Three-layered nanoplates and amorphous/crystalline interface synergism boost CO2 photoreduction on bismuth oxychloride nanospheres.

Structural features like 3D nano-size, ultrathin thickness and amorphous/crystalline interfaces play crucial roles in regulating charge separation and active sites of photocatalysts. However, their co-occurrence in a single catalyst and exploitation in photocatalytic CO2 reduction (PCR) remains challenging. Herein, nano-sized bismuth oxychloride spheres (BiOCl-NS) confining three-layered nanoplates (∼2.2 nm ultrathin) and an amorphous/crystalline interface are exclusively developed via intrinsic engineering for an enhanced sacrificial-reagent-free PCR system. The results uncover a unique synergism wherein the three-layered nanoplates accelerate electron-hole separation, and the amorphous/crystalline interface exposes electron-localized active sites (Bi-Ovac-Bi). Consequently, BiOCl-NS exhibit efficient CO2 adsorption and activation with the lowering of rate-determining-step energy barriers, leading to remarkable CO production (102.72 µmol g-1 h-1) with high selectivity (>99%), stability (>30 h), and apparent quantum efficiency (0.51%), outperforming conventional counterparts. Our work provides a facile structural engineering approach for boosting PCR and offers distinct synergism for advancing diverse materials.

Rubidium Doped Cs2AgBiBr6 Hierarchical Microsphere for Enhanced Photocatalytic CO2 Reduction.

Halide perovskites have garnered significant attention for their unique optoelectronic properties in solar-to-fuel conversions. However, the efficiency of halide perovskites in the field of photocatalytic CO2 reduction is largely limited by serious charge recombination and a lack of efficient active sites. In this work, a rubidium (Rb) doped Cs2AgBiBr6 (Rb:CABB) hierarchical microsphere is developed for photocatalytic CO2 reduction. Experimental and theoretical analysis discloses that partially substituting Rb+ for Ag+ can effectively modulate the electronic structure of CABB, favoring charge separation and making adjacent Bi atoms an electron-rich active site. Further investigations indicated that Rb doping also reduces the energy barriers of the rate-determining step in CO2 reduction. As a result, Rb:CABB demonstrated an enhanced CO yield compared to its undoped counterpart. This work presents a promising approach to optimizing the electronic structures of photocatalysts and paving a new way for exploring halide perovskites for photocatalytic CO2 reduction.

Enrichment of Bioactive Lipids in Urinary Extracellular Vesicles and Evidence of Apoptosis in Kidneys of Hypertensive Diabetic Cathepsin B Knockout Mice after Streptozotocin Treatment.

Cathepsin B (CtsB) is a ubiquitously expressed cysteine protease that plays important roles in health and disease. Urinary extracellular vesicles (uEVs) are released from cells associated with urinary organs. The antibiotic streptozotocin (STZ) is known to induce pancreatic islet beta cell destruction, diabetic nephropathy, and hypertension. We hypothesized that streptozotocin-induced diabetic kidney disease and hypertension result in the release of bioactive lipids from kidney cells that induce oxidative stress and renal cell death. Lipidomics was performed on uEVs isolated from CtsB knockout mice treated with or without STZ, and their kidneys were used to investigate changes in proteins associated with cell death. Lysophosphatidylethanolamine (LPE) (18:1), lysophosphatidylserine (LPS) (22:6), and lysophosphatidylglycerol (LPG) (22:5) were among the bioactive lipids enriched in uEVs from CtsB knockout mice treated with STZ compared to untreated CtsB mice (n = 3 uEV preparations per group). Anti-oxidant programming was activated in the kidneys of the CtsB knockout mice treated with STZ, as indicated by increased expression of glutathione peroxidase 4 (GPX4) and the cystine/glutamate antiporter SLC7A11 (XCT) (n = 4 mice per group), which was supported by a higher reactivity to 4-hydroxy-2-nonenal (4-HNE), a marker for oxidative stress (n = 3 mice per group). Apoptosis but not ferroptosis was the ongoing form of cell death in these kidneys as cleaved caspase-3 levels were significantly elevated in the STZ-treated CtsB knockout mice (n = 4 mice per group). There were no appreciable differences in the pro-ferroptosis enzyme acyl-CoA synthetase long-chain family member 4 (ACSL4) or the inflammatory marker CD93 in the kidneys (n = 3 mice per group), which further supports apoptosis as the prevalent mechanism of pathology. These data suggest that STZ treatment leads to oxidative stress, inducing apoptotic injury in the kidneys during the development of diabetic kidney disease and hypertension.

