Synergistic Enhancement of CO2 photoreduction through sulfur defects in (3D/2D) CdS-nanoflowers/CN Binary heterojunction photocatalyst under visible light.

Global warming is the biggest threat to the entire world owing to the continuous release of greenhouse gases such as CO2 from various sources. Herein, we have utilized renewable energy for the conversion of CO2 to valuable feedstocks through a semiconductor-mediated photocatalytic system. The cadmium sulfide nanoflowers (CS-NFs) decorated graphitic carbon nitride (CN) through a solvothermal route to form a Z-scheme CSCN heterojunction. The as-synthesized material has been characterized by various spectroscopic and microscopic tools. The optimal CSCN-0.5 (1:0.5) photocatalyst achieves a CO production rate of 130.9 µmol g-1 under visible light irradiation of 4h (λ > 420 nm), doubling that of pristine CS-NFs and CN. CO, along with CH4 (3.4 µmol g-1) and C2H6 (2.9 µmol g-1), is the sole product detected. Experimental results indicate that the CSCN-0.5 photocatalyst spatially separates electron-hole pairs, suppresses charge carrier recombination, and maintains robust redox ability, enhancing CO2 photoreduction. The CO2 reduction mechanism over CSCN heterojunction was also studied through in-situ DRIFTS and electron spin resonance (ESR) measurements. Therefore, CSCN proves that it could be used as a robust photocatalyst for the CO2 reduction reactions towards C1 and C2 feedstocks.

Mass Balance, Metabolic Pathways, Absolute Bioavailability, and Pharmacokinetics of Giredestrant in Healthy Subjects.

Giredestrant is a potent and selective small-molecule estrogen receptor degrader. The objectives of this study were to assess the absolute bioavailability (aBA) of giredestrant and to determine the mass balance, routes of elimination, and metabolite profile of [14C]giredestrant. In part 1 (mass balance), a single 30.8-mg oral dose of [14C]giredestrant (105 µCi) was administered to women of nonchildbearing potential (WNCBP; n = 6). The mean recovery of total radioactivity in excreta was 77.0%, with 68.0% of the dose excreted in feces and 9.04% excreted in urine over a 42-day sample collection period. The majority of the circulating radioactivity (56.8%) in plasma was associated with giredestrant. Giredestrant was extensively metabolized, with giredestrant representing only 20.0% and 1.90% of the dose in feces and urine, respectively. All metabolites in feces resulted from oxidative metabolism and represented 44.7% of the dose. In part 2 (aBA), WNCBP (n = 10) received an oral (30-mg capsule) or intravenous (30-mg solution) dose of giredestrant. The aBA of giredestrant after oral administration was 58.7%. Following the intravenous dose, giredestrant had a plasma clearance and volume of distribution of 5.31 L/h and 266 L, respectively. In summary, giredestrant was well tolerated, rapidly absorbed, and showed moderate oral bioavailability with low recovery of the dose as parent drug in excreta. Oxidative metabolism followed by excretion in feces was identified as the major route of elimination of giredestrant. SIGNIFICANCE STATEMENT: This study provides definitive insight into the absorption, distribution, metabolism, and excretion of giredestrant in humans. The results show that giredestrant exhibits low clearance, a high volume of distribution, and moderate oral bioavailability in humans. In addition, the data show that oxidative metabolism followed by excretion in feces is the primary elimination route of giredestrant in humans. These results will be used to further inform the clinical development of giredestrant.

Electronic Structure of Mg-, Si-, and Zn-Doped SnO2 Nanowires: Predictions from First Principles.

