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Many ensemble-based data assimilation (DA) methods use observation space localization to mitigate the sampling errors due to the insufficient ensemble members. Observation space localization is simpler and more timesaving than model space localization in implementation, but more difficult to directly assimilate satellite radiance observations, a kind of non-local observations. The vertical locations of radiance observations are undetermined and the transmission of observational information is thereby obstructed. To determine the vertical coordinates of radiance observations, a weighted average hypsometry is proposed. Using this hypsometry, AMSU-A radiance observations are directly assimilated with an ensemble four-dimensional variational (En4DVar) DA system. It consists of a four-dimensional ensemble-variational (4DEnVar) system providing ensemble covariance and a 4DVar system. Observing system simulation experiments show that the hypsometry alleviates the degradations in the late period of medium-range forecast in the Northern Extratropics that occur in the traditional peak-based hypsometry. It obviously improves the analysis qualities and forecast skills of the En4DVar system and its two components, especially in the Southern Extratropics, when incorporating AMSU-A radiance observations. The improvement in the En4DVar-initialized forecast is comparable to that in the 4DVar-initialized forecast in the Southern Extratropics and Tropics. It indicates that a proper hypsometry enables efficient extraction of useful information from AMSU-A radiance observations by 4DEnVar with observation space localization. Therefore, the 4DEnVar provides high-quality ensemble covariances for En4DVar.

Fluorescence anisotropy has been widely used in developing biosensors and immunoassays, by virtue of the self-reference and environment-sensitive properties. However, fluorescence anisotropic chemical sensors on inorganic ions are limited by the total anisotropy change. To this end, we demonstrate here fluorescence anisotropic ion-selective optodes based on the homo-FRET (Förster resonance energy transfer) of the crowded chromoionophores. The conventional fluorescence on-off mode is transformed into the anisotropic mode. Variation of the target ion concentration changes the inter-chromoionophore distance in the organic sensing phase, leading to different extents of homo-FRET and steady-state anisotropy. A theoretical model is developed by coupling homo-FRET and anisotropy. Anisotropic detections of pH, K

Ocean waves, especially extreme waves, are vital for air-sea interaction and shipping. However, current wave models still have significant biases, especially under extreme wind conditions. Based on a numerical wave model and a deep learning model, we accurately predict the significant wave height (SWH) of the Northwest Pacific Ocean. For each day in 2017-2021, we conducted a 3-day hindcast experiment using WAVEWATCH3 (WW3) to obtain the SWH forecasts at lead times of 24, 48, and 72hr, forced by GFS real-time forecast surface winds. The deep learning-based bias correction method is BU-Net by adding batch normalization layers to a U-Net, which could improve the accuracy. Due to the use of BU-Net, the mean Root Mean Squared Errors (RMSEs) of the SWH forecast from WW3 at lead times of 24, 48, and 72hr are reduced from 0.35m to 0.21m, 0.39m to 0.24m, and 0.43m to 0.30m, corresponding to drop percentages of 40%, 38%, and 30%, respectively. During typhoon passages, the drop percentages of RMSEs reach 45%, 42%, and 35% for three lead times. Therefore, combining numerical models and deep learning algorithms is very promising in ocean wave forecasting.

