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Caltech campus executive LDRD

Shepodd, Timothy J.

The environment most brain systems of humans and other animals are almost constantly confronted with is complex and continuously changing, with each time step updating a potentially bewildering set of opportunities and demands for action. Far from the controlled, discrete trials used in most neuro- and psychological investigations, behavior outside the lab at Caltech is a seamless and continuous process of monitoring (and error correction) of ongoing action, and of evaluating persistence in the current activity with respect to opportunities to switch tasks as alternatives become available. Prior work on frontopolar and prefrontal task switching, use tasks within the same modality (View a stream of symbols on a screen and perform certain response mappings depending on task rules). However, in these task switches the effector is constant: only the mapping of visual symbols to the specific button changes. In this task, the subjects are choosing what kinds of future action decisions they want to perform, where they can control either which body part will act, or which direction they will orient an instructed body action. An effector choice task presents a single target and the subject selects which effector to use to reach the target (eye or hand). While the techniques available for humans can be less spatially resolved compared to non-human primate neural data, they do allow for experimentation on multiple brain areas with relative ease. Thus, we address a broader network of areas involved in motor decisions. We aim to resolve a current dispute regarding the specific functional roles of brain areas that are often co-activated in studies of decision tasks, dorsal premotor cortex(PMd) and posterior parietal cortex(PPC). In one model, the PPC distinctly drives intentions for action selection, whereas PMd stimulation results in complex multi-joint movements without any awareness of, nor subjective feeling of, willing the elicited movement, thus seems to merely help execute the chosen action.

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Savannah River Site/K Area Complex getter life extension report

Shepodd, Timothy J.

The K Area Complex (KAC) at the Savannah River Site (SRS) has been utilizing HiTop hydrogen getter material in 9975 Shipping Containers to prevent the development of flammable environments during storage of moisture-containing plutonium oxides. Previous testing and subsequent reports have been performed and produced by Sandia National Laboratories (SNL) to demonstrate the suitability and longevity of the getter during storage at bounding thermal conditions. To date, results have shown that after 18 months of continuous storage at 70 C, the getter is able to both recombine gaseous hydrogen and oxygen into water when oxygen is available, and irreversibly getter (i.e. scavenge) hydrogen from the vapor space when oxygen is not available, both under a CO{sub 2} environment. [Refs. 1-5] Both of these reactions are catalytically enhanced and thermodynamically favorable. The purpose of this paper is to establish the justification that maintaining the current efforts of biannual testing is no longer necessary due to the robust performance of the getter material, the very unlikely potential that the recombination reaction will fail during storage conditions in KAC, and the insignificant aging effects that have been seen in the testing to date.

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Update to SAND2007-0095, SAND2007-1789P, and SAND2007-7165P: 18-Month 70°C Aging Study of HiTop Hydrogen Getter for WSRC

Buffleben, George M.; Nissen, April E.; Shepodd, Timothy J.

Hydrogen getters were tested for use in storage of plutonium-bearing materials in accordance with DOE's Criteria for Interim Safe Storage of Plutonium Bearing Materials. The original studies, documented in Sandia Report SAND2007-0095, included HiTop getter material aged for 3 months at 70°C. This material was aged for an additional 3 months for a total of 6 months at 70°C, and the performance of the getter was evaluated again and documented in Sandia Report SAND2007-1789P. This material was then aged for an additional 7 months for a total of 13 months at 70°C, and the performance of the getter under recombination and gettering conditions was evaluated. A sample of the 13 months aged getter was exposed to radiation at SRNL, and the performance of this sample was also evaluated. The results of the 13 months study is reported in SAND2007-7165P. The HiTop material was aged for an additional 5 months for a total of 18 months. This material was split into two samples with the second sample being exposed to radiation at SRNL. The performance of the 18 month aged HiTop material is covered in this report. The 18-month aged material showed similar performance under gettering conditions to the previously aged material: the recombination rate is well above the required rate of 45 std. cc H2/h, and the gettering reaction occurs in the absence of oxygen at a slower rate. Both pressure drop measurements and 1H NMR analyses support these conclusions. 1H NMR analyses show extremely minor changes in the 18-month aged material, which can be possibly attributed to slight decomposition of the HiTop material or absorption of contaminants during the aging process.