We investigated the electronic structure of Mg-, Si-, and Zn-doped four-faceted [001]- and [110]-oriented SnO2 nanowires using first-principles calculations based on the linear combination of atomic orbitals (LCAO) method. This approach, employing atomic-centered Gaussian-type functions as a basis set, was combined with hybrid density functional theory (DFT). Our results show qualitative agreement in predicting the formation of stable point defects due to atom substitutions on the surface of the SnO2 nanowire. Doping induces substantial atomic relaxation in the nanowires, changes in the covalency of the dopant-oxygen bond, and additional charge redistribution between the dopant and nanowire. Furthermore, our calculations reveal a narrowing of the band gap resulting from the emergence of midgap states induced by the incorporated defects. This study provides insights into the altered electronic properties caused by Mg, Si, and Zn doping, contributing to the further design of SnO2 nanowires for advanced electronic, optoelectronic, photovoltaic, and photocatalytic applications.

Fluorinated photoreduced graphene oxide with semi-ionic C-F bonds: An effective carbon based photocatalyst for the removal of volatile organic compounds.

There is much interest in developing metal-free halogenated graphene such as fluorinated graphene for various catalytic applications. In this work, a fluorine-doped graphene oxide photocatalyst was investigated for photocatalytic oxidation (PCO) of a volatile organic compound (VOC), namely gaseous methanol. The fluorination process of graphene oxide (GO) was carried out via a novel and facile solution-based photoirradiation method. The fluorine atoms were doped on the surface of the GO in a semi-ionic C-F bond configuration. This presence of the semi-ionic C-F bonds induced a dramatic 7-fold increment of the hole charge carrier density of the photocatalyst. The fluorinated GO photocatalyst exhibited excellent photodegradation up to 93.5% or 0.493 h-1 according pseudo-first order kinetics for methanol. In addition, 91.7% of methanol was mineralized into harmless carbon dioxide (CO2) under UV-A irradiation. Furthermore, the photocatalyst demonstrated good stability in five cycles of methanol PCO. Besides methanol, other VOCs such as acetone and formaldehyde were also photodegraded. This work reveals the potential of fluorination in producing effective graphene-based photocatalyst for VOC removal.

RadImageNet: An Open Radiologic Deep Learning Research Dataset for Effective Transfer Learning.

Purpose: To demonstrate the value of pretraining with millions of radiologic images compared with ImageNet photographic images on downstream medical applications when using transfer learning. Materials and Methods: This retrospective study included patients who underwent a radiologic study between 2005 and 2020 at an outpatient imaging facility. Key images and associated labels from the studies were retrospectively extracted from the original study interpretation. These images were used for RadImageNet model training with random weight initiation. The RadImageNet models were compared with ImageNet models using the area under the receiver operating characteristic curve (AUC) for eight classification tasks and using Dice scores for two segmentation problems. Results: The RadImageNet database consists of 1.35 million annotated medical images in 131 872 patients who underwent CT, MRI, and US for musculoskeletal, neurologic, oncologic, gastrointestinal, endocrine, abdominal, and pulmonary pathologic conditions. For transfer learning tasks on small datasets-thyroid nodules (US), breast masses (US), anterior cruciate ligament injuries (MRI), and meniscal tears (MRI)-the RadImageNet models demonstrated a significant advantage (P < .001) to ImageNet models (9.4%, 4.0%, 4.8%, and 4.5% AUC improvements, respectively). For larger datasets-pneumonia (chest radiography), COVID-19 (CT), SARS-CoV-2 (CT), and intracranial hemorrhage (CT)-the RadImageNet models also illustrated improved AUC (P < .001) by 1.9%, 6.1%, 1.7%, and 0.9%, respectively. Additionally, lesion localizations of the RadImageNet models were improved by 64.6% and 16.4% on thyroid and breast US datasets, respectively. Conclusion: RadImageNet pretrained models demonstrated better interpretability compared with ImageNet models, especially for smaller radiologic datasets.Keywords: CT, MR Imaging, US, Head/Neck, Thorax, Brain/Brain Stem, Evidence-based Medicine, Computer Applications-General (Informatics) Supplemental material is available for this article. Published under a CC BY 4.0 license.See also the commentary by Cadrin-Chênevert in this issue.

