A microflame-based detector suit has been developed for sensing of a broad range of chemical analytes. This detector combines calorimetry, flame ionization detection (FID), nitrogen-phosphorous detection (NPD) and flame photometric detection (FPD) modes into one convenient platform based on a microcombustor. The microcombustor consists in a micromachined microhotplate with a catalyst or low-work function material added to its surface. For the NPD mode a low work function material selectively ionizes chemical analytes; for all other modes a supported catalyst such as platinum/alumina is used. The microcombustor design permits rapid, efficient heating of the deposited film at low power. To perform calorimetric detection of analytes, the change in power required to maintain the resistive microhotplate heater at a constant temperature is measured. For FID and NPD modes, electrodes are placed around the microcombustor flame zone and an electrometer circuit measures the production of ions. For FPD, the flame zone is optically interrogated to search for light emission indicative of deexcitation of flame-produced analyte compounds. The calorimetric and FID modes respond generally to all hydrocarbons, while sulfur compounds only alarm in the calorimetric mode, providing speciation. The NPD mode provides 10,000:1 selectivity of nitrogen and phosphorous compounds over hydrocarbons. The FPD can distinguish between sulfur and phosphorous compounds. Importantly all detection modes can be established on one convenient microcombustor platform, in fact the calorimetric, FID and FPD modes can be achieved simultaneously on only one microcombustor. Therefore, it is possible to make a very universal chemical detector array with as little as two microcombustor elements. A demonstration of the performance of the microcombustor in each of the detection modes is provided herein.
Functional organic nanostructures such as well-formed tubes or fibers that can easily be fabricated into electronic and photonic devices are needed in many applications. Especially desirable from a national security standpoint are nanostructures that have enhanced sensitivity for the detection of chemicals and biological (CB) agents and other environmental stimuli. We recently discovered the first class of highly responsive and adaptive porphyrin-based nanostructures that may satisfy these requirements. These novel porphyrin nanostructures, which are formed by ionic self-assembly of two oppositely charged porphyrins, may function as conductors, semiconductors, or photoconductors, and they have additional properties that make them suitable for device fabrication (e.g., as ultrasensitive colorimetric CB microsensors). Preliminary studies with porphyrin nanotubes have shown that these nanostructures have novel optical and electronic properties, including strong resonant light scattering, quenched fluorescence, and electrical conductivity. In addition, they are photochemically active and capable of light-harvesting and photosynthesis; they may also have nonlinear optical properties. Remarkably, the nanotubes and potentially other porphyrin nanostructure are mechanically responsive and adaptive (e.g., the rigidity of the micrometers-long nanotubes is altered by light, ultrasound, or chemicals) and they self-heal upon removal the environmental stimulus. Given the tremendous degree of structural variation possible in the porphyrin subunits, additional types of nanostructures and greater control over their morphology can be anticipated. Molecular modification also provides a means of controlling their electronic, photonic, and other functional properties. In this work, we have greatly broadened the range of ionic porphyrin nanostructures that can be made, and determined the optical and responsivity properties of the nanotubes and other porphyrin nanostructures. We have also explored means for controlling their morphology, size, and placement on surfaces. The research proposed will lay the groundwork for the use of these remarkable porphyrin nanostructures in micro- and nanoscale devices, by providing a more detailed understanding of their molecular structure and the factors that control their structural, photophysical, and chemical properties.
In this investigation, we conduct a literature study of the best experimental and theoretical data available for thin and thick atmospheres on THz radiation propagation from 0.1 to 10 THz. We determined that for thick atmospheres no data exists beyond 450 GHz. For thin atmospheres data exists from 0.35 to 1.2 THz. We were successful in using FASE code with the HITRAN database to simulate the THz transmission spectrum for Mauna Kea from 0.1 to 2 THz. Lastly, we successfully measured the THz transmission spectra of laboratory atmospheres at relative humidities of 18 and 27%. In general, we found that an increase in the water content of the atmosphere led to a decrease in the THz transmission. We identified two potential windows in an Albuquerque atmosphere for THz propagation which were the regions from 1.2 to 1.4 THz and 1.4 to 1.6 THz.
