Advanced Two-Dimensional Heterojunction Photocatalysts of Stoichiometric and Non-Stoichiometric Bismuth Oxyhalides with Graphitic Carbon Nitride for Sustainable Energy and Environmental Applications

Semiconductor-based photocatalysis has been identified as an encouraging approach for solving the two main challenging problems, viz., remedying our polluted environment and the generation of sustainable chemical energy. Stoichiometric and non-stoichiometric bismuth oxyhalides (BiOX and BixOyXz where X = Cl, Br, and I) are a relatively new class of semiconductors that have attracted considerable interest for photocatalysis applications due to attributes, viz., high stability, suitable band structure, modifiable energy bandgap and two-dimensional layered structure capable of generating an internal electric field. Recently, the construction of heterojunction photocatalysts, especially 2D/2D systems, has convincingly drawn momentous attention practicably owing to the productive influence of having two dissimilar layered semiconductors in face-to-face contact with each other. This review has systematically summarized the recent progress on the 2D/2D heterojunction constructed between BiOX/BixOyXz with graphitic carbon nitride (g-C3N4). The band structure of individual components, various fabrication methods, different strategies developed for improving the photocatalytic performance and their applications in the degradation of various organic contaminants, hydrogen (H2) evolution, carbon dioxide (CO2) reduction, nitrogen (N2) fixation and the organic synthesis of clean chemicals are summarized. The perspectives and plausible opportunities for developing high performance BiOX/BixOyXz-g-C3N4 heterojunction photocatalysts are also discussed

Long‐Term Variability and Tendencies in Middle Atmosphere Temperature and Zonal Wind From WACCM6 Simulations During 1850–2014

Long‐term variability of middle atmosphere temperature (T) and zonal wind (U) is investigated using a three‐member ensemble of historical simulations of NCAR's Whole Atmospheric Community Climate Model latest version 6 (WACCM6) for 1850–2014 (165 years). The model reproduces the climatological features of T and U. The contributions of Quasi Biennial Oscillation (QBO) at 10 and 30 hPa, solar cycle (SC), El Niño‐Southern Oscillation (ENSO), ozone depleting substances (ODS), carbon dioxide (CO2), and stratospheric sulfate aerosol (volcanic eruptions) to change in monthly zonal mean T and U are analyzed using multiple linear regression. The signal due to CO2 increase dominates as a predictor of the net multidecadal global annual mean temperature change at all levels in the middle atmosphere. Contributions from ODS also affect the net multidecadal global mean temperature trend in the stratosphere. Because of similarities in the time evolution of the emissions of CO2 and ODS, the analysis of existing model output cannot accurately separate the attributions of cooling to these two dominant forcing processes. On shorter time scales, solar flux variations are the largest source of variability in the mesosphere while volcanic eruptions are the largest in the stratosphere. In the stratosphere and mesosphere, both QBO and ENSO can significantly impact zonal mean temperature and zonal‐mean zonal wind depending on latitudes, but their impact on the multidecadal global mean temperature trend is very small

Microwave assisted growth of stannous ferrite microcubes as electrodes for potentiometric nonenzymatic H2O2 sensor and supercapacitor applications

Electrochemical sensors and supercapacitors are two noteworthy applications of electrochemistry. Herein, we report the synthesis of SnFe2O4 microcubes and Fe2O3 nanorods through a facile microwave assisted technique which are employed in fabricating the electrodes for nonenzymatic hydrogen peroxide (H2O2) sensor and supercapacitor applications. SnFe2O4 microcubes exhibited an enhanced specific capacitance of 172Fg−1 at a scan rate of 5mVs−1 in comparison to Fe2O3 nanorods (70Fg−1). Furthermore, the H2O2 sensing performance of the fabricated SnFe2O4 electrodes through chronopotentiometry studies in 0.1M PBS solution (at pH 7) with a wide linear range revealed a good sensitivity of 2.7mVμM−1μg−1 with a lowest detection limit of 41nM at a signal-to-noise ratio of 3. These results indicate that SnFe2O4 microcubes are excellent materials for the cost effective design and development of efficient supercapacitors as well as nonenzymatic sensors