Crystallinity and lattice vacancies of different mesoporous g-C3N4 for photodegradation of tetracycline and its cytotoxic implication.

Tetracycline (TC) antibiotic removal from water bodies is important to provide clean water and sanitation. Mesoporous graphitic carbon nitride (GCN) photocatalyst derived from three different types of precursors manages to remove TC effectively under visible light irradiation. Among urea, thiourea, and melamine precursors, melamine-prepared GCN (MGCN) via thermal polymerization has the highest efficiency to photodegrade tetracycline (TC) antibiotics up to 99.5% (0.0122 min-1) within 240 min. The COD for TC removal by using MGCN was up to 77.5% after 240 min of degradation. This is due to the slow charge recombination and rapid charge carrier migration. The MGCN encounters different properties such as high crystallinity, dense structure allowing fast charges migration, and nitrogen vacancies that create a defect state that suppresses charge recombination. It was found that the conduction band (CB) of MGCN was located at a more negative position (ECB = -0.33 V) than (O2/O2•-) and the valence band (VB) was placed at a more positive position (EVB = 2.30 V) than (H2O/OH•), which allows generation of both radicals for photodegradation. Based on the cell viability test, the photodegraded TC in the water how non-toxicity toward Balb/c 3T3 cells after being irradiated (λ > 420 nm) for 240 min under visible light. The MGCN prepared in this study demonstrated the highest effectiveness and recyclable photocatalyst for the removal of TC among all GCNs.

All clinical stressors are not created equal: Differential task stress in a simulated clinical environment.

Background: A variety of stressors are encountered while working in the emergency department and are often recreated in simulation-based medical education. We seek to examine the physiologic and stress state response of participants in a simulated clinical environment to commonly encountered stressors. Methods: Emergency medicine (EM) residents participated in a randomized, controlled trial of six simulated patient encounters with one of three stressors, medical difficulty, interpersonal challenge, and technology/equipment failure, randomized into each scenario. Participants wore smart shirts to measure heart rate variability (HRV) at rest and just after the introduced stressor and completed the Short Stress State Questionnaire (SSSQ) before and after each scenario. Results: Twenty-seven EM residents participated in the study. Interpersonal challenge resulted in increased distress as measured by SSSQ compared to the other two stressors (one way ANOVA, F[2,144] = 9.95, p < 0.001). There was no difference in worry or task engagement across stressors. HRV decreased significantly from rest for all stressors (p = 0.0003, p = 0.0112, p = 0.0027 for medical difficulty, interpersonal challenge, and equipment failure, respectively), but there was no statistically significant difference between mean change in HRV across stressors (one way ANOVA, F[2,120] = 0.17, p = 0.8452). Conclusions: Interpersonal challenge stressor was significantly associated with an increase in distress in EM residents during the simulated encounters as compared to the other stressors. While heart rate variability decreased from rest for each stressor as expected following stressor introduction, differing stressors did not produce a differential change.

Exposure to polystyrene microplastics impairs hippocampus-dependent learning and memory in mice.

Microplastics (MPs) pollution has become a serious environmental issue worldwide, but its potential effects on health remain unknown. The administration of polystyrene MPs (PS-MPs) to mice for eight weeks impaired learning and memory behavior. PS-MPs were detected in the brain especially in the hippocampus of these mice. Concurrently, the hippocampus had decreased levels of immediate-early genes, aberrantly enhanced synaptic glutamate AMPA receptors, and elevated neuroinflammation, all of which are critical for synaptic plasticity and memory. Interestingly, ablation of the vagus nerve, a modulator of the gut-brain axis, improved the memory function of PS-MPs mice. These results indicate that exposure to PS-MPs in mice alters the expression of neuronal activity-dependent genes and synaptic proteins, and increases neuroinflammation in the hippocampus, subsequently causing behavioral changes through the vagus nerve-dependent pathway. Our findings shed light on the adverse impacts of PS-MPs on the brain and hippocampal learning and memory.