The formation and functions of living materials and organisms are fundamentally different from those of synthetic materials and devices. Synthetic materials tend to have static structures, and are not capable of adapting to the functional needs of changing environments. In contrast, living systems utilize energy to create, heal, reconfigure, and dismantle materials in a dynamic, non-equilibrium fashion. The overall goal of the project was to organize and reconfigure functional assemblies of nanoparticles using strategies that mimic those found in living systems. Active assembly of nanostructures was studied using active biomolecules to drive the organization and assembly of nanocomposite materials. In this system, kinesin motor proteins and microtubules were used to direct the transport and interactions of nanoparticles at synthetic interfaces. In addition, the kinesin/microtubule transport system was used to actively assemble nanocomposite materials capable of storing significant elastic energy. Novel biophysical measurement tools were also developed for measuring the collective force generated by kinesin motor proteins, which will provide insight on the mechanical constraints of active assembly processes. Responsive reconfiguration of nanostructures was studied in terms of using active biomolecules to mediate the optical properties of quantum dot (QD) arrays through modulation of inter-particle spacing and associated energy transfer interaction. Design rules for kinesin-based transport of a wide range of nanoscale cargo (e.g., nanocrystal quantum dots, micron-sized polymer spheres) were developed. Three-dimensional microtubule organizing centers were assembled in which the polar orientation of the microtubules was controlled by a multi-staged assembly process. Overall, a number of enabling technologies were developed over the course of this project, and will drive the exploitation of energy-driven processes to regulate the assembly, disassembly, and dynamic reorganization of nanomaterials.
Polymers and fiber-reinforced polymer matrix composites play an important role in many Defense Program applications. Recently an advanced nonlinear viscoelastic model for polymers has been developed and incorporated into ADAGIO, Sandia's SIERRA-based quasi-static analysis code. Standard linear elastic shell and continuum models for fiber-reinforced polymer-matrix composites have also been added to ADAGIO. This report details the use of these models for advanced adhesive joint and composites simulations carried out as part of an Advanced Simulation and Computing Advanced Deployment (ASC AD) project. More specifically, the thermo-mechanical response of an adhesive joint when loaded during repeated thermal cycling is simulated, the response of some composite rings under internal pressurization is calculated, and the performance of a composite container subjected to internal pressurization, thermal loading, and distributed mechanical loading is determined. Finally, general comparisons between the continuum and shell element approaches for modeling composites using ADAGIO are given.
Understanding the properties and behavior of biomembranes is fundamental to many biological processes and technologies. Microdomains in biomembranes or ''lipid rafts'' are now known to be an integral part of cell signaling, vesicle formation, fusion processes, protein trafficking, and viral and toxin infection processes. Understanding how microdomains form, how they depend on membrane constituents, and how they act not only has biological implications, but also will impact Sandia's effort in development of membranes that structurally adapt to their environment in a controlled manner. To provide such understanding, we created physically-based models of biomembranes. Molecular dynamics (MD) simulations and classical density functional theory (DFT) calculations using these models were applied to phenomena such as microdomain formation, membrane fusion, pattern formation, and protein insertion. Because lipid dynamics and self-organization in membranes occur on length and time scales beyond atomistic MD, we used coarse-grained models of double tail lipid molecules that spontaneously self-assemble into bilayers. DFT provided equilibrium information on membrane structure. Experimental work was performed to further help elucidate the fundamental membrane organization principles.