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Performance testing of HITOP polymer hydrogen getter materials in a carbon dioxide atmosphere

Nissen, April E.; Buffleben, George M.; Shepodd, Timothy J.

Legacy plutonium-bearing materials are stored in shipping containers at the Savannah River Site (SRS) until their final disposition can be determined. This material has been stabilized and is maintained per the DOE’s standard for long-term storage of Pu-containing materials, DOE-STD-3013. As a part of its ongoing storage mission, Washington Savannah River Company’s (WSRC) Nuclear Materials Management (NMM) organization is tasked with a surveillance program that will ensure these materials have remained in their expected condition over the several years of storage. Information from this program will be used by multiple entities to further validate the safe storage of Pu-bearing materials per DOE-STD-3013. Part of the program entails cutting open selected 3013 containers and sampling the materials inside. These samples will then be analyzed by Savannah River National Laboratory (SRNL). The remaining material not used for samples will then be repackaged in non-3013 containers to be placed back into shipping packages for storage until disposition at SRS. These repackaged materials will be stored per the requirements of DOE’s Criteria for Interim Safe Storage of Plutonium Bearing Materials (ISSC).

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Biological detection and tagging using tailorable, reactive, highly fluorescent chemosensors

McElhanon, James R.; Zifer, Thomas Z.; Rahn, Larry A.; Shepodd, Timothy J.

This program was focused on the development of a fluorogenic chemosensor family that could tuned for reaction with electrophilic (e.g. chemical species, toxins) and nucleophilic (e.g. proteins and other biological molecules) species. Our chemosensor approach utilized the fluorescent properties of well-known berberine-type alkaloids. In situ chemosensor reaction with a target species transformed two out-of-plane, weakly conjugated, short-wavelength chromophores into one rigid, planar, conjugated, chromophore with strong long wavelength fluorescence (530-560 nm,) and large Stokes shift (100-180 nm). The chemosensor was activated with an isourea group which allowed for reaction with carboxylic acid moieties found in amino acids.

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Development of a high-throughput microfluidic integrated microarray for the detection of chimeric bioweapons

Hux, Gary A.; Shepodd, Timothy J.

The advancement of DNA cloning has significantly augmented the potential threat of a focused bioweapon assault, such as a terrorist attack. With current DNA cloning techniques, toxin genes from the most dangerous (but environmentally labile) bacterial or viral organism can now be selected and inserted into robust organism to produce an infinite number of deadly chimeric bioweapons. In order to neutralize such a threat, accurate detection of the expressed toxin genes, rather than classification on strain or genealogical decent of these organisms, is critical. The development of a high-throughput microarray approach will enable the detection of unknowns chimeric bioweapons. The development of a high-throughput microarray approach will enable the detection of unknown bioweapons. We have developed a unique microfluidic approach to capture and concentrate these threat genes (mRNA's) upto a 30 fold concentration. These captured oligonucleotides can then be used to synthesize in situ oligonucleotide copies (cDNA probes) of the captured genes. An integrated microfluidic architecture will enable us to control flows of reagents, perform clean-up steps and finally elute nanoliter volumes of synthesized oligonucleotides probes. The integrated approach has enabled a process where chimeric or conventional bioweapons can rapidly be identified based on their toxic function, rather than being restricted to information that may not identify the critical nature of the threat.

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Performance testing of aged hydrogen getters against criteria for interim safe storage of plutonium bearing materials

Nissen, April E.; Buffleben, George M.; Shepodd, Timothy J.

