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Apiose is a naturally occurring, uncommon branched-chain pentose found in plant cell walls as part of the complex polysaccharide Rhamnogalacturonan II (RG-II). The structural elucidation of the three-dimensional structure of RG-II by nuclear magnetic resonance (NMR) spectroscopy is significantly complicated by the ability of apiose to cross-link via borate ester linkages to form RG-II dimers. Here, we developed a computational approach to gain insight into the structure–spectra relationships of apio–borate complexes in an effort to complement experimental assignments of NMR signals in RG-II. Our protocol involved structure optimizations using density functional theory (DFT) followed by isotropic magnetic shielding constant calculations using the gauge-invariant atomic orbital (GIAO) approach to predict chemical shifts. We evaluated the accuracy of 23 different functional–basis set (FBS) combinations with and without implicit solvation for predicting the experimental 1 H and 13 C shifts of a methyl apioside and its three borate derivatives. The computed NMR predictions were evaluated on the basis of the overall shift accuracy, relative shift ordering, and the ability to distinguish between dimers and monomers. We demonstrate that the consideration of implicit solvation during geometry optimizations in addition to the magnetic shielding constant calculations greatly increases the accuracy of NMR chemical shift predictions and can correctly reproduce the ordering of the 13 C shifts and yield predictions that are, on average, within 1.50 ppm for 13 C and 0.12 ppm for 1 H shifts for apio–borate compounds.
The basis of H-1 and C-13 high-resolution NMR investigations of solid polymers is outlined. The C-13 NMR spectra of solid syndiotactic and isotactic polypropene are discussed and their interpretation in terms of conformation and chain-packing effects are reviewed. The effects of decreasing temperature on the C-13 high-resolution spectrum of an annealed sample of isotactic polypropene is described and interpreted in terms of the crystal structure. The question of the proportion of the sample giving rise to C-13 signals is addressed and some results reported. The main cause for observing only part of the total sample is shown to be the H-1 rotating frame spin-lattice relaxation behavior. The H-1 spin-lattice relaxation and spectral characteristics of a number of polyolefin samples are summarized and the role of spin-diffusion discussed.
An ongoing joint NASA/Army program to study the effects of ice accretion on unprotected helicopter rotor aerodynamic performance is discussed. This program integrates flight testing, wind tunnel testing, and analytical modeling. Results are discussed for helicopter flight testing in the Canadian NRC hover spray rig facility to measure rotor aero performance degradation and document rotor ice accretion characteristics. The results of dry wind tunnel testing of airfoil sections with artificial ice accretions and predictions of rotor performance degradation using available rotor performance codes and the wind tunnel data are presented. An alternative approach to conducting future helicopter icing flight programs is discussed.
An ongoing joint NASA/Army program to study the effects of ice accretion on unprotected helicopter rotor aerodynamic performance is discussed. This program integrates flight testing, wind tunnel testing, and analytical modeling. Results are discussed for helicopter flight testing in the Canadian NRC hover spray rig facility to measure rotor aero performance degradation and document rotor ice accretion characteristics. The results of dry wind tunnel testing of airfoil sections with artificial ice accretions and predictions of rotor performance degradation using available rotor performance codes and the wind tunnel data are presented. An alternative approach to conducting future helicopter icing flight programs is discussed.
We announce the discovery of an eclipsing nova-like cataclysmic variable (CV) as the optical counterpart to the HEAO 1 X-ray source 1H1752 + 081. This CV has an orbital period of 1.882801 hr, a high equivalent width of H-beta, and an average m(sub v) of 16.4 out of the eclipse. A geometric model is constructed from observations of the eclipse ingress and egress in many optical bandpasses. The broad-band emission originates primarily in two regions; the disk/accretion stream 'hot spot' and a compact central component, which may be a spot on the white dwarf surface, the entire white dwarf surface or the boundary layer between the accretion disk and the white dwarf surface. Based on the durations and offsets of the two eclipses we determined the mass ratio q = 2.5 +/- 0.6 and the angle of inclination i = 77 deg +/- 2 deg. If the central component is the entire white dwarf surface the masses of the stars are M(sub 1) = 0.80 +/- 0.06 solar masses and M(sub 2) = 0.32 +/- 0.06 solar masses. The disk is faint and small (R(sub D) = 0.25 +/- 0.05 r(sub L1), where r(sub L1) is the distance from the primary to the L(sub 1) point), compared to other eclipsing CVs. The small disk may result from the removal of angular momentum from the accretion disk by the magnetic field of the white dwarf; this CV may be a DQ Her type with a slowly rotating white dwarf. The emission-line velocities do not show the 'Z-wave' expected from the eclipse of a Keplerian accretion disk, nor do they have the correct phasing to originate near the white dwarf. The most likely origin of the line emission is the hot spot. The secondary star is visible at wavelengths greater than or equal to 6000 A during eclipse. We estimate a spectral type approximately M6 which, together with the observed m(sub 1) = 16.94 during eclipse, results in a distance estimate of 150 +/- 27 pc.