Deoxyribonucleic acid (DNA) molecules represent Nature's genetic database, encoding the information necessary for all cellular processes. From a materials engineering perspective, DNA represents a nanoscale scaffold with highly refined structure, stability across a wide range of environmental conditions, and the ability to interact with a range of biomolecules. The ability to mass-manufacture functionalized DNA strands with Angstrom-level resolution through DNA replication technology, however, has not been explored. The long-term goal of the work presented in this report is focused on exploiting DNA and in vitro DNA replication processes to mass-manufacture nanocomposite materials. The specific objectives of this project were to: (1) develop methods for replicating DNA strands that incorporate nucleotides with ''chemical handles'', and (2) demonstrate attachment of nanocrystal quantum dots (nQDs) to functionalized DNA strands. Polymerase chain reaction (PCR) and primer extension methodologies were used to successfully synthesize amine-, thiol-, and biotin-functionalized DNA molecules. Significant variability in the efficiency of modified nucleotide incorporation was observed, and attributed to the intrinsic properties of the modified nucleotides. Noncovalent attachment of streptavidin-coated nQDs to biotin-modified DNA synthesized using the primer extension method was observed by epifluorescence microscopy. Data regarding covalent attachment of nQDs to amine- and thiol-functionalized DNA was generally inconclusive; alternative characterization tools are necessary to fully evaluate these attachment methods. Full realization of this technology may facilitate new approaches to manufacturing materials at the nanoscale. In addition, composite nQD-DNA materials may serve as novel recognition elements in sensor devices, or be used as diagnostic tools for forensic analyses. This report summarizes the results obtained over the course of this 1-year project.
Nearly every manufacturing and many technologies central to Sandia's business involve physical processes controlled by interfacial wetting. Interfacial forces, e.g. conjoining/disjoining pressure, electrostatics, and capillary condensation, are ubiquitous and can surpass and even dominate bulk inertial or viscous effects on a continuum level. Moreover, the statics and dynamics of three-phase contact lines exhibit a wide range of complex behavior, such as contact angle hysteresis due to surface roughness, surface reaction, or compositional heterogeneities. These thermodynamically and kinetically driven interactions are essential to the development of new materials and processes. A detailed understanding was developed for the factors controlling wettability in multicomponent systems from computational modeling tools, and experimental diagnostics for systems, and processes dominated by interfacial effects. Wettability probed by dynamic advancing and receding contact angle measurements, ellipsometry, and direct determination of the capillary and disjoining forces. Molecular scale experiments determined the relationships between the fundamental interactions between molecular species and with the substrate. Atomistic simulations studied the equilibrium concentration profiles near the solid and vapor interfaces and tested the basic assumptions used in the continuum approaches. These simulations provide guidance in developing constitutive equations, which more accurately take into account the effects of surface induced phase separation and concentration gradients near the three-phase contact line. The development of these accurate models for dynamic multicomponent wetting allows improvement in science based engineering of manufacturing processes previously developed through costly trial and error by varying material formulation and geometry modification.
The objective of this project is the investigation of compliant membranes for the development of a MicroElectrical Mechanical Systems (MEMS) microphone using the Sandia Ultraplanar, Multilevel MEMS Technology (SUMMiT V) fabrication process. The microphone is a dual-backplate capacitive microphone utilizing electrostatic force feedback. The microphone consists of a diaphragm and two porous backplates, one on either side of the diaphragm. This forms a capacitor between the diaphragm and each backplate. As the incident pressure deflects the diaphragm, the value of each capacitor will change, thus resulting in an electrical output. Feedback may be used in this device by applying a voltage between the diaphragm and the backplates to balance the incident pressure keeping the diaphragm stationary. The SUMMiT V fabrication process is unique in that it can meet the fabrication requirements of this project. All five layers of polysilicon are used in the fabrication of this device. The SUMMiT V process has been optimized to provide low-stress mechanical layers that are ideal for the construction of the microphone's diaphragm. The use of chemical mechanical polishing in the SUMMiT V process results in extremely flat structural layers and uniform spacing between the layers, both of which are critical to the successful fabrication of the MEMS microphone. The MEMS capacitive microphone was fabricated at Sandia National Laboratories and post-processed, packaged, and tested at the University of Florida. The microphone demonstrates a flat frequency response, a linear response up to the designed limit, and a sensitivity that is close to the designed value. Future work will focus on characterization of additional devices, extending the frequency response measurements, and investigating the use of other types of interface circuitry.