Highly Efficient Photothermal Reduction of CO2 on Pd2Cu Dispersed TiO2 Photocatalyst and Operando DRIFT Spectroscopic Analysis of Reactive Intermediates.

The photocatalytic conversion of CO2 to fuels using solar energy presents meaningful potential in the mitigation of global warming, solar energy conversion, and fuel production. Photothermal catalysis is one promising approach to convert chemically inert CO2 into value-added chemicals. Herein, we report the selective hydrogenation of CO2 to ethanol by Pd2Cu alloy dispersed TiO2 (P25) photocatalyst. Under UV-Vis irradiation, the Pd2Cu/P25 showed an efficient CO2 reduction photothermally at 150 °C with an ethanol production rate of 4.1 mmol g-1 h-1. Operando diffuse reflectance infrared Fourier transform (DRIFT) absorption studies were used to trace the reactive intermediates involved in CO2 hydrogenation in detail. Overall, the Cu provides the active sites for CO2 adsorption and Pd involves the oxidation of H2 molecule generated from P25 and C-C bond formation.

Ultrasensitive SERS detection of Rhodamine 6G using a silver enriched MOF-derived CuFe2O4 microcubes substrate.

Recently, spinel ferrites have attracted great attention as a SERS-active substrate for the detection of organic contaminants. In this paper, we report the synthesis of silver enriched MOF-derived CuFe2O4 (Ag-CFO) composite using a simple MOF template process. The as-synthesized Ag-CFO exhibits an excellent sensitivity towards the detection of Rhodamine 6G dye at the lowest concentration of 10-14 M. Using noble metal nanoparticles in conjunction with CuFe2O4 provides an excellent SERS performance based on the synergistic effect resulting from uniform Ag distribution on the cubic morphology leading to the high electromagnetic effect and chemical mechanism of CuFe2O4. Ag-CFO microcubes also demonstrated remarkable recyclability, reproducibility, and chemical stability. Moreover, the substrate showed good sensitivity when it was examined in tap and river water for practical applications. The results confirm that Ag-CFO microcubes substrate has great potential as a reusable material for the rapid detection of environmental pollutants.

Silver enriched silver phosphate microcubes as an efficient recyclable SERS substrate for the detection of heavy metal ions.

A rapid, cost-effective and accurate detection of heavy metal ions is crucial for human health monitoring and environmental protection. Surface-enhanced Raman spectroscopy (SERS) has become a reliable method due to its outstanding performance for the identification of contaminants. In this paper, silver phosphate microcubes (Ag3PO4) were fabricated using two different precipitation methods for ultrasensitive SERS detection of heavy metal ions. The use of an organic linker (BPy) with Ag3PO4 enabled the immobilization of Hg2+ and Pb2+ ions. The formation of Ag3PO4 was confirmed by XRD, UV-DRS, FESEM coupled with EDX and HRTEM. The analytical enhancement factor (AEF) obtained was 1010 with a detection limit of 10-15 M indicating high sensitivity. Based on these results, the possible SERS mechanism has been proposed and discussed. Moreover, an excellent reusability of Ag3PO4 substrate for at least four cycles was achieved upon the light exposure on heavy metal loaded substrate due to its superior catalytic ability for the degradation of heavy metal ions. The as-prepared substrate demonstrated remarkable stability, selectivity and SERS sensitivity towards real samples. The results conclude that Ag3PO4 microcubes offer a great prospect in recyclable SERS applications.

Rehardening and the Protective Effect of Gamma-Polyglutamic Acid/Nano-Hydroxyapatite Paste on Surface-Etched Enamel.