A new ocean-atmosphere-wave regional coupled model named Windwave version 1.0 for simulating and predicting winds and waves has been developed for the Northwest Pacific Ocean. In particular, the global-to-regional nesting technique is adopted for the ocean component to alleviate the bias due to the inconsistency in the lateral boundary. This paper is devoted to describing the coupling details of Windwave and the initialization scheme and assessing its basic performance, especially in predicting surface winds and significant wave heights (SWH) on the weather timescale. The control experiment set contains 31 experiments for August 2020, with seven typhoons passing through the Northwest Pacific. Each experiment starts at 0:00 am UTC of each day and runs for three days. Experiment results show that the new coupled model performs well in predicting surface winds, SWH, surface air temperature, and sea surface temperature on the weather timescale. In particular, the Root Mean Square Errors (RMSEs) of surface winds at 10 m height over the Northwest Pacific of the control experiment are 1.82 m s-1, 2.22 m s-1, and 2.59 m s-1, respectively, at lead times of 24 h, 48 h, and 72 h. Meanwhile, the RMSEs of SWH at lead times of 24 h, 48 h, and 72 h are 0.39 m, 0.43 m, and 0.51 m. In addition, we have explored the impacts of the different sea surface aerodynamic roughness parameterization schemes on predicting surface winds and SWH. In total, five different sea surface aerodynamic roughness parameterization schemes are adopted, corresponding to one control set and four sensitivity sets of experiments. Under normal conditions, the sea surface aerodynamic roughness parameterization scheme considering the effects of wind-wave direction tends to perform better for winds and waves, while that depending on wave age and SWH tends to perform worse. Under extreme wind and wave conditions, the schemes considering the effects of wind-wave direction and that considering wave age and peak wave length have better performance. These findings can provide new insights for developing a more advanced sea surface aerodynamic roughness parameterization scheme.

Supported noble metals offer key advantages over homogeneous catalysts for in vivo applications of parahydrogen-based hyperpolarization. However, their performance is compromised by randomization of parahydrogen spin order resulting from rapid hydrogen adatom diffusion. The diffusion on Pt surfaces can be suppressed by introduction of Sn to form Pt-Sn intermetallic phases. Herein, an unprecedented pairwise selectivity of 19.7 ± 1.1% in the heterogeneous hydrogenation of propyne using silica encapsulated Pt-Sn intermetallic nanoparticles is reported. This high level of selectivity exceeds that of all supported metal catalysts by at least a factor of 3. Moreover, the pairwise selectivity for alkyne hydrogenation is about 2 times higher than for alkene hydrogenation, an observation attributed to the higher coverage of the former and its effect on diffusion. Lastly, PtSn@mSiO

The land surface is a potential source of climate predictability over the Northern Hemisphere midlatitudes but has received less attention than sea surface temperature in this regard. This study quantified the degree to which realistic land initialization contributes to interannual climate predictability over Europe based on a coupled climate system model named FGOALS-g2. The potential predictability provided by the initialization, which incorporates the soil moisture and soil temperature of a land surface reanalysis product into the coupled model with a dimension-reduced projection four-dimensional variational data assimilation (DRP-4DVar)-based weakly coupled data assimilation (WCDA) system, was analyzed first. The effective predictability (i.e., prediction skill) of the hindcasts by FGOALS-g2 with realistic and well-balanced initial conditions from the initialization were then evaluated. Results show an enhanced interannual prediction skill for summer surface air temperature and precipitation in the hindcast over Europe, demonstrating the potential benefit from realistic land initialization. This study highlights the significant contributions of land surface to interannual predictability of summer climate over Europe.

A unique electrocatalytic oxidative dehydrogenation of aldehydes and its facile kinetics on a Cu-based porous electrode enables an ultra-low voltage bipolar H2 production system with industrial-relevant current densities.

ConspectusIntermetallic nanoparticles (iNPs) have been the subject of many recent reports for their demonstrated applications as highly active and selective heterogeneous catalysts. As a subclass o...

In this work, the mechanical lap joint of commercial ReBCO tape from SHSC is prepared. The tape is reinforced with stainless steel bar in both side to reduce the effect of bending moment in the joint tensile test. We use Indium and GaInSn as interlayer material, respectively, and different pressures are applied on the joint by jig during testing. The relationship between joint resistance and applied tensile stress was measured at 77 K. The results shows that for all measured joints under pressure, the voltage rise duo to tensile stress is small at first and then sharply grows until a certain value of stress is reached. The maximum tensile stress is higher for the joint which has lower resistance. Comparing two types of mechanical lap joints with Indium and GaInSn, the former joint shows smaller dispersion on joint resistance than the latter under pressure above 40 Mpa. It is also shown that the joint with Indium can tolerate higher tensile stress than the joint with GaInSn by using the Weibull distribution function analysis.