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In late 2022, the Human Autonomy Teaming Lab (NASA Ames Research Center) conducted a manned, human-in-the-loop (HITL) simulation. This HITL was the lab’s second Hazard Perception and Avoidance (HPA) technical work under NASA’s Advanced Air Mobility (AAM), Automated Flight and Contingency Management (AFCM) Sub-Project. The goals were to assess detect and avoid technology for manned, electric vertical takeoff and landing (eVTOL) aircraft. This simulation tested Resolution Advisory (RA) responses and return-to-course (RTC) maneuvers for the second version of the Airborne Collision Avoidance System’s (ACAS) rotary-wing (Xr) variant. This was conducted at the center's Vertical Motion Simulator (VMS), on a motion-based platform, and was configured to fly eVTOL aircraft while maneuvering for intruding traffic. Variables for this study included ACAS Xr modes (i.e., TA/RA and DAA) and phases of flight (i.e., Cruise, Hover, and Approach). The data collected included response times, losses of well clear, and pilots' noncompliances to alerts and guidance as well as subjective ratings like acceptability and perceived workload. Additional details and future anticipations are also discussed.
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1,3-Dimethyl-2,3-dihydrobenzo[ d ]imidazoles, 1H , and 1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[ d ]imidazoles, 1 2 , are of interest as n-dopants for organic electron-transport materials. Salts of 2-(4-(dimethylamino)phenyl)-4,7-dimethoxy-, 2-cyclohexyl-4,7-dimethoxy-, and 2-(5-(dimethylamino)thiophen-2-yl)benzo[ d ]imidazolium ( 1g–i + , respectively) have been synthesized and reduced with NaBH 4 to 1gH , 1hH , and 1iH , and with Na:Hg to 1g 2 and 1h 2 . Their electrochemistry and reactivity were compared to those derived from 2-(4-(dimethylamino)phenyl)- ( 1b + ) and 2-cyclohexylbenzo[ d ]imidazolium ( 1e + ) salts. E ( 1 + / 1 • ) values for 2-aryl species are less reducing than for 2-alkyl analogues, i.e., the radicals are stabilized more by aryl groups than the cations, while 4,7-dimethoxy substitution leads to more reducing E ( 1 + / 1 • ) values, as well as cathodic shifts in E ( 1 2 •+ / 1 2 ) and E ( 1H •+ / 1H ) values. Both the use of 3,4-dimethoxy and 2-aryl substituents accelerates the reaction of the 1H species with PC 61 BM. Because 2-aryl groups stabilize radicals, 1b 2 and 1g 2 exhibit weaker bonds than 1e 2 and 1h 2 and thus react with 6,13-bis(triisopropylsilylethynyl)pentacene ( VII ) via a “cleavage-first” pathway, while 1e 2 and 1h 2 react only via “electron-transfer-first”. 1h 2 exhibits the most cathodic E ( 1 2 •+ / 1 2 ) value of the dimers considered here and, therefore, reacts more rapidly than any of the other dimers with VII via “electron-transfer-first”. Crystal structures show rather long central C–C bonds for 1b 2 (1.5899(11) and 1.6194(8) Å) and 1h 2 (1.6299(13) Å).