The natural gas industry seeks inexpensive sensors and instrumentation to rapidly measure gas heating value in widely distributed locations. For gas pipelines, this will improve gas quality during transfer and blending, and will expedite accurate financial accounting. Industrial endusers will benefit through continuous feedback of physical gas properties to improve combustion efficiency during use. To meet this need, Sandia has developed a natural gas heating value monitoring instrument using existing and modified microfabricated components. The instrument consists of a silicon micro-fabricated gas chromatography column in conjunction with a catalytic micro-calorimeter sensor. A reference thermal conductivity sensor provides diagnostics and surety. This combination allows for continuous calorimetric determination with a 1 minute analysis time and 1.5 minute cycle time using air as a carrier gas. This system will find application at remote natural gas mining stations, pipeline switching and metering stations, turbine generators, and other industrial user sites. Microfabrication techniques will allow the analytical components to be manufactured in production quantities at a low per-unit cost.
Sodium aluminum hydride, NaAlH{sub 4}, has been studied for use as a hydrogen storage material. The effect of Ti, as a few mol. % dopant in the system to increase kinetics of hydrogen sorption, is studied with respect to changes in lattice structure of the crystal. No Ti substitution is found in the crystal lattice. Electronic structure calculations indicate that the NaAlH{sub 4} and Na{sub 3}AlH{sub 6} structures are complex-ionic hydrides with Na{sup +} cations and AlH{sub 4}{sup -} and AlH{sub 6}{sup 3-} anions, respectively. Compound formation studies indicate the primary Ti-compound formed when doping the material at 33 at. % is TiAl{sub 3} , and likely Ti-Al compounds at lower doping rates. A general study of sorption kinetics of NaAlH{sub 4}, when doped with a variety of Ti-halide compounds, indicates a uniform response with the kinetics similar for all dopants. NMR multiple quantum studies of solution-doped samples indicate solvent interaction with the doped alanate. Raman spectroscopy was used to study the lattice dynamics of NaAlH{sub 4}, and illustrated the molecular ionic nature of the lattice as a separation of vibrational modes between the AlH{sub 4}{sup -} anion-modes and lattice-modes. In-situ Raman measurements indicate a stable AlH{sub 4}{sup -} anion that is stable at the melting temperature of NaAlH{sub 4}, indicating that Ti-dopants must affect the Al-H bond strength.
The design, simulation, fabrication, packaging, electrical characterization and testing analysis of a microfabricated a cylindrical ion trap ({mu}CIT) array is presented. Several versions of microfabricated cylindrical ion traps were designed and fabricated. The final design of the individual trap array element consisted of two end cap electrodes, one ring electrode, and a detector plate, fabricated in seven tungsten metal layers by molding tungsten around silicon dioxide (SiO{sub 2}) features. Each layer of tungsten is then polished back in damascene fashion. The SiO{sub 2} was removed using a standard release processes to realize a free-hung structure. Five different sized traps were fabricated with inner radii of 1, 1.5, 2, 5 and 10 {micro}m and heights ranging from 3-24 {micro}m. Simulations examined the effects of ion and neutral temperature, the pressure and nature of cooling gas, ion mass, trap voltage and frequency, space-charge, fabrication defects, and other parameters on the ability of micrometer-sized traps to store ions. The electrical characteristics of the ion trap arrays were determined. The capacitance was 2-500 pF for the various sized traps and arrays. The resistance was in the order of 1-2 {Omega}. The inductance of the arrays was calculated to be 10-1500 pH, depending on the trap and array sizes. The ion traps' field emission characteristics were assessed. It was determined that the traps could be operated up to 125 V while maintaining field emission currents below 1 x 10{sup -15} A. The testing focused on using the 5-{micro}m CITs to trap toluene (C{sub 7}H{sub 8}). Ion ejection from the traps was induced by termination of the RF voltage applied to the ring electrode and current measured on the collector electrode suggested trapping of ions in 1-10% of the traps. Improvements to the to the design of the traps were defined to minimize voltage drop to the substrate, thereby increasing trapping voltage applied to the ring electrode, and to allow for electron injection into, ion ejection from, and optical access to the trapping region.
Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes as adaptive or smart materials. Dimensional adjustments of adaptive polymer films depend on controlled charge deposition. Predicting their long-term performance requires a detailed understanding of the piezoelectric material features, expected to suffer due to space environmental degradation. Hence, the degradation and performance of PVDF and its copolymers under various stress environments expected in low Earth orbit has been reviewed and investigated. Various experiments were conducted to expose these polymers to elevated temperature, vacuum UV, {gamma}-radiation and atomic oxygen. The resulting degradative processes were evaluated. The overall materials performance is governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure is evident as depoling, loss of orientation and surface erosion. The effects of combined vacuum UV radiation and atomic oxygen resulted in expected surface erosion and pitting rates that determine the lifetime of thin films. Interestingly, the piezo responsiveness in the underlying bulk material remained largely unchanged. This study has delivered a comprehensive framework for material properties and degradation sensitivities with variations in individual polymer performances clearly apparent. The results provide guidance for material selection, qualification, optimization strategies, feedback for manufacturing and processing, or alternative materials. Further material qualification should be conducted via experiments under actual space conditions.
This report documents research to develop robust and efficient solution techniques for solving large-scale systems of nonlinear equations. The most widely used method for solving systems of nonlinear equations is Newton's method. While much research has been devoted to augmenting Newton-based solvers (usually with globalization techniques), little has been devoted to exploring the application of different models. Our research has been directed at evaluating techniques using different models than Newton's method: a lower order model, Broyden's method, and a higher order model, the tensor method. We have developed large-scale versions of each of these models and have demonstrated their use in important applications at Sandia. Broyden's method replaces the Jacobian with an approximation, allowing codes that cannot evaluate a Jacobian or have an inaccurate Jacobian to converge to a solution. Limited-memory methods, which have been successful in optimization, allow us to extend this approach to large-scale problems. We compare the robustness and efficiency of Newton's method, modified Newton's method, Jacobian-free Newton-Krylov method, and our limited-memory Broyden method. Comparisons are carried out for large-scale applications of fluid flow simulations and electronic circuit simulations. Results show that, in cases where the Jacobian was inaccurate or could not be computed, Broyden's method converged in some cases where Newton's method failed to converge. We identify conditions where Broyden's method can be more efficient than Newton's method. We also present modifications to a large-scale tensor method, originally proposed by Bouaricha, for greater efficiency, better robustness, and wider applicability. Tensor methods are an alternative to Newton-based methods and are based on computing a step based on a local quadratic model rather than a linear model. The advantage of Bouaricha's method is that it can use any existing linear solver, which makes it simple to write and easily portable. However, the method usually takes twice as long to solve as Newton-GMRES on general problems because it solves two linear systems at each iteration. In this paper, we discuss modifications to Bouaricha's method for a practical implementation, including a special globalization technique and other modifications for greater efficiency. We present numerical results showing computational advantages over Newton-GMRES on some realistic problems. We further discuss a new approach for dealing with singular (or ill-conditioned) matrices. In particular, we modify an algorithm for identifying a turning point so that an increasingly ill-conditioned Jacobian does not prevent convergence.