Achieving kinetic control to synthesize metastable compounds is a challenging task, especially in solid-state reactions where the diffusion is slow. Another challenge is the unambiguous crystal structure determination for metastable compounds when high-quality single crystals suitable for single-crystal X-ray diffraction are inaccessible. In this work, we report an unconventional means of synthesis and an effective strategy to solve the crystal structure of an unprecedented metastable compound LiNi

Applying metal-organic frameworks (MOFs) on the surface of other materials to form multifunctional materials has recently attracted great attention; however, directing the MOF overgrowth is challenging due to the orders of magnitude differences in structural dimensions. In this work, we developed a universal strategy to mediate MOF growth on the surface of metal nanoparticles (NPs), by taking advantage of the dynamic nature of weakly adsorbed capping agents. During this colloidal process, the capping agents gradually dissociate from the metal surface, replaced

The pursuit of two-dimensional (2D) borides, MBenes, has proven to be challenging, not the least because of the lack of a suitable precursor prone to the deintercalation. Here, we studied room-temperature topochemical deintercalation of lithium from the layered polymorphs of the LiNiB compound with a considerable amount of Li stored in between [NiB] layers (33 at. % Li). Deintercalation of Li leads to novel metastable borides (Li similar to 0.5NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HCl under ambient conditions. Scanning transmission electron microscopy and solid-state Li-7 and B-1(1) NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of (Li similar to 0.5NiB) and the mechanism of Li-deintercalation. We have shown that the deintercalation of Li proceeds via a "zip-lock" mechanism, leading to the condensation of single [NiB] layers into double or triple layers bound via covalent bonds, resulting in structural fragments with Li[NiB](2) and Li[NiB](3) compositions. The crystal structure of Li similar to 0.5NiB is best described as an intergrowth of the ordered single [NiB], double [NiB](2), or triple [NiB](3) layers alternating with single Li layers; this explains its structural complexity. The formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperature-independent paramagnets in the parent LiNiB compounds to the spin-glassiness in the deintercalated Li similar to 0.5NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).

Prolactin levels are increased in chronic kidney disease (CKD) as a result of reduced clearance and increased secretion. Hyperprolactinemia manifests as galactorrhea and hypogonadism. Treatment of hyperprolactinemia should focus on improving bothersome galactorrhea or hypogonadism by using dopamine agonists and/or replacement of sex hormone(s). Changes in the hypothalamic-pituitary-adrenal axis in CKD are characterized by increases in adrenocorticotropic hormone (ACTH) and cortisol levels, largely preserved circadian rhythms of ACTH and cortisol, and a normal response of cortisol to ACTH, metyrapone, and insulin-induced hypoglycemia. However, the hypothalamic-pituitary-adrenal axis is less inhibited by 1 mg dexamethasone but retains normal suppression by higher-dose dexamethasone. Diagnosis of adrenal insufficiency in CKD patients, as in normal subjects, usually is made by finding a subnormal cortisol response to ACTH. The mainstay of treatment of adrenal insufficiency is to replace glucocorticoid hormone. Cushing's disease in CKD is difficult to diagnose and relies on the dexamethasone suppression test and the midnight salivary cortisol test because the 24-hour urine free cortisol test is not useful because it is increased already in CKD. Treatment of Cushing's disease involves surgery, complemented by radiation and/or medical therapy if necessary. Growth hormone levels are increased and insulin-like growth factor 1 levels are normal in patients with CKD. In a normal patient with CKD, as in one with acromegaly, there can be a paradoxic increase in growth hormone after an oral glucose load. Therefore, diagnosis of acromegaly in renal insufficiency is challenging. The treatment of choice for acromegaly is surgery, although data for medical treatment for acromegaly in CKD are rare. In patients with renal impairment, arginine vasopressin levels are increased as a result of decreased clearance, and there also is impairment of arginine vasopressin signaling in renal tubules. Diabetes insipidus can be masked in advanced kidney disease until kidney transplantation. Diagnosis of the syndrome of inappropriate antidiuretic hormone is similar in mild or moderate kidney disease as in normal subjects, but is challenging in patients with advanced kidney disease owing to the impairment in urine dilution.