This report presents an enhanced performance evaluation of motor-driven pumps (MDPs) at U.S. commercial nuclear power plants. The data used in this study are based on the operating experience failure reports from calendar year 1998 through 2020 as reported in the Institute of Nuclear Power Operations (INPO) Industry Reporting and Information System (IRIS). The MDP failure modes considered for standby systems are fail to start (FTS), fail to run (FTR) for one hour of operation (FTR≤1H), FTR after one hour of operation (FTR>1H), and for normally running systems FTS and FTR. An eight-hour unreliability estimate is also calculated and trended. The component reliability estimates and the reliability data are trended for the most recent 10-year period while yearly estimates for reliability are provided for the entire study period. The following increasing trends were identified for MDPs for the most recent 10-year period: • Standby MDP frequency of start demands (demands per reactor year) • Standby MDP frequency of FTR≤1H hours (hours per reactor year) • Standby MDP frequency of FTR>1H hours • Normally running MDP frequency of run hours. The following decreasing trends were identified for MDPs for the most recent 10-year period: • Standby MDP FTR≤1H failure probability • Normally running MDP FTR failure rate • Standby MDP unavailability • Normally running MDP total unreliability (8-hour mission) • Standby MDP frequency of FTR≤1H events (failures per reactor year) • Normally running MDP frequency of FTR events.
This dataset contains solid-state 1H and 13C NMR relaxometry data, differential scanning calorimetry (DSC) data, and size exclusion chromatography (SEC/GPC) data supporting the study of sub-glass-transition (sub-Tg) molecular dynamics in a composition- and sequence-controlled series of diphenyl-substituted polysiloxanes (PDMS, 14Ph, 33Ph, 50Ph, 67Ph, and 100Ph; 0–100% diphenylsiloxane content by mole).All solid-state NMR data were acquired on a 200 MHz Bruker Avance III HD spectrometer using a static 7 mm HX probe or a 4 mm HX probe under 4 kHz magic-angle spinning. Raw Bruker TopSpin experiment folders are included for: (1) variable-temperature 1H lineshape measurements used to determine linewidth (FWHM) as a function of temperature across the glass transition; (2) 1H T1 (saturation recovery with solid-echo detection), probing nanosecond-scale dynamics near the 1H Larmor frequency; (3) 1H T1rho (direct spin-lock, 62.5 kHz), probing microsecond-scale segmental dynamics; (4) 13C-detected Lee–Goldburg cross-polarization 1H T1rho (LGCPH T1rho) for 33Ph and 50Ph, resolving aromatic and aliphatic proton environments; and (5) 13C T1 relaxation for 33Ph and 50Ph. Differential scanning calorimetry data (TA Instruments DSC 25, −150 to +120 °C, up to +300 °C for 100Ph, 10 °C/min) are included for all six compositions and support the glass-transition temperatures in Table 1 and Figure 1. Size exclusion chromatography data (Agilent 1200 Series, PL-Gel 300 mixed-C column, THF mobile phase, polystyrene calibration standards) are included for the three synthesized copolymers (33Ph, 50Ph, 67Ph) and support the number-average molecular weights in Table 1. Processed data include per-composition relaxation-time summaries (Excel), curve-fitting and Bloembergen-Purcell-Pound (BPP) model analysis notebooks (Jupyter/Python), and Igor Pro (.pxp) master files used to generate the manuscript's figures.
A microseismic data set was acquired at Hydraulic Fracturing Test Site 2 (HFTS2) in the Delaware Basin (Texas, USA) by the HFTS2 consortium as a part of data-collection program designed to help maximize the efficiency of hydraulic fracturing, understand the impacts of nearby depleted zones, and increase the production of hydrocarbons. Advanced methods of microseismic monitoring applied at HFTS2 include 1) native synchronization of five monitor arrays, 2) real-time location of microseismic events, 3) joint event hypocenter/ velocity-model inversion that locates microseismic events simultaneously with constructing azimuthally anisotropic velocity models, 4) high-resolution reservoir imaging, utilizing microseismic events as downhole sources. HFTS2 microseismic data set illustrated the influence of geologic complexity, variations in treatment designs, and the presence of parent wells on the efficiency of hydraulic fracturing. Three Wolfcamp wells, Boxwood 1H, 2H, and 4H, were stimulated sequentially, exhibiting very different patterns of microseismicity. When the Boxwood 1H well is stimulated, its toe stages quickly reacted to the presence of depleted Bitterroot section to the east of the Boxwood pad, extending microseismic events over 3,000 ft to the east. This behavior changes dramatically after the treatment passes the Bitterroot section at the toe, and the heel stages in 1H showed tight microseismic grouping around the stimulated well, indicative of treatment of virgin reservoir rock. The Boxwood 2H demonstrates this same pattern of behavior between the toe and heel stages of the well, suggesting that the depleted Bitterroot section remains easier to refracture than adjacent non-depleted rock. Microseismic activity associated with Boxwood 4H treatment is distinctly different from those in Boxwood wells 1H and 2H. The events generated during stimulation of 4H are hardly influenced by the depleted Bitterroot section and fill the space between the previously stimulated 1H and 2H wells. Altogether, microseismic patterns suggest that treatment fluids tend to find the weakest passages through geologic formations, and the relative well positions and treatment sequence have a significant impact on fracture geometry, as indicated by microseismic event locations.