Regulating the Active Sites of Cs2 AgBiCl6 by Doping for Efficient Coupling of Photocatalytic CO2 Reduction and Benzyl Alcohol Oxidation.

Halide perovskites exhibit outstanding optoelectronic properties, which make them an ideal choice for photocatalytic CO2 reduction and benzyl alcohol (BA) oxidation. Nevertheless, the simultaneous realization of the above redox coupling reactions on halide perovskites remains a great challenge, as it requires distinct catalytic sites for different target reactions. Herein, the catalytic sites of Cs2 AgBiCl6 (CABC) are regulated by doping Fe for efficient coupling of photocatalytic CO2 reduction and BA oxidation. The Fe-doped CABC (Fe: CABC) exhibits an enhanced visible-light response and effective charge separation. Experimental results and theoretical calculations reveal a synergistic interplay between Bi and Fe sites, where the Bi and Fe sites have lower activation energies toward CO2 reduction and BA oxidation. Further investigations demonstrate that electrons and holes prefer to accumulate at the Bi site and Fe site under light irradiation, respectively, which creates favorable conditions for facilitating CO2 reduction and BA oxidation. The resultant Fe: CABC achieves a high photocatalytic performance toward CO (18.5 µmol g-1  h-1 ) and BD (1.1 mmol g-1  h-1 ) generation, which surpasses most of the state-of-the-art halide photocatalysts. This work demonstrates a facile strategy for regulating the catalytic site for redox coupling reactions, which will pave a new way for designing halide perovskites for photocatalysis.

Metformin Alleviates Diabetes-Associated Hypertension by Attenuating the Renal Epithelial Sodium Channel.

Diabetic nephropathy is the primary cause of morbidity in type 2 diabetes mellitus (T2DM) patients. New data indicate that hypertension, a common comorbidity in T2DM, can worsen outcomes of diabetic nephropathy. While metformin is a commonly prescribed drug for treating type 2 diabetes, its blood pressure regulating ability is not well documented. The aim of this study was to investigate the effect of metformin on normalizing blood pressure in salt-loaded hypertensive diabetic db/db mice. Sixteen-week-old male and female diabetic db/db mice were individually placed in metabolic cages and then randomized to a control vehicle (saline) or metformin treatment group. We evaluated the blood pressure reducing ability of metformin in salt-induced hypertension and progression of nephropathy in db/db mice. We observed that metformin- normalized systolic blood pressure in hypertensive diabetic mice. Mechanistically, metformin treatment reduced renal cathepsin B expression. Low cathepsin B expression was associated with reduced expression and activity of the epithelial sodium channel (ENaC), sodium retention, and thus control of hypertension. In addition, we identified that urinary extracellular vesicles (EVs) from the diabetic mice are enriched in cathepsin B. Compared to treatment with urinary EVs of vehicle-treated hypertensive diabetic mice, the amiloride-sensitive transepithelial current was significantly attenuated upon exposure of renal collecting duct cells to urinary EVs isolated from metformin-treated db/db mice or cathepsin B knockout mice. Collectively, our study identifies a novel blood pressure reducing role of metformin in diabetic nephropathy by regulating the cathepsin B-ENaC axis.

Barriers and motivators to specializing in geriatrics and strategies for recruitment: Scoping review.

While the barriers to specializing in geriatrics are known, motivators behind why medical trainees choose geriatrics are not as well understood. It is also unknown if recruitment strategies in the literature address these barriers and motivators. The aim of this systematic scoping review is to examine the current literature on recruitment strategies alongside motivators and barriers for specializing in geriatrics. Eligible articles for this scoping review either focused on motivators or barriers among trainees (medical students, resident-physicians, fellows) or recruitment strategies. A scoping search was conducted in MEDLINE, Embase, CINAHL, and PsychINFO. Data was extracted on article characteristics and themes. 88 of 2064 articles were eligible and included. Personal fulfillment emerged as the most common theme for motivators, contrary to prior studies that cite positive role modeling. Financial disincentive remained the most common barrier, followed by limited exposure and "futile" practice. Promising interventions beyond financial compensation include defining geriatrics better, emphasizing the high job satisfaction rates, increasing clinical exposure for medical students, and additional funding for academic centers to recruit academic geriatricians. Policymakers and medical educators should consider multiple strategies that target the motivators, as well as the barriers to pursuing geriatrics.