Long‐Term Variability and Tendencies in Migrating Diurnal Tide From WACCM6 Simulations During 1850–2014

Long‐term variability and tendencies in migrating diurnal tide (DW1) are investigated for the first time using a three‐member ensemble of historical simulations by NCAR's Whole Atmosphere Community Climate Model, latest Version 6 (WACCM6) for 1850–2014 (165 years). The model reproduces the climatological features of the tide in temperature (T), zonal wind (U), and meridional wind (V). The amplitudes peak in the upper mesosphere and lower thermosphere (above ~0.001 hPa) at the equator for T (~10 K) and over 20–30°N and S latitudes for U (~15 m/s) and V (~25 m/s). The contributions of solar cycle (SC), quasi biennial oscillation (QBO) at 10 and 30 hPa, El Niño–Southern Oscillation (ENSO), ozone depleting substances (ODS), carbon dioxide (CO2), and stratospheric sulfate aerosols (volcanic eruptions) to change in annual mean amplitudes are analyzed using multiple linear regression. The tidal amplitudes in three components show a long‐term increase in the upper stratosphere (0.95–10.7 hPa) and the upper mesosphere (0.0001–0.01 hPa), predominantly due to increasing CO2 with a smaller contribution from the trend in ENSO. Interestingly, the global mean tidal amplitude in T decreases sharply after 1950–1960 until 1995 and then increases in association with changes in ODSs. The seasonal differences in tidal responses to the above indices can be as large as the overall signals. All the responses are stronger in the upper mesosphere; however, there is also a pronounced negative response of temperature tide to ODSs over middle to high latitudes around the stratopause (~1 hPa) during all seasons

Biofunctionalized CdS Quantum Dots: A Case Study on Nanomaterial Toxicity in the Photocatalytic Wastewater Treatment Process

The toxic nature of inorganic nanostructured materials as photocatalysts is often not accounted for in traditional wastewater treatment reactions. Particularly, some inorganic nanomaterials employed as photocatalysts may release secondary pollutants in the form of ionic species that leach out due to photocorrosion. In this context, this work is a proof-of-concept study for exploring the environmental toxicity effect of extremely small-sized nanoparticles (2+) metal ions due to the poor photocorrosion stability of CdS is a matter of serious concern. Therefore, in this report, a cost-effective strategy is devised for biofunctionalizing the active surface of CdS QDs by employing tea leaf extract, which is expected to hinder photocorrosion and prevent the leaching of toxic Cd2+ ions. The coating of tea leaf moieties (chlorophyll and polyphenol) over the CdS QDs (referred to hereafter as G-CdS QDs) was confirmed through structural, morphological, and chemical analysis. Moreover, the enhanced visible-light absorption and emission intensity of G-CdS QDs in comparison to that of C-CdS QDs synthesized through a conventional chemical synthesis approach confirmed the presence of chlorophyll/polyphenol coating. Interestingly, the polyphenol/chlorophyll molecules formed a heterojunction with CdS QDs and enabled the G-CdS QDs to exhibit enhanced photocatalytic activity in the degradation of methylene blue dye molecules over C-CdS QDs while effectively preventing photocorrosion as confirmed from cyclic photodegradation studies. Furthermore, detailed toxicity studies were conducted by exposing zebrafish embryos to the as-synthesized CdS QDs for 72 h. Surprisingly, the survival rate of the zebrafish embryos exposed to G-CdS QDs was equal to that of the control, indicating a significant reduction in the leaching of Cd2+ ions from G-CdS QDs in comparison to C-CdS QDs. The chemical environment of C-CdS and G-CdS before and after the photocatalysis reaction was examined by X-ray photoelectron spectroscopy. These experimental findings prove that biocompatibility and toxicity could be controlled by simply adding tea leaf extract during the synthesis of nanostructured materials, and revisiting green synthesis techniques can be beneficial. Furthermore, repurposing the discarded tea leaves may not only facilitate the control of toxicity of inorganic nanostructured materials but can also help in enhancing global environmental sustainability