Many revolutionary approaches are on the way pertaining to the high occurrence of tooth decay, which is an enduring challenge in the field of preventive dentistry. However, an ideal dental care material has yet to be fully developed. With this aim, this research reports a dramatic enhancement in the rehardening potential of surface-etched enamels through a plausible synergistic effect of the novel combination of γ-polyglutamic acid (γ-PGA) and nano-hydroxyapatite (nano-HAp) paste, within the limitations of the study. The percentage of recovery of the surface microhardness (SMHR%) and the surface parameters for 9 wt% γ-PGA/nano-HAp paste on acid-etched enamel were investigated with a Vickers microhardness tester and an atomic force microscope, respectively. This in vitro study demonstrates that γ-PGA/nano-HAp treatment could increase the SMHR% of etched enamel to 39.59 ± 6.69% in 30 min. To test the hypothesis of the rehardening mechanism and the preventive effect of the γ-PGA/nano-HAp paste, the surface parameters of mean peak spacing (Rsm) and mean arithmetic surface roughness (Ra) were both measured and compared to the specimens subjected to demineralization and/or remineralization. After the treatment of γ-PGA/nano-HAp on the etched surface, the reduction in Rsm from 999 ± 120 nm to 700 ± 80 nm suggests the possible mechanism of void-filling within a short treatment time of 10 min. Furthermore, ΔRa-I, the roughness change due to etching before remineralization, was 23.15 ± 3.23 nm, while ΔRa-II, the roughness change after remineralization, was 11.99 ± 3.90 nm. This statistically significant reduction in roughness change (p < 0.05) implies a protective effect against the demineralization process. The as-developed novel γ-PGA/nano-HAp paste possesses a high efficacy towards tooth microhardness rehardening, and a protective effect against acid etching.

In-situ preparation of CuO nanoparticles decorated In2O3 pn heterojunction composite for the photoelectrochemical detection of ornidazole.

The eco-friendly synthesis of metal oxides pn junction composite with high visible light absorption and its photoelectrochemical monitoring on antibiotics is reported. The In2O3-CuO pn heterojunction composite was successfully prepared by in-situ hydrothermal decoration of CuO on the prepared In2O3 using a simple reflux method. The obtained nanorods like In2O3-CuO pn heterojunction exhibited high conductivity with excellent stability for the facilitated photoelectrochemical detection of ornidazole (ONZ) that plays a role in aquatic toxicology. The photo-stability and optical characteristics of the In2O3-CuO heterojunction composite were analyzed through photocurrent and UV-visible studies. Mechanism of ONZ signaling has been proposed with appropriate band levels derived by Mott-Schottky analysis. An optimized In2O3-CuO heterojunction detects ONZ in the range 0.05-65.3 nM with 0.0092 nM as the limit of detection at - 0.45 V (vs. Ag/AgCl) working potential. The practical applicability of the sensor device was tested in chicken meat, human urine, and lake water samples containing ONZ. The recoveries of real samples were above 95% and results obtained were compared with electrochemical methods.

Highly Mesoporous g-C3N4 with Uniform Pore Size Distribution via the Template-Free Method to Enhanced Solar-Driven Tetracycline Degradation.

A highly mesoporous graphitic carbon nitride g-C3N4 (GCN) has been produced by a template-free method and effectively photodegrade tetracycline (TC) antibiotic under solar light irradiation. The mesoporous GCN (GCN-500) greatly improves the photoactivity (0.0247 min-1) by 2.13 times, as compared to that of bulk GCN (0.0116 min-1). The efficiently strengthened photoactivity is ascribed to the high porosity (117.05 m2/g), and improves the optical absorption under visible light (Eg = 2.65 eV) and good charge carrier separation efficiency. The synthesized mesoporous GCN shows a uniform pore size (~3 nm) distribution. GCN-500 shows large pore volume (0.210 cm3/g) compared to GCN-B (0.083 cm3/g). Besides, the GCN-500 also exhibits good recyclability and photostability for TC photodegradation. In conclusion, GCN-500 is a recyclable photocatalyst for the removal of TC under visible light irradiation.

Operando Investigation of Structural and Chemical Origin of Co3O4 Stability in Acid under Oxygen Evolution Reaction.