Differences of Search Engine Digital Footprints Between Podiatrists and Foot and Ankle Orthopaedic Surgeons: A Need to Join the Digital Era.

BACKGROUND: Search engines generate lists of the most relevant websites using a keyword or phrase query and are integral in guiding consumer preferences. Digital information is important in the field of medicine, influencing what patients learn about their conditions and who they choose as providers. When two types of healthcare providers, such as podiatry and foot and ankle orthopaedic surgeons (FAOSs), share an overlapping consumer market, whichever group has a larger digital footprint receives increased digital engagement. METHODS: The Google search engine was used to query nine common foot and ankle-associated terms using a "search term + zip code" format for 150 zip codes divided into urban, suburban, and rural population densities. The first 10 results of each search were classified into one of five categories. Site content was classified as podiatry-oriented, other MD/DO-oriented, or FAOS-oriented. Separately, a ratio between podiatrists and FAOSs was calculated for each population density group. Data were then normalized using this ratio and reanalyzed with the Wilcoxon signed-rank test with significance at P < 0.05. RESULTS: Of 13,500 total search results, 4,992 (36.9%) were podiatry-oriented, 2,109 (15.6%) were other MD/DO-oriented, and 436 (3.2%) were FAOS-oriented. All geographic areas featured a higher number of podiatry than FAOS-oriented sites. FAOSs have more results per provider in urban areas (P < 0.001), although podiatrists had more in suburban and rural areas (P < 0.001, P < 0.001). Podiatrists have greater digital engagement in descriptive search terms. "Ankle replacement" has greater FAOS engagement in all three geographic areas. DISCUSSION: Foot and ankle-related Internet search terms results are overwhelmingly composed of podiatry-oriented sites. Per provider, regional differences are demonstrated, with FAOS having more sites in urban areas only. FAOS scope-of-practice terms such as "ankle replacement" still retain greater engagement by FAOSs. Search engine optimization and saturation strategies should be considered. LEVEL OF EVIDENCE: Level 3 (observational study).

Tempol Alters Urinary Extracellular Vesicle Lipid Content and Release While Reducing Blood Pressure during the Development of Salt-Sensitive Hypertension.

Salt-sensitive hypertension resulting from an increase in blood pressure after high dietary salt intake is associated with an increase in the production of reactive oxygen species (ROS). ROS are known to increase the activity of the epithelial sodium channel (ENaC), and therefore, they have an indirect effect on sodium retention and increasing blood pressure. Extracellular vesicles (EVs) carry various molecules including proteins, microRNAs, and lipids and play a role in intercellular communication and intracellular signaling in health and disease. We investigated changes in EV lipids, urinary electrolytes, osmolality, blood pressure, and expression of renal ENaC and its adaptor protein, MARCKS/MARCKS Like Protein 1 (MLP1) after administration of the antioxidant Tempol in salt-sensitive hypertensive 129Sv mice. Our results show Tempol infusion reduces systolic blood pressure and protein expression of the alpha subunit of ENaC and MARCKS in the kidney cortex of hypertensive 129Sv mice. Our lipidomic data show an enrichment of diacylglycerols and monoacylglycerols and reduction in ceramides, dihydroceramides, and triacylglycerols in urinary EVs from these mice after Tempol treatment. These data will provide insight into our understanding of mechanisms involving strategies aimed to inhibit ROS to alleviate salt-sensitive hypertension.

Comparison of Clinical Efficacy of Alectinib Versus Crizotinib in ALK-Positive Non-Small Cell Lung Cancer: A Meta-Analysis.