Multiuser Cognitive Radio Networks: An Information Theoretic Perspective

Achievable rate regions and outer bounds are derived for three-user interference channels where the transmitters cooperate in a unidirectional manner via a noncausal message-sharing mechanism. The three-user channel facilitates different ways of message-sharing between the primary and secondary (or cognitive) transmitters. Three natural extensions of unidirectional message-sharing from two users to three users are introduced: (i) Cumulative message sharing; (ii) primary-only message sharing; and (iii) cognitive-only message sharing. To emphasize the notion of interference management, channels are classified based on different rate-splitting strategies at the transmitters. Standard techniques, superposition coding and Gel'fand-Pinsker's binning principle, are employed to derive an achievable rate region for each of the cognitive interference channels. Simulation results for the Gaussian channel case are presented; they enable visual comparison of the achievable rate regions for different message-sharing schemes along with the outer bounds. These results also provide useful insights into the effect of rate-splitting at the transmitters, which aids in better interference management at the receivers.Comment: 50 pages, 15 figures, submitted to IEEE Transactions on Information Theor

Sequential screening for lung cancer in a high-risk group: randomised controlled trial: LungSEARCH: a randomised controlled trial of Surveillance using sputum and imaging for the EARly detection of lung Cancer in a High-risk group.

BACKGROUND: Low-dose computed tomography (LDCT) screening detects early-stage lung cancer and reduces mortality. We proposed a sequential approach targeted to a high-risk group as a potentially efficient screening strategy. METHODS: LungSEARCH was a national multicentre randomised trial. Current/ex-smokers with mild/moderate chronic obstructive pulmonary disease (COPD) were allocated (1:1) to have 5 years surveillance or not. Screened participants provided annual sputum samples for cytology and cytometry, and if abnormal were offered annual LDCT and autofluorescence bronchoscopy (AFB). Those with normal sputum provided annual samples. The primary end-point was the percentage of lung cancers diagnosed at stage I/II (nonsmall cell) or limited disease (small cell). RESULTS: 1568 participants were randomised during 2007-2011 from 10 UK centres. 85.2% of those screened provided an adequate baseline sputum sample. There were 42 lung cancers among 785 screened individuals and 36 lung cancers among 783 controls. 54.8% (23 out of 42) of screened individuals versus 45.2% (14 out of 31) of controls with known staging were diagnosed with early-stage disease (one-sided p=0.24). Relative risk was 1.21 (95% CI 0.75-1.95) or 0.82 (95% CI 0.52-1.31) for early-stage or advanced cancers, respectively. Overall sensitivity for sputum (in those randomised to surveillance) was low (40.5%) with a cumulative false-positive rate (FPR) of 32.8%. 55% of cancers had normal sputum results throughout. Among sputum-positive individuals who had AFB, sensitivity was 45.5% and cumulative FPR was 39.5%; the corresponding measures for those who had LDCT were 100% and 16.1%, respectively. CONCLUSIONS: Our sequential strategy, using sputum cytology/cytometry to select high-risk individuals for AFB and LDCT, did not lead to a clear stage shift and did not improve the efficiency of lung cancer screening

Facile Synthesis of Gram-Scale Mesoporous Ag/TiO₂ Photocatalysts for Pharmaceutical Water Pollutant Removal and Green Hydrogen Generation