The European Space Agency Climate Change Initiative Land Cover data (ESA CCI-LC, from 1992 to 2015) is introduced to the National Center for Atmospheric Research Community Earth System Model version 1.2.1 (NCAR CESM1.2.1). In comparison with the original land surface data in the Community Land Model version 4 (ORG), the new data features notable land use and land cover change (LULCC) with increased forests over northeastern Asia and Alaska by decreasing shrublands and grasslands. Overestimated bare land cover over the Tibetan Plateau (TP) and the Rocky Mountains in the ORG are corrected with the replacements by grasslands and shrublands respectively in the new data. The model simulation results show that with the introduction of the ESA CCI-LC, the simulated surface albedo, surface net radiation flux, sensible and latent heat fluxes are relatively improved over the regions where significant LULCC exists, such as northeastern Asia, Alaska, the TP, and Australia. Surface air temperature, precipitation, and atmospheric circulation are improved in boreal winter but degraded in summer. The winter warming over northeastern Asia results from increased longwave downwelling flux and adiabatic heating while the notable winter cooling over Alaska is attributed to strong cold advection followed by reduced longwave downwelling flux. LULCC alters precipitation by influencing water vapor content. In winter, LULCC affects atmospheric circulation via modulating baroclinicity while in summer, it influences land-sea thermal contrast, thus affecting the intensity of East Asian summer monsoon. LULCC also alters the simulated dust burden.

Optical control of exotic properties in strongly correlated electron materials is very attractive owing to their potential applications in optical and electronic devices. Herein, we demonstrate a vertical heterojunction made of a correlated electron oxide thin film VO2 and a conductive 0.05 wt% Nb-doped TiO2 single crystal, whose metal-insulator transition (MIT) across the nanoscale heterointerface can be efficiently modulated by visible light irradiation. The magnitude of the MIT decreases from ~350 in the dark state to ~7 in the illuminated state, obeying a power law with respect to the light power density. The junction resistance is switched in a reversible and synchronous manner by turning light on and off. The optical tunability of it is also exponentially proportional to the light power density, and a 320-fold on/off ratio is achieved with an irradiance of 65.6 mW cm−2 below the MIT temperature. While the VO2 thin film is metallic above the MIT temperature, the optical tunability is remarkably weakened, with a one-fold change remaining under light illumination. These results are co-attributed to a net reduction (~15 meV) in the apparent barrier height and the photo-carrier-injection-induced metallization of the VO2 heterointerface through a photovoltaic effect, which is induced by deep defect level transition upon the visible light irradiance at low temperature. Additionally, the optical tunability is minimal, resulting from the quite weak modulation of the already metallic band structure in the Schottky-type junction above the MIT temperature. This work enables a remotely optical scheme to manipulate the MIT, implying potential uncooled photodetection and photoswitch applications.

Encapsulating metal nanoparticles (NPs) in metal–organic frameworks (MOFs) to control catalytic selectivity has recently attracted great attention; however, an understanding of the NP–MOF interface...

Tibetan Plateau (TP) summer precipitation, whose first leading mode presents a dipole oscillation between the northeastern and southeastern TP, plays important roles in the water cycle and atmospheric circulation. Using a weakly coupled data assimilation (WCDA) system to constrain the atmospheric component in a coupled model with a global atmospheric reanalysis product, this study demonstrates significant improvements in predicting the interannual variation of summer precipitation over the eastern TP, capturing the strong reversal mode between the northeastern and southeastern TP. These improvements are mainly attributed to the strong air–sea coupling over the North Atlantic (NA) and its remote impacts on the TP precipitation. This coupling allows observation-constrained atmosphere to significantly influence initial conditions (ICs) of sea surface temperature (SST) in the NA area and then obviously affect predictions of both NA SST and summer North Atlantic Oscillation (SNAO), which affects the downstream TP atmospheric circulation through the wave train of Eliassen-Palm (EP) stationary wave flux. This study highlights the importance of NA air–sea coupling in the interannual predictability of TP precipitation and suggests a new source of interannual predictability of TP precipitation.