OBJECTIVE: To systematically evaluate the efficacy and safety of alectinib versus crizotinib in the treatment of anaplastic lymphoma kinase (ALK) positive non-small-cell lung cancer. METHODS: Studies about the efficacy of alectinib versus crizotinib in the treatment of ALK-positive non-small cell lung cancer were searched in PubMed, Scopus, Embase and the Cocharane Library from inception to February 15, 2020. Two reviewers independently screened these studies, extracted the data, assessed the risk of bias in the included studies by using the Cochrane risk assessment tool, and then used review manager 5.3 software for meta-analysis. RESULTS: Three studies comprising a total of 697 patients with ALK-positive non-small cell lung cancer were included, 380 in the alectinib group and 317 in the crizotinib group. The dose of alectinib (300 mg) in J-ALEX were lower than the approved dose (600 mg), however the crizotinib group in all three studies received the recommended dose (250 mg). Performance bias was high in all three studies whereas, and the attrition bias was high in two studies (Toyoaki Hida 2017 and Solange peters 2017). The results of meta-analysis showed that: the overall response rate [OR = 2.07, 95% CI (1.41, 3.06), P = 0.0002], the progression free survival [HR = 0.34, 95% CI (0.21, 0.55), P <0.0001], the partial response [OR = 1.71, 95% CI (1.19, 2.46), P = 0.003], P = 0.001], in alectinib group were higher than that of crizotinib group. Though the total number of events in complete response and the disease control rate were more in alectinib group than that of crizotinib group, the meta-analysis results shows no significant differences between two drugs in the disease control rate [OR = 2.24, 95% CI (0.56, 8.88), P = 0.25], the complete response [OR = 1.82, 95% CI (0.75, 4.45), P = 0.19]. In addition, the number of events in the stable disease [OR = 0.45, 95% CI (0.28, O.74), P = 0.001], and the adverse events [OR = 0.50, 95% CI (0.23, 0.81), P = <0.0001] in alectinib group were lower than that of crizotinib group. CONCLUSION: Alectinib in terms of overall response rate, progression-free survival and partial response is superior to crizotinib in the treatment of ALK-positive non-small cell lung cancer and is well tolerated. Compared with crizotinib, alectinib is more effective than crizotinib and has a lower incidence of total adverse reactions. Meta-analysis results confirm the strong base for alectinib as a first-line treatment for ALK-positive NSCLC.

One-pot, ligand-free, room-temperature synthesis of Au/Pd/ZnO nanoclusters with ultra-low noble metal loading and synergistically improved photocatalytic performances.

Au/Pd/ZnO nanoclusters with ultra-low noble metal loadings were prepared by a one-step and ligand-free method at room temperature. HRTEM, ICP-MS, XPS, and elemental mapping analysis confirmed that the obtained Au/Pd/ZnO nanoclusters were composed of ZnO nanoclusters decorated with well-dispersed AuPd nanoparticles. Au/Pd/ZnO nanoclusters exhibited higher photocatalytic activity compared with those of pristine ZnO, Au/ZnO and Pd/ZnO. Moreover, the high catalytic activity of Au/Pd/ZnO nanoclusters could be maintained even after 5 cycles of photocatalytic reaction. A mechanism for the enhanced photocatalytic performance was also suggested, which was in light of the synergistic effects of the SPR effect from Au and the improved photogenerated charge carrier separation from Pd.

A CTAB-mediated antisolvent vapor route to shale-like Cs4PbBr6 microplates showing an eminent photoluminescence.

Compared with nanoscale quantum dots (QDs), the large-sized perovskite crystals not only possess better stability but also are convenient for application exploration. Herein, we develop a facile and efficient antisolvent vapor-assisted recrystallization approach for the synthesis of large-sized Cs4PbBr6 perovskite crystal microplates. In this method, for the first time, the shale-like Cs4PbBr6 microplates with lateral dimensions of hundreds of microns are fabricated by employing cetyltriethylammnonium bromide (CTAB) as a morphology-directing agent. FESEM, TEM, and AFM characterizations indicate that the as-obtained shale-like Cs4PbBr6 microplates are actually formed by 6-8 nm thick Cs4PbBr6 nanosheets with orientational stacking. Importantly, such highly crystalline Cs4PbBr6 microplates with shale-like morphology exhibit a narrow and intense green PL emission with a 59% PL quantum yield. Moreover, the planar structure of shale-like Cs4PbBr6 microplates makes it easy to form a preferred orientation on a substrate, which endow them with promising potential in optoelectronic devices such as lighting and displays.