Replacement of an expensive anode electrocatalyst in proton exchange membrane water electrolysis is of great importance. Recently explored Co3O4 shows good activity and stability toward oxygen evolution reaction (OER) in acid; however, the stability is not adequately explained. Lack of such information delays the design of an acid-stable OER electrocatalyst. Here, we investigate the structural origin of cobalt dissolution by various local atomic configurations of Co3O4. Operando Raman studies and voltammetric data reveal that chemical reduction of the CoO2 intermediate accompanied by lattice oxygen loss leads to undercoordinated CoO sites, which then react with water and form an amorphous three-dimensional (3D) porous network of CoO(OH)x, called the hydrous oxide layer (HOL). Growth of HOL mainly depends on the oxygen vacancies and near-surface OI- that impair the crystalline integrity and favor dissolution. These insights provide a fundamental relation between OER activity and stability and offer a specific guideline for the electrocatalyst design.

Preparation of novel nanostructured WO3/CuMnO2 p-n heterojunction nanocomposite for photoelectrochemical detection of nitrofurazone.

Herein this research, a visible light active tungsten oxide/copper manganate (WO3/CuMnO2) p-n heterojunction nanocomposite was prepared and has been applied for a signal on photoelectrochemical sensing of antibiotic nitrofurazone (NFZ). Firstly, the n-WO3 nanotiles were synthesized from the cetrimonium bromide (CTAB) assisted hydrothermal method and the p-CuMnO2 nanoparticles were synthesized by using the ultrasound-assisted hydrothermal method. The photoelectrochemical NFZ sensing performance of WO3/CuMnO2 nanocomposite was 1.9 times higher than that of as-synthesized pure WO3 nanotiles. The resulting higher photoelectrochemical performance of the nanocomposite is due to more visible light absorption ability and synergy from p-n heterojunction formation. The designed WO3/CuMnO2 nanocomposite sensor gives satisfactory photocurrent signals for the detection of NFZ in the range of 0.015-32 µM with the detection limit (LOD) of 1.19 nM. The practical applicability of the nanocomposite sensor was monitored in pork liver and tap water samples.

Virtual Telesimulation for Medical Students During the COVID-19 Pandemic.

PROBLEM: In March 2020, the novel coronavirus 2019 (COVID-19) became a global pandemic. Medical schools around the United States faced difficult decisions, temporarily suspending hospital-based clerkship rotations for medical students due to potential shortages of personal protective equipment and a need to social distance. This decision created a need for innovative, virtual learning opportunities to support undergraduate medical education. APPROACH: Educators at Yale School of Medicine developed a novel medical student curriculum converting high-fidelity, mannequin-based simulation into a fully online virtual telesimulation format. By using a virtual videoconferencing platform to deliver remote telesimulation as an immersive educational experience for widely dispersed students, this novel technology retains the experiential strengths of simulation-based learning while complying with needs for social distancing during the pandemic. The curriculum comprises simulated clinical scenarios that include live patient actors; facilitator interactions; and real-time assessment of vital signs, labs, and imaging. Each 90-minute session includes 2 sets of simulation scenarios and faculty-led teledebriefs. A team of 3 students performs the first scenario, while an additional team of 3 students observes. Teams reverse roles for the second scenario. OUTCOMES: The 6-week virtual telesimulation elective enrolled the maximum 48 medical students and covered core clinical clerkship content areas. Communication patterns within the virtual telesimulation format required more deliberate turn-taking than normal conversation. Using the chat function within the videoconferencing platform allowed teams to complete simultaneous tasks. A nurse confederate provided cues not available in the virtual telesimulation format. NEXT STEPS: Rapid dissemination of this program, including online webinars and live demonstration sessions with student volunteers, supports the development of similar programs at other universities. Evaluation and process improvement efforts include planned qualitative evaluation of this new format to further understand and refine the learning experience. Future work is needed to evaluate clinical skill development in this educational modality.