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DOE OSTI2020

Roles of D1-Glu189 and D1-Glu329 in O 2 Formation by the Water-Splitting Mn 4 Ca Cluster in Photosystem II

During the catalytic step that precedes O–O bond formation in Photosystem II, a water molecule deprotonates and moves next to the water-splitting Mn 4 Ca cluster’s O5 oxo bridge. The relocated oxygen, known as O6 or Ox, may serve as a substrate, combining with O5 to form O 2 during the final step in the catalytic cycle, or may be positioned to become a substrate during the next catalytic cycle. Recent serial femtosecond X-ray crystallographic studies show that the flexibility of D1-E189 plays a critical role in facilitating the relocation of O 6 /Ox. In this study, the D1-E189G and D1-E189S mutations were characterized with FTIR difference spectroscopy. The data show that both mutations support Mn 4 Ca cluster assembly, substantially inhibit advancement beyond the S 2 state, and alter the network of H bonds that surrounds the Mn 4 Ca cluster. Previously, the D1-E189Q, D1-E189K, and D1-E189R mutations were shown to have little impact on the activity, electron transfer rates, or spectral properties of Photosystem II. A rationale for this behavior is presented. The residue D1-E329 interacts with water molecules in the O1 water network that has been suggested recently to supply substrate during the catalytic cycle. Characterization of the D1-E329A mutant with FTIR difference spectroscopy shows that this mutation does not substantially perturb the structure of PSII or the water molecules whose O–H stretching modes change during the catalytic cycle. Furthermore, this result provides additional evidence that the water molecules whose vibrational properties change during the S 1 to S 2 transition are confined approximately to the region bounded by D1-N87, D1-N298, and D2-K317.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Raman signatures from age-dating PuO 2 since last calcination

The self-irradiation of PuO 2 has been shown to affect the attributes of fifteen vibrational bands in the Raman spectrum. The vibrational bands correspond to the Raman allowed vibrational mode T 2g , overtones, defects, and bands from electronic origin. Defects in the crystal lattice from low-calcination temperature and alpha decay origins are responsible for the changes in the band attributes (band position, full-width half maximum (FWHM), intensity). Crystal lattice defects are also responsible for the growth of the defect bands. The temporal behavior of the vibrational bands can be used to estimate the age of the material since last calcination. Laser annealing was used to reset the material to full crystallinity prior to the aging study. 240 PuO 2 , with an alpha decay rate of 3.67 greater than the decay rate of 239 PuO 2 , was primarily used to assess the alpha decay-induced damage within 3 years. The aging study focused on the time-dependent properties of the T 2g band and the growth of defect bands. The FWHM of the T 2g band and the ratio of the areas of the defect bands/T 2g band were measured through a time period in excess of 3 years. The data from this study were found very close to the data describing the temporal evolution of the lattice constant measured with the X-ray diffraction (XRD) technique. The local physical properties of the material measured with Raman spectroscopy and the lattice parameter constant measured with XRD indicates a strong correlation between the two techniques. Although both techniques provide similar age-dating information, in contrast to the few milligram quantities required for XRD, Raman spectroscopy requires a 10 µm diameter PuO 2 particle to provide an estimate of the material age since last calcination.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1995