The structures, water stabilities and photoluminescence properties of two types of iodocuprate(i)-based hybrids.

Although great progress has been made in hybrid iodocuprates(i) as lighting phosphors, the effects of aromatic and aliphatic structure directing agents (SDAs) on their water stability, structure and photoluminescence (PL) properties are still not clear. Herein, aromatic N-heterocyclic 1,2-di(4-pyridyl)ethylene (dpe), aliphatic N-heterocyclic 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu) and N-aminoethylpiperazine (app) were selected to be SDAs to construct two types of hybrid iodocuprates(i) via a facile in situ approach. Aromatic dpe-derived cations are successfully directed to form (Me2dpe)(CuI3) (1), (Me2dpe)n(Cu4I6)n (2), (Et2dpe)2(Cu6I10) (3), and (H2dpe)n(Cu2I4)n (4). Three of them contain unprecedented inorganic iodocuprate clusters or chains. The aliphatic N-heterocyclic dbu- and app-derivative cations are responsible for the formation of (Hdbu)n(Cu2I3)n (5) and (H3app)2(Cu2I6)·2I·2H2O (6), which contain a (Cu2I3)- chain and a (Cu2I6)4- binuclear cluster, respectively. For the first time, the influence mechanisms of the water stabilities of iodocuprate-based PL materials were disclosed, by analyzing the possible interactions between SDAs and water molecules. 1-2 are PL silent due to their "self-quenching effect". 3, 4 and5 exhibit bright red, orange and yellow solid-state PL emissions at room temperature respectively, originating from the charge transfer between inorganic iodocuprate species and organic N-heterocycles. The co-template approach leads to multiple charge transfers in 6, which features a tunable PL behavior from bluish green to white by varying the excitation light, and has a quantum yield up to 43% (the highest value among hybrid iodocuprates containing (Cu2I6)4- clusters). The comparative study not only helps us to rationally synthesize iodocuprate-based PL materials with enhanced performance, but also provides a new method to obtain wavelength-dependent PL materials.

Multilayered Echo State Machine: A Novel Architecture and Algorithm.

In this paper, we present a novel architecture and learning algorithm for a multilayered echo state machine (ML-ESM). Traditional echo state networks (ESNs) refer to a particular type of reservoir computing (RC) architecture. They constitute an effective approach to recurrent neural network (RNN) training, with the (RNN-based) reservoir generated randomly, and only the readout trained using a simple computationally efficient algorithm. ESNs have greatly facilitated the real-time application of RNN, and have been shown to outperform classical approaches in a number of benchmark tasks. In this paper, we introduce a novel criteria for integrating multiple layers of reservoirs within the ML-ESM. The addition of multiple layers of reservoirs are shown to provide a more robust alternative to conventional RC networks. We demonstrate the comparative merits of this approach in a number of applications, considering both benchmark datasets and real world applications.

Thoracic splenosis: know it--avoid unnecessary investigations, interventions, and thoracotomy.

Thoracic splenosis (TS) is autoimplantation of ectopic splenic tissue in the thoracic cavity that occurs following splenic injury. Most cases of TS are asymptomatic and are diagnosed during the course of an evaluation of incidentally discovered pulmonary lesions. Some cases may be difficult to diagnose, especially if features suggesting TS are not recognized. This may lead to an extensive workup and unnecessary invasive diagnostic procedures including thoracotomy. Multiple, asymptomatic, left-sided pleura-based lesions associated with a history of thoracoabdominal injury and splenectomy are the key points that should alert one to suspect TS, which can then simply be confirmed with a (99m)Tcsulfa colloid radionuclide scan. If TS is suspected and radionuclide imaging studies are performed, further extensive investigations, such as bronchoscopy, biopsy, thoracoscopy, and thoracotomy, are not required as the radionuclide scan is definitive for diagnosis. Most cases are asymptomatic, so further treatment is rarely required; all cases are managed conservatively. We emphasize that all physicians, radiologists, pathologists, and interventionalists should recognize key features that suggest the diagnosis of TS, order appropriate imaging when it is suspected, and avoid unnecessary invasive diagnostic procedures including thoracotomy.