This work covers three distinct aspects of deformation and fracture during indentations. In particular, we develop an approach to verification of nanoindentation induced film fracture in hard film/soft substrate systems; we examine the ability to perform these experiments in harsh environments; we investigate the methods by which the resulting deformation from indentation can be quantified and correlated to computational simulations, and we examine the onset of plasticity during indentation testing. First, nanoindentation was utilized to induce fracture of brittle thin oxide films on compliant substrates. During the indentation, a load is applied and the penetration depth is continuously measured. A sudden discontinuity, indicative of film fracture, was observed upon the loading portion of the load-depth curve. The mechanical properties of thermally grown oxide films on various substrates were calculated using two different numerical methods. The first method utilized a plate bending approach by modeling the thin film as an axisymmetric circular plate on a compliant foundation. The second method measured the applied energy for fracture. The crack extension force and applied stress intensity at fracture was then determined from the energy measurements. Secondly, slip steps form on the free surface around indentations in most crystalline materials when dislocations reach the free surface. Analysis of these slip steps provides information about the deformation taking place in the material. Techniques have now been developed to allow for accurate and consistent measurement of slip steps and the effects of crystal orientation and tip geometry are characterized. These techniques will be described and compared to results from dislocation dynamics simulations.
A probabilistic performance assessment has been conducted to evaluate the fate and transport of radionuclides (americium-241, cesium-137, cobalt-60, plutonium-238, plutonium-239, radium-226, radon-222, strontium-90, thorium-232, tritium, uranium-238), heavy metals (lead and cadmium), and volatile organic compounds (VOCs) at the Mixed Waste Landfill (MWL). Probabilistic analyses were performed to quantify uncertainties inherent in the system and models for a 1,000-year period, and sensitivity analyses were performed to identify parameters and processes that were most important to the simulated performance metrics. Comparisons between simulated results and measured values at the MWL were made to gain confidence in the models and perform calibrations when data were available. In addition, long-term monitoring requirements and triggers were recommended based on the results of the quantified uncertainty and sensitivity analyses. At least one-hundred realizations were simulated for each scenario defined in the performance assessment. Conservative values and assumptions were used to define values and distributions of uncertain input parameters when site data were not available. Results showed that exposure to tritium via the air pathway exceeded the regulatory metric of 10 mrem/year in about 2% of the simulated realizations when the receptor was located at the MWL (continuously exposed to the air directly above the MWL). Simulations showed that peak radon gas fluxes exceeded the design standard of 20 pCi/m{sup 2}/s in about 3% of the realizations if up to 1% of the containers of sealed radium-226 sources were assumed to completely degrade in the future. If up to 100% of the containers of radium-226 sources were assumed to completely degrade, 30% of the realizations yielded radon surface fluxes that exceeded the design standard. For the groundwater pathway, simulations showed that none of the radionuclides or heavy metals (lead and cadmium) reached the groundwater during the 1,000-year evaluation period. Tetrachloroethylene (PCE) was used as a proxy for other VOCs because of its mobility and potential to exceed maximum contaminant levels in the groundwater relative to other VOCs. Simulations showed that PCE reached the groundwater, but only 1% of the realizations yielded aquifer concentrations that exceeded the regulatory metric of 5 {micro}g/L. Based on these results, monitoring triggers have been proposed for the air, surface soil, vadose zone, and groundwater at the MWL. Specific triggers include numerical thresholds for radon concentrations in the air, tritium concentrations in surface soil, infiltration through the vadose zone, and uranium and select VOC concentrations in groundwater. The proposed triggers are based on U.S. Environmental Protection Agency and Department of Energy regulatory standards. If a trigger is exceeded, then a trigger evaluation process will be initiated which will allow sufficient data to be collected to assess trends and recommend corrective actions, if necessary.
LDRD Project 86361 provided support to upgrade the chemical and material spectral signature measurement and detection capabilities of Sandia National Laboratories using the terahertz (THz) portion of the electromagnetic spectrum, which includes frequencies between 0.1 to 10 THz. Under this project, a THz time-domain spectrometer was completed. This instrument measures sample absorption spectra coherently, obtaining both magnitude and phase of the absorption signal, and has shown an operating signal-to-noise ratio of 10{sub 4}. Additionally, various gas cells and a reflectometer were added to an existing high-resolution THz Fourier transform spectrometer, which greatly extend the functionality of this spectrometer. Finally, preliminary efforts to design an integrated THz transceiver based on a quantum cascade laser were begun.