This review covers recent progress in using single molecule fluorescence microscopy imaging to understand the nanoconfinement in porous materials. The single molecule approach unveils the static and dynamic heterogeneities from seemingly equal molecules by removing the ensemble averaging effect. Physicochemical processes including mass transport, surface adsorption/desorption, and chemical conversions within the confined space inside porous materials have been studied at nanometer spatial resolution, at the single nanopore level, with millisecond temporal resolution, and under real chemical reaction conditions. Understanding these physicochemical processes provides the ability to quantitatively measure the inhomogeneities of nanoconfinement effects from the confining properties, including morphologies, spatial arrangement, and trapping domains. Prospects and limitations of current single molecule imaging studies on nanoconfinement are also discussed.

The study of the reaction mechanism and complex network for heterogeneously catalyzed tandem reactions is challenging but can guide reaction design and optimization. Here, we describe a case study using bifunctional metal–organic framework supported Pd nanoparticles (Pd/UiO-66(HCl)) for the one-pot tandem synthesis of substituted tetrahydroquinolines via the Claisen–Schmidt condensation and reductive intramolecular cyclization. The directly observed evolution of intermediates and products, including reactive species containing hydroxylamine group and unstable intermediate 2-phenyl-3,4-dihydroquinoline, was enabled by operando magic angle spinning nuclear magnetic resonance studies under 50 bar H2. The reaction network of the tandem reaction is deduced based on reaction kinetic information obtained from the operando study. The optimized procedure was applied to various acetophenone and nitrobenzaldehyde derivatives carrying different functional groups, and eight valuable substituted tetrahydroquinolines were obtained in moderate to good yields. This work provides a molecular-level understanding of the catalytic system and brings up new opportunities for efficient and sustainable synthesis of medicinally relevant building blocks.

Objective: To establish suggested gestational weight gain (GWG) using several distinct methods in a Chinese population. Methods: This study analyzed data from the medical records of singleton pregnancy women during 2011–2017 in Beijing, China. Suggested GWG was calculated using four distinct methods. In method 1, suggested GWG was identified by the interquartile method. Subsequently, risk models for small for gestational age (SGA) and large for gestational age (LGA) with respect to GWG were constructed. GWG was treated as a continuous variable in method 2, and as a categorized variable in methods 3 and 4. Results: An average GWG of 15.78 kg with a prevalence of LGA at 19.34% and SGA at 2.12% was observed among the 34,470 participants. Methods 1 and 2 did not yield clinically applicable results. The suggested GWGs were 11–17/11–16 kg, 9–19/9–15 kg, 4–12/4–10 kg, and 0–12/0–6 kg by method 3/method 4 for underweight, normal-weight, overweight, and obese women, respectively. The GWG range suggested by method 3 resulted in a larger proportion of participants (62.03%) within range, while the suggested GWG range by method 4 was associated with a lower risk of LGA compared to that conferred by the Institute of Medicine (IOM) criteria. Conclusion: This study suggests a modest GWG goal compared to IOM recommendations based on a large Chinese cohort.

Harmful algae blooms represent a serious problem for natural waters around the world, and have a great impact on water quality, local economies and human health. To tackle the above challenge, we successfully prepare fluorine-doped titanium oxide (F-TiO2) nanocomposites by a hydrothermal method as a photocatalytic algaecide. The synthesized nanocomposites were characterized by SEM (scanning electron microscope), EDS (energy dispersive spectrometer), XPS (X-ray photoelectron spectroscopy), XRD (X-ray diffraction), and EPR (electron paramagnetic resonance). The results of this study indicated that the crystallinity of anatase in F-TiO2 is enhanced significantly upon fluorine doping. F-TiO2 with a dosage of 0.75 g L−1 exhibited the best anti-algae activity, and the removal rate of algae cells is above 97.5% under solar irradiation for 8 h. When the potential of hydrogen (pH) value was 10.0, F-TiO2 had a good treatment effect. When the pH value was lower than 6.25, it was beneficial to the decline of the chlorophyll a content. The inactivation process of F-TiO2 inhibiting Microcystis aeruginosa fits well with the improved Chick–Waston model and Hom model. During the photocatalytic destruction, fluorine-doped TiO2 oxidized the algae cell walls and membranes, simultaneously degrading the metabolic products and microcystin-LR with high efficiency. The reactive oxygen species contribution of the F-TiO2 photocatalyst in the process of photocatalytic algae removal is h+ > ˙OH > ˙O2−. Compared with traditional algae removal methods, photocatalytic algaecides can rapidly prevent secondary pollution while improving efficiency, and using solar light as an energy source is more suitable for in situ remediation of natural water bodies.

