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  • Engineering (General)  (3)
  • Magnetic anisotropy  (2)
  • 1
    ISSN: 1572-9001
    Keywords: Magnetic anisotropy ; NMR ; shielding cone ; shielding value ; GIAO ; ethene ; alkenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Nuclei of hydrogen atoms located over a carbon-carbon double bond in the presence of a strong magnetic field experience a perturbed magnetic field caused primarily by the magnetic anisotropy of the π bond. However, the commonly used theoretical model for predicting the shielding effect of an alkene double bond on hydrogen nuclei is sometimes inconsistent with the observed proton NMR chemical shifts in structures that have covalently bonded hydrogens located over a carbon-carbon double bond. We have used the ab initio gauge including atomic orbital (GIAO) method to calculate isotropic shielding values and to determine the proton NMR shielding increments for a simple model system: methane held at various positions over ethene. These shielding increments calculated for one proton of methane have been mapped as a function of their position in Cartesian coordinates relative to the center of ethene. A mathematical function has been fit to this three-dimensional shielding increment surface at each of four distances from the face of the ethene molecule. Additionally, a single mathematical equation has been developed for predicting the shielding caused by the carbon-carbon double bond in ethene. In contrast to the traditionally employed shielding model, our results predict deshielding for protons within 3 Å above the center of a carbon-carbon double bond, consistent with experimental observations in several molecular systems. The NMR shielding increments predicted by this equation are compared to observed shielding increments in some test alkenes.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-9001
    Keywords: Magnetic anisotropy ; NMR ; shielding cone ; isotropic shielding ; GIAO ; (de)shielding surface ; alkenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In a strong magnetic field, nuclei located over a carbon-carbon double bond experience NMR shielding effects that are the net result of the magnetic anisotropy of the nearby double bond and various other intramolecular shielding effects. We have used GIAO, a subroutine in Gaussian 4, to calculate isotropic shielding values and to predict the proton NMR shielding increment for a simple model system: methane held in various orientations and positions over ethene. The average proton NMR shielding increments of several orientations of methane have been plotted versus the Cartesian coordinates of the methane protons relative to the center of ethene. A single empirical equation for predicting the NMR shielding experienced by protons over a carbon-carbon double bond has been developed from these data. The predictive capability of this equation has been validated by comparing the shielding increments for several alkenes calculated using our equation to the experimentally observed shielding increments. This equation predicts the NMR shielding effects more accurately than a previous model that was based on only one orientation of methane over ethene. Deshielding is predicted by this equation for protons over the center and within about 3 Å of a carbon-carbon double bond. This result is in contrast to predictions made by the long-held “shielding cone” model based on the McConnell equation found in nearly every textbook on NMR, but is consistent with experimental observations.
    Type of Medium: Electronic Resource
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  • 3
    Publication Date: 2019-07-13
    Description: Stirling Radioisotope Power Systems (RPS) are being developed by NASA's RPS Program in collaboration with the U.S. Department of Energy (DOE). Efforts ranging from 2001 to 2015 enabled development of the Technology Demonstration Convertor (TDC) for use in the 110-watt Stirling Radioisotope Generator (SRG-110) and the Advanced Stirling Convertor (ASC) for use in the Advanced Stirling Radioisotope Generator (ASRG). The DOE selected Lockheed Martin Space Systems Company (LMSSC) as the system integration contractor for both flight development efforts. The SRG-110 housed two TDCs fabricated by Infinia and resulted in the production of 16x demonstration units and 2x engineering units. The project was redirected in 2006 to make use of a more efficient and lower mass ASCs under development by Sunpower Inc. The DOE managed the flight contract with LMSSC and subcontractor Sunpower Inc. from 2007 to 2013 to build the ASRG, with support from NASA Glenn Research Center (GRC). Sunpower Inc. held two parallel contracts to produce ASCs, one with Lockheed Martin to produce ASC-F flight units and one with GRC for the production of ASC-E3 engineering unit pathfinders that were used to refine the flight design and production processes. The DOE initiated termination of the ASRG contract in late 2013. After ASRG had ended, GRC completed characterization testing of the ASRG Engineering Unit #2 (EU2) and the GRC contract with Sunpower was also completed. The NASA RPS Program Office has recently initiated a new Dynamic Power Conversion development effort which includes the potential maturation of Stirling, Brayton, and Rankine power convertors for the next generation of RPS. The effort started with the request for proposal and review of submits. Contracts are anticipated for release in 2017 and will initially focus on a design phase prior to fabrication and testing. This new effort will focus on robustness in addition to high efficiency, specific power, and reliability. Also, some requirements introduced during the ASRG contract have also been included in the new effort, such as constant lateral loading. Due to the focus on robustness and new requirements relative to the older TDC design, the Stirling Cycle Development Project has initiated an assessment of government owned hardware to help inform requirements evolution and evaluation of future designs. While lessons learned from the ASRG flight development project have been taken into consideration, the evaluation of the TDC design had not been completed for some existing environments or relatively new requirements. To further assess the TDC design, a series of tasks were initiated to evaluate degradation for units that have operated unattended for over 105,000 hours, demonstrate robustness to a random vibration environment, characterize and evaluate performance for varying lateral load profiles. The status for each task are described.
    Keywords: Engineering (General)
    Type: GRC-E-DAA-TN43782 , International Energy Conversion Engineering Conference; Jul 10, 2017 - Jul 12, 2017; Atlanta, GA; United States
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  • 4
    Publication Date: 2019-07-13
    Description: NASA's dynamic power convertor development in support of high-efficiency RPS is progressing as planned, and shows promise. This presentation gives dynamic conversion power system background, development path, and key convertor performance goals. It also gives information on the Flexure Isotope Stirling Convertor, Turbo-Brayton Convertor, Thermo-Acoustic Power Convertor, Sunpower Robust Stirling Convertor, Stirling Convertor Extended Operation, TDC #14 Disassembly and Inspection, and Launch Vibration Exposure on SES #2.
    Keywords: Engineering (General)
    Type: GRC-E-DAA-TN56093 , 2018 Power Community TDT/CLT; May 02, 2018; Cleveland, OH; United States
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  • 5
    Publication Date: 2019-07-13
    Description: NASA's dynamic power convertor development in support of high-efficiency RPS is progressing as planned, and shows promise. Ongoing research utilizing existing hardware supports viability of dynamic power conversion for RPS.
    Keywords: Engineering (General)
    Type: GRC-E-DAA-TN55689 , IAPG Mechanical Working Group Meeting; May 01, 2018 - May 03, 2018; Philadelphia, PA; United States
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