This report contains an algorithm for decomposing higher-order finite elementsinto regions appropriate for isosurfacing and proves the conditions under which thealgorithm will terminate. Finite elements are used to create piecewise polynomialapproximants to the solution of partial differential equations for which no analyticalsolution exists. These polynomials represent fields such as pressure, stress, and mo-mentim. In the past, these polynomials have been linear in each parametric coordinate.Each polynomial coefficient must be uniquely determined by a simulation, and thesecoefficients are called degrees of freedom. When there are not enough degrees of free-dom, simulations will typically fail to produce a valid approximation to the solution.Recent work has shown that increasing the number of degrees of freedom by increas-ing the order of the polynomial approximation (instead of increasing the number offinite elements, each of which has its own set of coefficients) can allow some typesof simulations to produce a valid approximation with many fewer degrees of freedomthan increasing the number of finite elements alone. However, once the simulation hasdetermined the values of all the coefficients in a higher-order approximant, tools donot exist for visual inspection of the solution.This report focuses on a technique for the visual inspection of higher-order finiteelement simulation results based on decomposing each finite element into simplicialregions where existing visualization algorithms such as isosurfacing will work. Therequirements of the isosurfacing algorithm are enumerated and related to the placeswhere the partial derivatives of the polynomial become zero. The original isosurfacingalgorithm is then applied to each of these regions in turn.3 AcknowledgementThe authors would like to thank David Day and Louis Romero for their insight into poly-nomial system solvers and the LDRD Senior Council for the opportunity to pursue thisresearch. The authors were supported by the United States Department of Energy, Officeof Defense Programs by the Labratory Directed Research and Development Senior Coun-cil, project 90499. Sandia is a multiprogram laboratory operated by Sandia Corporation,a Lockheed-Martin Company, for the United States Department of Energy under contractDE-AC04-94-AL85000.4
We have developed a new nanotagging technology for detecting and imaging the self-organization of proteins and other components of membranes at nanometer resolution for the purpose of investigating cell signaling and other membrane-mediated biological processes. We used protein-, lipid-, or drug-bound porphyrin photocatalysts to grow in-situ nanometer-sized metal particles, which reveal the location of the porphyrin-labeled molecules by electron microscopy. We initially used photocatalytic nanotagging to image assembled multi-component proteins and to monitor the distribution of lipids and porphyrin labels in liposomes. For example, by exchanging the heme molecules in hemoproteins with a photocatalytic tin porphyrin, a nanoparticle was grown at each heme site of the protein. The result obtained from electron microscopy for a tagged multi-subunit protein such as hemoglobin is a symmetric constellation of a specific number of nanoparticle tags, four in the case of the hemoglobin tetramer. Methods for covalently linking photocatalytic porphyrin labels to lipids and proteins were also developed to detect and image the self-organization of lipids, protein-protein supercomplexes, and membrane-protein complexes. Procedures for making photocatalytic porphyrin-drug, porphyrin-lipid, and porphyrin-protein hybrids for non-porphyrin-binding proteins and membrane components were pursued and the first porphyrin-labeled lipids was investigated in liposomal membrane models. Our photocatalytic nanotagging technique may ultimately allow membrane self-organization and cell signaling processes to be imaged in living cells. Fluorescence and plasmonic spectra of the tagged proteins might also provide additional information about protein association and membrane organization. In addition, a porphyrin-aspirin or other NSAID hybrid may be used to grow metal nanotags for the pharmacologically important COX enzymes in membranes so that the distribution of the protein can be imaged at the nanometer scale.
There are several engineering obstacles that need to be solved before key management and encryption under the bounded storage model can be realized. One of the critical obstacles hindering its adoption is the construction of a scheme that achieves reliable communication in the event that timing synchronization errors occur. One of the main accomplishments of this project was the development of a new scheme that solves this problem. We show in general that there exist message encoding techniques under the bounded storage model that provide an arbitrarily small probability of transmission error. We compute the maximum capacity of this channel using the unsynchronized key-expansion as side-channel information at the decoder and provide tight lower bounds for a particular class of key-expansion functions that are pseudo-invariant to timing errors. Using our results in combination with Dziembowski et al. [11] encryption scheme we can construct a scheme that solves the timing synchronization error problem. In addition to this work we conducted a detailed case study of current and future storage technologies. We analyzed the cost, capacity, and storage data rate of various technologies, so that precise security parameters can be developed for bounded storage encryption schemes. This will provide an invaluable tool for developing these schemes in practice.
