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Concentrations of metal(loid)s, Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Se, Sr, V and Zn, were determined in rice on sale in Las Vegas. The rice samples were grown in five different countries, the USA, Thailand, India, Pakistan, and Bangladesh. The elemental concentrations in rice grain were determined using inductively coupled plasma mass spectrometry (ICP-MS) following hot block-assisted digestion. The accuracy of the laboratory procedure was verified by the analysis of rice flour standard reference material (NIST SRM 1568b). The mean metal(loid) contents in rice of various geographic origins were 3.18–5.91 mg kg−1 for Al, 0.05–0.12 mg kg−1 for As, 3.64–41 μg kg−1 for Cd, 5.11–12 μg kg−1 for Co, 0.12–0.14 mg kg−1 for Cr, 1.5–1.91 mg kg−1 for Cu, 3.04–4.98 mg kg−1 for Fe, 4.2–10.4 mg kg−1 for Mn, 0.21–0.41 mg kg−1 for Ni, 0.02–0.07 mg kg−1 for Se, 0.68–0.88 mg kg−1 for Sr, 3.64–5.26 μg kg−1 for V, and 16.6–19.9 mg kg−1 for Zn. respectively. The mean concentration of As in US rice was significantly higher than in Indian, Pakistani, and Bangladeshi rice. On the other hand, it was found a significantly low mean level of Cd in US-grown rice. It was also found that the concentrations of metal(loid)s in black and brown rice on sale in Las Vegas were statistically similar, except for Mn and Se. The geographic origin traceability of rice grain involved the use of ICP-MS analysis coupled with chemometrics that allowed their differentiation based on the rice metal(loid) profile, thus confirming their origins. Data were processed by linear discriminant analysis, and US and Thai rice samples were cross-validated with higher accuracy (100%). This authentication quickly discriminates US rice from the other regions and adds verifiable food safety measures for consumers.

We study the process of grain boundary sliding through the motion of grain boundary dislocations, utilizing molecular dynamics and embedded atom method (EAM) interatomic potentials. For a Σ = 5 [001]{310} symmetrical tilt boundary in bcc Fe, the sliding process was found to occur through the nucleation and glide of partial grain boundary dislocations, with a secondary grain boundary structure playing an important role in the sliding process. While the homogeneous nucleation of these grain boundary dislocations requires shear strain levels higher than 7%, preexisting grain boundary dislocations are shown to glide at applied shear levels of 1.5%. The glide of the dislocations results in coupled motion of the boundary in the directions parallel and perpendicular to itself. Finally, interstitial impurities and vacancies were introduced in the grain boundary to study the effects on the sliding resistance of the boundary. While vacancies and H interstitials act as preferred nucleation sites, C interstitials do not. Both hydrogen and C interstitials stop dislocation glide whereas vacancies do not. A detailed study of the dynamic properties of these dislocations is also presented.

Molecular dynamics simulations were conducted to fundamentally evaluate the yield and failure behavior of cross-linked phenolic resins at temperatures below the glass transition. Yield stress was investigated at various temperatures, strain rates, and degrees of cross-linking. The onset of non-linear behavior in the cross-linked phenolic structures was caused by localized irreversible molecular rearrangements through the rotation of methylene linkers followed by the formation or annihilation of neighboring hydrogen bonds. The yield stress results, with respect to temperature and strain rate, could be fit by existing models used to describe yield behavior of amorphous glasses. The degree of cross-linking only indirectly influences the maximum yield stress through its influence on glass transition temperature (Tg), however there is a strong relationship between the degree of cross-linking and the failure mechanism. Low cross-linked samples were able to separate through void formation, whereas the highly cross-linked structures exhibited bond scission.