The mechanism of the deactivation and regeneration of PtSn intermetallic compound nanoparticle (iNP) catalysts was studied by in situ TEM investigation. Our study reveals the reversible dynamic structural transition of the iNPs during deactivation and regeneration, which provides a direct correlation between the atomic structure and the catalytic activity of the iNPs.

Background Osilodrostat, a potent cortisol synthesis inhibitor, demonstrated safety and efficacy in the treatment of Cushing's disease (CD). No information is available describing use of osilodrostat in non-pituitary Cushing's syndrome (CS) in US patients. Data from a real-world study in US patients with non-pituitary CS is presented. Methods The ILLUSTRATE study is a real-world characterization of osilodrostat usage in patients with endogenous CS treated May 1, 2020 - October 29, 2021. Forty-two adult patients with a confirmed diagnosis of endogenous CS and a prescription for osilodrostat were included in this real-world study. We report patient characteristics, osilodrostat dose, efficacy, and safety in the subset of patients with non-pituitary CS (n=8,19%). Results The 8 non-pituitary CS patients enrolled comprised 5 with adrenal CS and 3 with ectopic CS. Baseline urinary free cortisol (UFC) was 2.57–75.2×ULN in patients with ectopic CS, and 0.42–27.76×ULN in the 4 adrenal patients with baseline UFC available. In the adrenal CS patients, starting dose ranged from 1–4 mg daily. In adrenal patients with more than one documented clinical encounter (n=4): 2 remained on starting doses of 1 mg BID and 2 mg BID, 1 increased from 1 mg QD to 2 mg BID on day (D) 50, and 1 increased from 2 mg BID to 4 mg BID on D5 and required down-titration on D18 with treatment interruption on D27. The 3 patients with ectopic CS were all initiated at 2 mg BID: 1 patient's dose was unchanged throughout the observation period, and the other 2 patients were up-titrated, both on D91 to 4 mg BID or 5 mg QD. The two ectopic CS patients with available UFC data experienced substantial UFC | reductions (from 57.1×ULN to 2.9×ULN at D91 and 75.2×ULN to 0. 076×ULN at D134). The one adrenal CS patient with available UFC data and prior medical therapy for CS maintained UFC ≤ ULN during osilodrostat treatment. Osilodrostat was generally well tolerated and one ectopic CS patient had treatment interrupted on D214 for adrenal insufficiency (AI). Two of five adrenal CS patients (40%) had symptoms suggestive of glucocorticoid withdrawal (e. g., fatigue, nausea, and headache) and one had an interruption in therapy. Neither had documented AI. Conclusion In this real-world cohort of patients treated with osilodrostat for non-pituitary CS, large UFC reductions were seen in two patients with ectopic CS. All 8 were initiated on ≤2 mg BID, with 3 (38%) remaining on their original dose. In the majority of those up-titrated, there was an extended titration interval. The observed safety profile in this subset (albeit small) of non-pituitary CS patients was consistent with the known osilodrostat safety profile. Presentation: Monday, June 13, 2022 12:30 p.m. - 2:30 p.m.

Due to their high gyromagnetic ratio, there is considerable interest in measuring distances and correlations involving protons, but such measurements are compounded by the simultaneous recoupling of chemical shift anisotropy (CSA). This secondary recoupling adds additional modulations to the signal intensities that ultimately lead to t