addition, if the fabrication inaccuracy can be eliminated, an even larger performance enhancement is predicted. Since metal based additive manufacturing is still in the developmental stage, it is anticipated that with further refinement of the manufacturing process in future designs, the fabrication accuracy can be improved. For the polymer heat exchanger, by fabricating a very thin wall heat exchanger (150μm), the wall thermal resistance, which usually becomes the limiting side for polymer heat exchanger, was calculated to account for only up to 3% of the total thermal resistance. A comparison of air-side heat transfer coefficient of the polymer heat exchanger with some of the commercially available plain plate fin surface heat exchangers show that polymer heat exchanger performance is equal or superior to plain plate fin surfaces. This shows the promising potential for polymer heat exchangers to compete with conventional metallic heat exchangers when an additive manufacturing-enabled fabrication is utilized. Major contributions of this study are as follows: (1) For the first time demonstrated the potential of additive manufacturing in metal printing of heat exchangers that benefit from a sophisticated design to yield a performance substantially above the respective conventional systems. Such heat exchangers cannot be fabricated with the conventional fabrication techniques. (2) For the first time demonstrated the potential of additive manufacturing to produce polymer heat exchangers that by design minimize the role of thermal conductivity and deliver a thermal performance equal or better that their respective metallic heat exchangers. In addition of other advantages of polymer over metal like antifouling, anticorrosion, and lightweight. Details of the work are documented in respective chapters of this thesis.

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The work outlined in this dissertation will allow biochemists and cellular biologists to characterize polyubiquitin chains involved in their cellular environment by following a facile mass spectrometric based workflow. The characterization of polyubiquitin chains has been of interest since their discovery in 1984. The profound effects of ubiquitination on the movement and processing of cellular proteins depend exclusively on the structures of mono and polyubiquitin modifications anchored or unanchored on the protein within the cellular environment. However, structure-function studies have been hindered by the difficulty in identifying complex chain structures due to limited instrument capabilities of the past. Genetic mutations or reiterative immunoprecipitations have been used previously to characterize the polyubiquitin chains, but their tedium makes it difficult to study a broad ubiquitinome. Top-down and middle-out mass spectral based proteomic studies have been reported for polyubiquitin and have had success in characterizing parts of the chain, but no method to date has been successful at differentiating all theoretical ubiquitin chain isomers (ubiquitin chain lengths from dimer to tetramer alone have 1340 possible isomers). The workflow presented here can identify chain length, topology and linkages present using a chromatographic-time-scale compatible, LC-MS/MS based workflow. To accomplish this feat, the strategy had to exploit the most recent advances in top-down mass spectrometry. This included the most advanced electron transfer dissociation (ETD) activation and sensitivity for large masses from the orbitrap Fusion Lumos. The spectral interpretation had to be done manually with the aid of a graphical interface to assign mass shifts because of a lack of software capable to interpret fragmentation across isopeptide linkages. However, the method outlined can be applied to any mass spectral based system granted it results in extensive fragmentation across the polyubiquitin chain; making this method adaptable to future advances in the field.

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A basic requirement of a plasma etching process is fidelity of the patterned organic materials. In photolithography, a He plasma pretreatment (PPT) based on high ultraviolet and vacuum ultraviolet (UV/VUV) exposure was shown to be successful for roughness reduction of 193nm photoresist (PR). Typical multilayer masks consist of many other organic masking materials in addition to 193nm PR. These materials vary significantly in UV/VUV sensitivity and show, therefore, a different response to the He PPT. A delamination of the nanometer-thin, ion-induced dense amorphous carbon (DAC) layer was observed. Extensive He PPT exposure produces volatile species through UV/VUV induced scissioning. These species are trapped underneath the DAC layer in a subsequent plasma etch (PE), causing a loss of adhesion. Next to stabilizing organic materials, the major goals of this work included to establish and evaluate a cyclic fluorocarbon (FC) based approach for atomic layer etching (ALE) of SiO2 and Si; to characterize the mechanisms involved; and to evaluate the impact of processing parameters. Periodic, short precursor injections allow precise deposition of thin FC films. These films limit the amount of available chemical etchant during subsequent low energy, plasma-based Ar+ ion bombardment, resulting in strongly time-dependent etch rates. In situ ellipsometry showcased the self-limited etching. X-ray photoelectron spectroscopy (XPS) confirms FC film deposition and mixing with the substrate. The cyclic ALE approach is also able to precisely etch Si substrates. A reduced time-dependent etching is seen for Si, likely based on a lower physical sputtering energy threshold. A fluorinated, oxidized surface layer is present during ALE of Si and greatly influences the etch behavior. A reaction of the precursor with the fluorinated substrate upon precursor injection was observed and characterized. The cyclic ALE approach is transferred to a manufacturing scale reactor at IBM Research. Ensuring the transferability to industrial device patterning is crucial for the application of ALE. In addition to device patterning, the cyclic ALE process is employed for oxide removal from Si and SiGe surfaces with the goal of minimal substrate damage and surface residues. The ALE process developed for SiO2 and Si etching did not remove native oxide at the level required. Optimizing the process enabled strong O removal from the surface. Subsequent 90% H2/Ar plasma allow for removal of C and F residues.