The original LDRD proposal was to use a nonlinear diffusion solver to compute estimates for the material temperature that could then be used in a Implicit Monte Carlo (IMC) calculation. At the end of the first year of the project, it was determined that this was not going to be effective, partially due to the concept, and partially due to the fact that the radiation diffusion package was not as efficient as it could be. The second, and final year, of the project focused on improving the robustness and computational efficiency of the radiation diffusion package in ALEGRA. To this end, several new multigroup diffusion methods have been developed and implemented in ALEGRA. While these methods have been implemented, their effectiveness of reducing overall simulation run time has not been fully tested. Additionally a comprehensive suite of verification problems has been developed for the diffusion package to ensure that it has been implemented correctly. This process took considerable time, but exposed significant bugs in both the previous and new diffusion packages, the linear solve packages, and even the NEVADA Framework's parser. In order to manage this large suite of problem, a new tool called Tampa has been developed. It is a general tool for automating the process of running and analyzing many simulations. Ryan McClarren, at the University of Michigan has been developing a Spherical Harmonics capability for unstructured meshes. While still in the early phases of development, this promises to bridge the gap in accuracy between a full transport solution using IMC and the diffusion approximation.
The later time phase of electrical breakdown in water is investigated for the purpose of improving understanding of the discharge characteristics. One dimensional simulations in addition to a zero dimensional lumped model are used to study the spark discharge. The goal is to provide better electrical models for water switches used in the pulse compression section of pulsed power systems. It is found that temperatures in the discharge channel under representative drive conditions, and assuming small initial radii from earlier phases of development, reach levels that are as much as an order of magnitude larger than those used to model discharges in atmospheric gases. This increased temperature coupled with a more rapidly rising conductivity with temperature than in air result in a decreased resistance characteristic compared to preceding models. A simple modification is proposed for the existing model to enable the approximate calculation of channel temperature and incorporate the resulting conductivity increase into the electrical circuit for the discharge channel. Comparisons are made between the theoretical predictions and recent experiments at Sandia. Although present and past experiments indicated that preceding late time channel models overestimated channel resistance, the calculations in this report seem to underestimate the resistance relative to recent experiments. Some possible reasons for this discrepancy are discussed.
This report contains an algorithm for decomposing higher-order finite elements into regions appropriate for isosurfacing and proves the conditions under which the algorithm will terminate. Finite elements are used to create piecewise polynomial approximants to the solution of partial differential equations for which no analytical solution exists. These polynomials represent fields such as pressure, stress, and momentum. In the past, these polynomials have been linear in each parametric coordinate. Each polynomial coefficient must be uniquely determined by a simulation, and these coefficients are called degrees of freedom. When there are not enough degrees of freedom, simulations will typically fail to produce a valid approximation to the solution. Recent work has shown that increasing the number of degrees of freedom by increasing the order of the polynomial approximation (instead of increasing the number of finite elements, each of which has its own set of coefficients) can allow some types of simulations to produce a valid approximation with many fewer degrees of freedom than increasing the number of finite elements alone. However, once the simulation has determined the values of all the coefficients in a higher-order approximant, tools do not exist for visual inspection of the solution. This report focuses on a technique for the visual inspection of higher-order finite element simulation results based on decomposing each finite element into simplicial regions where existing visualization algorithms such as isosurfacing will work. The requirements of the isosurfacing algorithm are enumerated and related to the places where the partial derivatives of the polynomial become zero. The original isosurfacing algorithm is then applied to each of these regions in turn.