In this dissertation I present computational studies that focus on the unique characteristics of metallic nanowires. We generated virtual nanowires of nanocrystalline nickel (nc-Ni) and single crystalline silver (Ag) in order to investigate particular nanoscale effects. Three-dimensional atomistic molecular dynamics studies were performed for each sample using the super computer System X located at Virginia Tech. Thermal grain growth simulations were performed on 4 nm grain size nc-Ni by observing grain sizes over time for temperatures from 800K to 1450K and we discovered grain growth to be linearly time-dependant, contrary to coarse grained materials with square root dependence. Strain induced grain growth studies consisted of straining the nanostructures in tension at a strain rate of 3.3 x 108 s-1. Grain boundary movement was recorded to quantify grain boundary velocities and grain growth. It was shown that during deformation, there is interplay between dislocation-mediated plasticity and grain boundary accommodation of plasticity through grain boundary sliding. To further understand the effect of stress on nanocrystalline materials we performed tensile tests at different strain rates, varying from 2.22 x 107 s-1 to 1.33 x 109 s -1 for a 5 nm grain size nc-Ni nanowire with a 5 nm radius. The activation volume was given as ∼2b3, where b is the Burger's vector and is consistent with a grain boundary dominate deformation mechanism. We expanded our research to 10 nm grain size nc-Ni nanowires with radii from 5 nm to 18 nm. Each wire was deformed 15% in tension or compression at a strain rate of 3.3 x 108 s-1. Asymmetry was observed for all radii, in which larger radii produced higher flow stresses for compression and small radii yielded higher flow stresses in tension. A cross over in the tension-compression asymmetry is found to occur at a radius of ∼9 nm. A change in the dominate deformation mechanism in combination with the ease of grain boundary sliding contributes to the phenomena of the asymmetry. In the final chapter we focus on the energetic stability of multi-twinned Ag nanorods at the nanoscale. We used a combination of molecular statics and dynamics to find the local minimum energies for the multi-twinned nanorods and the non-twinned \"bulk\" materials and concluded that the stability of multi-twinned nanorods is highly influenced by the size of the sample and the existence of the ends. Using an analytical model we found the excess energy of the nanorods with ends and determined the critical aspect ratio below which five-twinned nanorods are stable.

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

Next generation ablative thermal protection systems are expected to consist of 3D woven composite architectures. It is well known that composites can be tailored to achieve desired mechanical and thermal properties in various directions and thus can be made fit-for-purpose if the proper combination of constituent materials and microstructures can be realized. In the present work, the first, multiscale, atomistically-informed, computational analysis of mechanical and thermal properties of a present day - Carbon/Phenolic composite Thermal Protection System (TPS) material is conducted. Model results are compared to measured in-plane and out-of-plane mechanical and thermal properties to validate the computational approach. Results indicate that given sufficient microstructural fidelity, along with lowerscale, constituent properties derived from molecular dynamics simulations, accurate composite level (effective) thermo-elastic properties can be obtained. This suggests that next generation TPS properties can be accurately estimated via atomistically informed multiscale analysis.

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

Genome-scale models (GEMs) of metabolism were constructed for 55 fully sequenced Escherichia coli and Shigella strains. The GEMs enable a systems approach to characterizing the pan and core metabolic capabilities of the E. coli species. The majority of pan metabolic content was found to consist of alternate catabolic pathways for unique nutrient sources. The GEMs were then used to systematically analyze growth capabilities in more than 650 different growth-supporting environments. The results show that unique strain-specific metabolic capabilities correspond to pathotypes and environmental niches. Twelve of the GEMs were used to predict growth on six differentiating nutrients, and the predictions were found to agree with 80% of experimental outcomes. Additionally, GEMs were used to predict strain-specific auxotrophies. Twelve of the strains modeled were predicted to be auxotrophic for vitamins niacin (vitamin B ₃), thiamin (vitamin B ₁), or folate (vitamin B ₉). Six of the strains modeled have lost biosynthetic pathways for essential amino acids methionine, tryptophan, or leucine. Genome-scale analysis of multiple strains of a species can thus be used to define the metabolic essence of a microbial species and delineate growth differences that shed light on the adaptation process to a particular microenvironment.