Hydrogen getters were tested for use in storage of plutonium-bearing materials in accordance with DOE's Criteria for Interim Safe Storage of Plutonium Bearing Materials. The hydrogen getter HITOP was aged for 3 months at 70 C and tested under both recombination and hydrogenation conditions at 20 and 70 C; partially saturated and irradiated aged getter samples were also tested. The recombination reaction was found to be very fast and well above the required rate of 45 std. cc H2h. The gettering reaction, which is planned as the backup reaction in this deployment, is slower and may not meet the requirements alone. Pressure drop measurements and {sup 1}H NMR analyses support these conclusions. Although the experimental conditions do not exactly replicate the deployment conditions, the results of our conservative experiments are clear: the aged getter shows sufficient reactivity to maintain hydrogen concentrations below the flammability limit, between the minimum and maximum deployment temperatures, for three months. The flammability risk is further reduced by the removal of oxygen through the recombination reaction. Neither radiation exposure nor thermal aging sufficiently degrades the getter to be a concern. Future testing to evaluate performance for longer aging periods is in progress.

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Microchip HPLC of peptides and proteins

Analytical Chemistry

Reichmuth, David S.; Shepodd, Timothy J.; Kirby, Brian J.

Rapid microchip reversed-phase HPLC of peptides and proteins at pressure gradients of 12 bar/cm (180 psi/cm) has been performed using a microdevice that integrates subnanoliter on-chip injection and separation with a miniaturized fluorescence detector. Proteins and peptides were separated on a C18 side-chain porous polymer monolith defined by contact lithography, and injection was achieved via a pressure-switchable fluoropolymer valve defined using projection lithography. Preliminary separations of peptide standards and protein mixtures were performed in 40-200 s, and switching between samples with no detectible sample carryover has been performed. The injections and separations were reproducible; the relative standard deviation (RSD) for retention time was 0.03%, and peak area RSD was 3.8%. Sample volumes ranging from 220 to 800 pL could be linearly metered by controlling the pressure injection pulse duration with conventional timing and valving. The current prototype system shows the potential for rapid and autonomous HPLC separations with varying modalities and the potential for direct connection to mass spectrometers at nanospray flow rates. © 2005 American Chemical Society.

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Processing of Lewisite munitions in the explosive destruction system

Didlake, John E.; Shepodd, Timothy J.; Bradshaw, Robert W.

The Explosive Destruction System (EDS) is a transportable system designed to treat chemical munitions. The EDS is transported on an open trailer that provides a mounting surface for major system components and an operator's work platform. The trailer is towed by a prime mover. An explosive containment vessel contains the shock, munition fragments, and the chemical agent during the munition opening process, and then provides a vessel for the subsequent chemical treatment of the agent. A fragmentation suppression system houses the chemical munition and protects the containment vessel from high velocity fragments. An explosive accessing system uses shaped charges to cut the munition open and attack the burster. A firing system detonates the shaped charges. A chemical feed system supplies neutralizing reagents and water to the containment vessel. A waste handling system drains the treated effluent.

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Rapid Ultrasensitive Chemical-Fingerprint Detection of Chemical and Biochemical Warfare Agents

Ashby, Carol I.; Ashby, Carol I.; Shepodd, Timothy J.; Yelton, William G.; Muron, David J.

Vibrational spectra can serve as chemical fingerprints for positive identification of chemical and biological warfare molecules. The required speed and sensitivity might be achieved with surface-enhanced Raman spectroscopy (SERS) using nanotextured metal surfaces. Systematic and reproducible methods for preparing metallic surfaces that maximize sensitivity have not been previously developed. This work sought to develop methods for forming high-efficiency metallic nanostructures that can be integrated with either gas or liquid-phase chem-lab-on-a-chip separation columns to provide a highly sensitive, highly selective microanalytical system for detecting current and future chem/bio agents. In addition, improved protein microchromatographic systems have been made by the creation of acrylate-based porous polymer monoliths that can serve as protein preconcentrators to reduce the optical system sensitivity required to detect and identify a particular protein, such as a bacterial toxin.

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17 Results
17 Results