This report presents an enhanced performance evaluation of motor-driven pumps (MDPs) at U.S. commercial nuclear power plants. The data used in this study are based on the operating experience failure reports from calendar year 1998 through 2022 as reported in the Institute of Nuclear Power Operations (INPO) Industry Reporting and Information System (IRIS). The MDP failure modes considered for standby systems are fail to start (FTS), fail to run (FTR) for one hour of operation (FTR=1H), FTR after one hour of operation (FTR>1H), and for normally running systems FTS and FTR. An eight-hour unreliability estimate is also calculated and trended. The component reliability estimates and the reliability data are trended for the most recent 10-year period while yearly estimates for reliability are provided for the entire study period. The following increasing trends were identified for MDPs for the most recent 10-year period: (1) Standby MDP frequency of start demands (demands per reactor year), (2) Standby MDP frequency of FTR=1H hours (hours per reactor year), (3) Standby MDP frequency of FTR>1H hours, and (4) Normally running MDP frequency of run hours. The following decreasing trends were identified for MDPs for the most recent 10-year period: (1) Standby MDP FTR=1H failure probability, (2) Normally running MDP FTR failure rate, (3) Standby MDP unavailability, (4) Standby MDP total unreliability (8-hour mission), and (5) Normally running MDP total unreliability (8-hour mission).
This report presents an enhanced performance evaluation of turbine driven pumps (TDPs) at U.S. commercial nuclear power plants. The data used in this study are based on the operating experience failure reports from calendar year 1998 through 2022 as reported in the Institute of Nuclear Power Operations (INPO) Industry Reporting and Information System (IRIS). The TDP failure modes considered for standby systems are fail to start (FTS), fail to run (FTR) for one hour of operation (FTR=1H), FTR after one hour of operation (FTR>1H), and for normally running systems FTS and FTR. An eight hour unreliability estimate is also calculated and trended. The component reliability estimates and the reliability data are trended for the most recent 10 year period while yearly estimates for reliability are provided for the entire study period. No increasing trends were identified for TDPs for the most recent 10 year period: The following decreasing trends were identified for TDPs for the most recent 10 year period: • Standby TDP FTR>1H failure rate • Normally running TDP FTR failure rate • Standby TDP unavailability • Standby MDP total unreliability (8-hour mission) • Standby TDP frequency of start demands (demands per reactor year) • Standby TDP frequency of FTR=1H hours (hours per reactor year) • Standby TDP frequency of FTR>1H events (failures per reactor year) • Normally running TDP frequency of start demands • Normally running TDP frequency of run hours • Normally running TDP frequency of FTR events.
1T-TaS2 is a layered charge density wave (CDW) crystal exhibiting sharp phase transitions and associated resistance changes. These resistance steps could be exploited for information storage, underscoring the importance of controlling and tuning the CDW states. Given the importance of out-of-plane interactions in 1T-TaS2, modulating interlayer interactions by heterostructuring is a promising method for tailoring CDW phase transitions. In this work, we investigate the optical and electronic properties of heterostructures comprising 1T-TaS2 and monolayer 1H-WSe2. By systematically varying the thickness of 1T-TaS2 and its azimuthal alignment with 1H-WSe2, we find that intrinsic moiré strain and interfacial charge transfer introduce CDW disorder in 1T-TaS2 and modify the CDW ordering temperature. Furthermore, our studies reveal that the interlayer alignment impacts the exciton dynamics in 1H-WSe2, indicating that heterostructuring can concurrently tailor the electronic phases in 1T-TaS2 and the optical properties of 1H-WSe2. This work presents a promising approach for engineering the optoelectronic behavior of heterostructures that integrate CDW materials and semiconductors.