This work demonstrates a two-step gram-scale synthesis of presynthesized silver (Ag) nanoparticles impregnated with mesoporous TiO2 and evaluates their feasibility for wastewater treatment and hydrogen gas generation under natural sunlight. Paracetamol was chosen as the model pharmaceutical pollutant for evaluating photocatalytic performance. A systematic material analysis (morphology, chemical environment, optical bandgap energy) of the Ag/TiO2 photocatalyst powder was carried out, and the influence of material properties on the performance is discussed in detail. The experimental results showed that the decoration of anatase TiO2 nanoparticles (size between 80 and 100 nm) with 5 nm Ag nanoparticles (1 wt %) induced visible-light absorption and enhanced charge carrier separation. As a result, 0.01 g/L Ag/TiO2 effectively removed 99% of 0.01 g/L paracetamol in 120 min and exhibited 60% higher photocatalytic removal than pristine TiO2. Alongside paracetamol degradation, Ag/TiO2 led to the generation of 1729 μmol H2 g–1 h–1. This proof-of-concept approach for tandem pollutant degradation and hydrogen generation was further evaluated with rare earth metal (lanthanum)- and nonmetal (nitrogen)-doped TiO2, which also showed a positive response. Using a combination of ab initio calculations and our new theory model, we revealed that the enhanced photocatalytic performance of Ag/TiO2 was due to the surface Fermi-level change of TiO2 and lowered surface reaction energy barrier for water pollutant oxidation. This work opens new opportunities for exploiting tandem photocatalytic routes beyond water splitting and understanding the simultaneous reactions in metal-doped metal oxide photocatalyst systems under natural sunlight

Software-Hardware Co-design for Fast and Scalable Training of Deep Learning Recommendation Models

Deep learning recommendation models (DLRMs) are used across many business-critical services at Facebook and are the single largest AI application in terms of infrastructure demand in its data-centers. In this paper we discuss the SW/HW co-designed solution for high-performance distributed training of large-scale DLRMs. We introduce a high-performance scalable software stack based on PyTorch and pair it with the new evolution of Zion platform, namely ZionEX. We demonstrate the capability to train very large DLRMs with up to 12 Trillion parameters and show that we can attain 40X speedup in terms of time to solution over previous systems. We achieve this by (i) designing the ZionEX platform with dedicated scale-out network, provisioned with high bandwidth, optimal topology and efficient transport (ii) implementing an optimized PyTorch-based training stack supporting both model and data parallelism (iii) developing sharding algorithms capable of hierarchical partitioning of the embedding tables along row, column dimensions and load balancing them across multiple workers; (iv) adding high-performance core operators while retaining flexibility to support optimizers with fully deterministic updates (v) leveraging reduced precision communications, multi-level memory hierarchy (HBM+DDR+SSD) and pipelining. Furthermore, we develop and briefly comment on distributed data ingestion and other supporting services that are required for the robust and efficient end-to-end training in production environments

Barrier-to-Autointegration Factor Proteome Reveals Chromatin-Regulatory Partners

Nuclear lamin filaments and associated proteins form a nucleoskeletal (“lamina”) network required for transcription, replication, chromatin organization and epigenetic regulation in metazoans. Lamina defects cause human disease (“laminopathies”) and are linked to aging. Barrier-to-autointegration factor (BAF) is a mobile and essential component of the nuclear lamina that binds directly to histones, lamins and LEM-domain proteins, including the inner nuclear membrane protein emerin, and has roles in chromatin structure, mitosis and gene regulation. To understand BAF's mechanisms of action, BAF associated proteins were affinity-purified from HeLa cell nuclear lysates using BAF-conjugated beads, and identified by tandem mass spectrometry or independently identified and quantified using the iTRAQ method. We recovered A- and B-type lamins and core histones, all known to bind BAF directly, plus four human transcription factors (Requiem, NonO, p15, LEDGF), disease-linked proteins (e.g., Huntingtin, Treacle) and several proteins and enzymes that regulate chromatin. Association with endogenous BAF was independently validated by co-immunoprecipitation from HeLa cells for seven candidates including Requiem, poly(ADP-ribose) polymerase 1 (PARP1), retinoblastoma binding protein 4 (RBBP4), damage-specific DNA binding protein 1 (DDB1) and DDB2. Interestingly, endogenous BAF and emerin each associated with DDB2 and CUL4A in a UV- and time-dependent manner, suggesting BAF and emerin have dynamic roles in genome integrity and might help couple DNA damage responses to the nuclear lamina network. We conclude this proteome is a rich source of candidate partners for BAF and potentially also A- and B-type lamins, which may reveal how chromatin regulation and genome integrity are linked to nuclear structure