Redox Chemistry and the Role of Trapped Molecular O2 in Li-Rich Disordered Rocksalt Oxyfluoride Cathodes.

In the search for high energy density cathodes for next-generation lithium-ion batteries, the disordered rocksalt oxyfluorides are receiving significant attention due to their high capacity and lower voltage hysteresis compared with ordered Li-rich layered compounds. However, a deep understanding of these phenomena and their redox chemistry remains incomplete. Using the archetypal oxyfluoride, Li2MnO2F, we show that the oxygen redox process in such materials involves the formation of molecular O2 trapped in the bulk structure of the charged cathode, which is reduced on discharge. The molecular O2 is trapped rigidly within vacancy clusters and exhibits minimal mobility unlike free gaseous O2, making it more characteristic of a solid-like environment. The Mn redox process occurs between octahedral Mn3+ and Mn4+ with no evidence of tetrahedral Mn5+ or Mn7+. We furthermore derive the relationship between local coordination environment and redox potential; this gives rise to the observed overlap in Mn and O redox couples and reveals that the onset potential of oxide ion oxidation is determined by the degree of ionicity around oxygen, which extends models based on linear Li-O-Li configurations. This study advances our fundamental understanding of redox mechanisms in disordered rocksalt oxyfluorides, highlighting their promise as high capacity cathodes.

Gamma entrainment frequency affects mood, memory and cognition: an exploratory pilot study.

Here we provide evidence with an exploratory pilot study that through the use of a Gamma 40 Hz entrainment frequency, mood, memory and cognition can be improved with respect to a 9-participant cohort. Participants constituted towards three binaural entrainment frequency groups: the 40 Hz, 25 Hz and 100 Hz. Participants attended a total of eight entrainment frequency sessions twice over the duration of a 4-week period. Additionally, participants were assessed based on their cognitive abilities, mood as well as memory, where the cognitive and memory assessments occurred before and after a 5-min binaural beat stimulation. The mood assessment scores were collected from sessions 1, 4 and 8, respectively. With respect to the Gamma 40 Hz entrainment frequency population, we observed a mean improvement in cognitive scores, elevating from 75% average to 85% average upon conclusion of the experimentation at weak statistical significance ([Formula: see text] = 0.10, p = 0.076). Similarly, memory score improvements at a greater significance ([Formula: see text] = 0.05, p = 0.0027) were noted, elevating from an average of 87% to 95%. In pertinence to the mood scores, a negative correlation across all populations were noted, inferring an overall increase in mood due to lower scores correlating with elevated mood. Finally, correlation analysis revealed a stronger R[Formula: see text] value (0.9838) within the 40 Hz group between sessions as well as mood score when compared across the entire frequency group cohort.

Photosystem II Acts as a Spin-Controlled Electron Gate during Oxygen Formation and Evolution.

The oxygen evolution complex (OEC) of photosystem II (PSII) is intrinsically more active than any synthetic alternative for the oxygen evolution reaction (OER). A crucial question to solve for the progress of artificial photosynthesis is to understand the influential interactions during water oxidation in PSII. We study the principles of interatomic electron transfer steps in OER, with emphasis on exchange interactions, revealing the influence of delocalizing ferromagnetic spin potentials during the catalytic process. The OEC is found to be an exchange coupled mixed-valence electron-spin acceptor where its orbital physics determine the unique activity of PSII. The two unpaired electrons needed in the triplet O2 molecule interact with the high spin state of the catalyst via exchange interactions; the optimal ferromagnetic catalyst and the resulting radical intermediates are spin paired. As a result, the active center of the CaMn4O5 cofactor, stimulated by the driving potential provided by photons, works as a spin valve to accelerate the formation and release of O2 from diamagnetic H2O.

Mass bias corrections for U-Pb isotopic analysis by secondary ion mass spectrometry: Implications for U-Pb dating of uraninite.

RATIONALE: Uranium (U)-lead (Pb) geochronology of uraninite is critical to the study of the genesis of U deposits throughout the world. Previous attempts at developing a technique to date uraninite using secondary ion mass spectrometry (SIMS) have, however, had limited success. Improper correction of mass bias results in incorrect reported U-Pb ratios. When these results are plotted on Concordia diagrams they produce erroneous ages, complicating the study of U deposits. METHODS: Uranium and Pb isotope ratios were measured in three uraninite reference materials (RMs) with varying Pb content and three samples with unknown U-Pb isotope compositions using a CAMECA 7f SIMS instrument. Measurements were made using a primary beam of O(-) accelerated at 12.5 kV. A mass resolving power of 1300 and a 50-V offset were used to minimize interferences. RESULTS: The study demonstrates that the mass bias for U-Pb isotope ratio measurements in uraninite by SIMS varies as a function of Pb content. A three-point calibration curve was developed using uraninite RMs with low-, intermediate- and high-Pb contents. Corrected ratios for both concordant and discordant uraninite were plotted on a Concordia diagram to demonstrate the effect that different correction techniques have on the resulting age. CONCLUSIONS: Accurate determination of U-Pb ratios in uraninite using a SIMS instrument requires a suite of RMs with varying Pb content and the construction of a calibration curve, or a uraninite RM with a Pb content similar to that of the unknowns. Failure to standardize correctly will result in erroneous ages being calculated using Concordia diagrams. Copyright © 2016 John Wiley & Sons, Ltd.