NASA Tech Briefs, November 1995

The contents include: 1) Mission Accomplished; 2) Resource Report: Marshall Space Flight Center; 3) NASA 1995 Software of the Year Award; 4) Microbolometers Based on Epitaxial YBa2Cu3O(sub 7-x) Thin Films; 5) Garnet Random-Access Memory; 6) Fabrication of SNS Weak Links on SOS Substrates; 7) High-Voltage MOSFET Switching Circuit; 8) Asymmetric Switching for a PWM H-Bridge Power Circuit; 9) Better Ohmic Contacts for InP Semiconductor Devices; 10) Low-Bandgap Thermovoltaic Materials and Devices; 11) Digital Frequency-Differencing Circuit; 12) Imaging Magnetometer; 13) Computer-Assisted Monitoring of a Complex System; 14) Buffered Telemetry Demodulator; 15) Compact Multifunction Inspection Head; 16) Optical Detection of Fractures in Ceramic Diaphragms; 17) Eddy-Current Detection of Cracks in Reinforced Carbon/Carbon; 18) Apparent Thermal Conductivity of Multilayer Insulation; 19) Optimizing Misch-Metal Compositions in Metal Hydride Anodes; 20) Device for Sampling Surface Contamination; 21) Probabilistic Failure Assessment for Fatigue; 22) Probabilistic Fatigue and Flaw-Propagation Analysis; 23) Windows Program for Driving the TDU-850 Printer; 24) Subband/Transform MATLAB Functions for Processing Images; 25) Computing Equilibrium Chemical Compositions; 26) Program Processes Thermocouple Readings; 27) ICAN-Second-Generation Integrated Composite Analyzer; 28) Integrated Composite Analyzer with Damping Capabilities; 29) Computing Efficiency of Transfer of Microwave Power; 30) Program Calculates Power Demands of Electronic Designs; 31) Cost-Estimation Program; 32) Program Estimates Areas Required by Electronic Designs; 33) Program to Balance Mapped Turbopump Assemblies; 34) BiblioTech; 35) Controlling Mirror Tilt With a Bimorph Actuator; 36) Burst-Disk Device Simulates Effect of Pyrotechnic Device; 37) Bearing-Mounting Concept Accommodates Thermal Expansion; 38) Parallel-Plate Acoustic Absorbers for Hot Environments; 39) Adjustable-Length Strut Withstands Large Cyclic Loads; 40) Tool Indicates Contact Angles in Bearing Raceways; 41) Gravity Slides With Magnetic Braking; 42) High-Torque, Lightweight, Pneumatically Driven Wrench for Small Spaces; 43) Device for Testing Compatibility of an O-Ring; 44) Magnetic Heat Pump Containing Flow Diverters; 45) Variable-Tilt Helicopter Rotor Mast; 46) "Beach-Ball" Robotic Rovers; 47) Apparatus Would Measure Temperatures of Ball Bearings; 48) Flexible Borescope for Inspecting Ducts; 49) Texturing Copper To Reduce Secondary Emission of Electrons; 50) Automated Laser Cutting in Three Dimensions; 51) Algorithm Helps Monitor Engine Operation; 52) Flexible Revision of Data-Processing Communications; 53) Software for Managing the Use of Land; 54) Thermal Strap Increases Cryocooling Efficiency; 55) Reversible Nut With Engagement Indication; 56) Control Algorithms for Kinematically Redundant Manipulators; 57) Computed Hydrogen-Flow Splits in a Rocket Engine; 58) Pressure and Thermal Modeling of Rocket Launches; 59) Field of View of a Spacecraft Antenna: Analysis and Software; 60) Digital Controller for Laser-Beam-Steering Subsystem; 61) More About Beam-Steering Subsystem for Laser Communication; 62) Digital Controller for Laser-Beam-Steering Subsystem: Part 2; 63) Interface Circuit Board for Space-Shuttle Communications; 64) Automated Planning of Spacecraft Telecommunications; 65) Artifacts of Spectral Analysis of Instrument Readings; 66) Neural-Network Controller for Vibration Suppression; 67) Adaptive Finite-Element Computation in Fracture Mechanics; 68) Attitude Control for the Cassini Spacecraft; 69) Analytical Model for Fluid Dynamics in a Microgravity Environment; 70) Study of Rocket-Engine Joints Bonded by NVCU/NARloy-Z; 71) Improved Silicon Nitride for Advanced Heat Engines; 72) Parameters for Welding Aluminum/Lithium Alloys; 73) Lightweight Composite Intertank Structure; 74) Foil Patches Seal Small Vacuum Leaks; 75) Data Base on Cables and Connectors; 76) Effect of Clock Mode on Radiation Hardnessf an ADC; and 77) Fault-Tolerant Control for a Robotic Inspection System.

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