The role of endarterectomy and stenting in the management of carotid artery stenosis: a 5-year Delphi survey.

INTRODUCTION: Ambiguity in the literature concerning potential benefits of carotid artery stenting (CAS) as an alternative to carotid endarterectomy (CEA) necessitated a 5-year Delphi-type survey, gauging the changing views over this period of relevant experts undertaking carotid intervention. METHODS: Delphi surveys performed in 2004 and 2009 involved 2 rounds of questions combined with feedback of results from the first round between them. The questionnaire was e-mailed to UK vascular surgeons, neurosurgeons, interventional radiologists, and cardiologists. RESULTS: In 2004 and 2009, the second round response rates were 69% and 51%, respectively. Over 5 years, there was a statistically significant reduction in support for ''general anesthesia risk'' and ''contralateral occlusion'' as indications for CAS and views that CAS ''increased patient satisfaction'' and ''decreased the length of hospital stay.'' Concerning the impact of recent trials on the professionals' treatment routines for symptomatic and asymptomatic patients with carotid disease, 65.8% and 76.3%, respectively, had not changed their overwhelming non-CAS routines, with 32.9% and 19.7% saying clinical trial results moved them toward CEA. CONCLUSIONS: A 2009 survey of vascular experts found no increase in preference for CAS as a treatment option for advanced carotid bifurcation atherosclerosis. This, in combination with the lack of change from and indeed move toward the ''gold-standard'' CEA, demonstrates a general decline in confidence with CAS.

Motivational determinants among physicians in Lahore, Pakistan.

INTRODUCTION: Human resource crises in developing countries have been identified as a critical aspect of poor quality and low accessibility in health care. Worker motivation is an important facet of this issue. Specifically, motivation among physicians, who are an important bridge between health systems and patients, should be considered. This study aimed to identify the determinants of job motivation among physicians, a neglected perspective, especially in developing countries. METHODS: A stratified random sample of 360 physicians was selected from public primary, public secondary and public and private tertiary health facilities in the Lahore district, Pakistan. Pretested, semi-structured, self-administered questionnaires were used. For the descriptive part of this study, physicians were asked to report their 5 most important work motivators and demotivators within the context of their current jobs and in general. Responses were coded according to emergent themes and frequencies calculated. Of the 30 factors identified, 10 were classified as intrinsic, 16 as organizational and 4 as socio-cultural. RESULTS: Intrinsic and socio-cultural factors like serving people, respect and career growth were important motivators. Conversely, demotivators across setups were mostly organizational, especially in current jobs. Among these, less pay was reported the most frequently. Fewer opportunities for higher qualifications was a demotivator among primary and secondary physicians. Less personal safety and poor working conditions were important in the public sector, particularly among female physicians. Among private tertiary physicians financial incentives other than pay and good working conditions were motivators in current jobs. Socio-cultural and intrinsic factors like less personal and social time and the inability to financially support oneself and family were more important among male physicians. CONCLUSION: Motivational determinants differed across different levels of care, sectors and genders. Nonetheless, the important motivators across setups in this study were mostly intrinsic and socio-cultural, which are difficult to affect while the demotivators were largely organizational. Many can be addressed even at the facility level such as less personal safety and poor working conditions. Thus, in resource limited settings a good strategic starting point could be small scale changes that may markedly improve physicians' motivation and subsequently the quality of health care.

Surgery still opens an unexpected bag of worms! An intraperitoneal live female Dirofilaria worm: case report and review of the literature.

BACKGROUND: Intra-abdominal filarial infection is extremely rare. METHODS: Case report and review of the literature. RESULTS: A 63-year-old man presented with a painful swelling in the peri-umbilical area. An urgent laparotomy was performed for suspected strangulated peri-umbilical hernia. A live intraperitoneal worm was retrieved during the repair of the hernial sac that proved to be a female Dirofilaria immitis. CONCLUSIONS: Only one previous case of intraperitoneal involvement by dirofilariasis is described in the medical literature. Ours is the first case report of a live dirofilarial worm in the abdominal cavity of a human being.