Scanning Tunneling Microscopy Visualization of Polaron Charge Trapping by Hydroxyls on TiO2(110).

Using scanning tunneling microscopy (STM), we investigate the spatial distribution of the bridging hydroxyl (OHb) bound excess electrons on the rutile TiO2(110) surface and its temperature dependence. By performing simultaneously recorded empty and filled state imaging on single OHbs at different temperatures in STM, we determine that the spatial distribution of the OHb bound excess electrons retains a symmetric four-lobe structure around the OHb at both 78 and 7 K. This indicates that OHbs are much weaker charge traps compared to bridging O vacancies (Ob-vac). In addition, by sequentially removing the capping H of each OHb using voltage pulses, we find that the annihilation of each OHb is accompanied by the disappearance of some lobes in the filled state STM, thus verifying the direct correlation between OHbs and their excess electrons.

Unravelling co-catalyst integration methods in Ti-based metal-organic gels for photocatalytic H2 production.

The synthesis, characterization and photocatalytic hydrogen evolution reaction (HER) performance of a series of metal-organic gels (MOGs) constructed from titanium(IV)-oxo clusters and dicarboxylato linkers (benzene-1,4-dicarboxylato and 2-aminobenzene-1,4-dicarboxylato) are described. All the MOGs exhibit a microstructure comprised of metal-organic nanoparticles intertwined into a highly meso-/macroporous structure, as demonstrated by cryogenic transmission electron microscopy and gas adsorption isotherms. Comprehensive chemical characterization enabled the estimation of the complex formula for these defective materials, which exhibit low crystallinity and linker vacancies. To gain deeper insights into the local structure, X-ray absorption fine structure (XAFS) spectroscopy experiments were performed and compared to that of the analogous crystalline metal-organic framework. Additionally, the ultraviolet-visible absorption properties and optical band gaps were determined from diffuse reflectance spectroscopy data. The MOGs were studied as light absorbers for the sacrificial photocatalytic HER under simulated solar light irradiation using a platinum co-catalyst by either (1) in situ photodeposition or (2) ex situ doping process, through a post-synthetic metalation of the MOG structure. The chemical analysis of the metalation, along with high-angle annular dark-field scanning transmission electron microscopy, revealed that although the in situ addition of the co-catalyst led to greater HER rates (227 vs. 110 µmolH2 gMOG-1 h-1 for in situ and ex situ, respectively), the ex situ modification provided a finer distribution of platinum nanoparticles along the porous microstructure and, as a result, it led to a more efficient utilization of the co-catalyst (45 vs. 110 mmolH2 gPt-1 h-1).

Dual Shield: Bifurcated Coating Analysis of Multilayered WO3/BiVO4/TiO2/NiOOH Photoanodes for Sustainable Solar-to-Hydrogen Generation from Challenging Waters.

The heterostructure WO3/BiVO4-based photoanodes have garnered significant interest for photoelectrochemical (PEC) solar-driven water splitting to produce hydrogen. However, challenges such as inadequate charge separation and photocorrosion significantly hinder their performance, limiting overall solar-to-hydrogen conversion efficiency. The incorporation of cocatalysts has shown promise in improving charge separation at the photoanode, yet mitigating photocorrosion remains a formidable challenge. Amorphous metal oxide-based passivation layers offer a potential solution to safeguard semiconductor catalysts. We examine the structural, surface morphological, and optical properties of two-step-integrated sputter and spray-coated TiO2 thin films and their integration onto WO3/BiVO4, both with and without NiOOH cocatalyst deposition. The J-V experiments reveal that the NiOOH cocatalyst enhances the photocurrent density of the WO3/BiVO4 photoanode in water splitting reactions from 2.81 to 3.87 mA/cm2. However, during prolonged operation, the photocurrent density degrades by 52%. In contrast, integrated sputter and spray-coated TiO2 passivation layer-coated WO3/BiVO4/NiOOH samples demonstrate a ∼88% enhancement in photocurrent density (5.3 mA/cm2) with minimal degradation, emphasizing the importance of a strategic coating protocol to sustain photocurrent generation. We further explore the feasibility of using natural mine wastewater as an electrolyte feedstock in PEC generation. Two-compartment PEC cells, utilizing both fresh water and metal mine wastewater feedstocks exhibit 66.6 and 74.2 µmol/h cm2 hydrogen generation, respectively. Intriguingly, the recovery of zinc (Zn2+) heavy metals on the cathode surface in the mine wastewater electrolyte is confirmed through surface morphology and elemental analysis. This work underscores the significance of passivation layer and cocatalyst coating methodologies in a sequential order to enhance charge separation and protect the photoanode from photocorrosion, contributing to sustainable hydrogen generation. Additionally, it suggests the potential of utilizing wastewater in electrolyzers as an alternative to freshwater resources.

Pharmacokinetics of oral ciprofloxacin in adult patients: A scoping review.

AIMS: To map the literature on oral ciprofloxacin's pharmacokinetics and its implications for dose adjustments in specific populations. METHODS: A scoping review was performed according to the Cochrane Collaboration and JBI and reported following the PRISMA-ScR. Systematic searches on electronic databases were conducted to integrate the current evidence on ciprofloxacin's pharmacokinetics. The quality of the included studies was assessed using ClinPK's checklist. RESULTS: The search yielded 55 relevant studies. Within the traditional pharmacokinetics studies (n = 46), 86 profiles were examined (72 involving healthy patients and 14 with various clinical conditions). Oral ciprofloxacin's pharmacokinetics were influenced by covariates such as drug interactions (ferrous ions, calcium carbonate, diclofenac and itraconazole), food interactions (calcium-rich foods), elderly populations and renal impairment. Notably, variability in pharmacokinetic parameters existed among subjects, regardless of their health status, underscoring the need for comprehensive population descriptions. Population pharmacokinetic studies (n = 9) identified significant covariates for hospitalized patients, such as creatinine clearance, plasma bicarbonate, estimated glomerular filtration rate, renal replacement therapy, age, sex, total bilirubin, fat-free mass, dietary factors in renal disease, rifampicin for clearance models and body weight for volume of distribution models. Most pharmacokinetic/pharmacodynamic assessments concluded that 1200 mg/day provides a high probability of target attainment for bacteria with minimum inhibitory concentration <0.5 mg L-1 , aiming for an area under the curve for 24 h/minimum inhibitory concentration >125 h. CONCLUSIONS: This study offers a comprehensive overview regarding oral ciprofloxacin's pharmacokinetics across various health conditions. It highlights the complexities of ciprofloxacin's pharmacokinetics, emphasizing the importance of considering multiple factors in dose adjustments.

Photoelectrocatalytic Surfactant Pollutant Degradation and Simultaneous Green Hydrogen Generation.

For the first time, we demonstrate a photoelectrocatalysis technique for simultaneous surfactant pollutant degradation and green hydrogen generation using mesoporous WO3/BiVO4 photoanode under simulated sunlight irradiation. The materials properties such as morphology, crystallite structure, chemical environment, optical absorbance, and bandgap energy of the WO3/BiVO4 films are examined and discussed. We have tested the anionic type (sodium 2-naphthalenesulfonate (S2NS)) and cationic type surfactants (benzyl alkyl dimethylammonium compounds (BAC-C12)) as model pollutants. A complete removal of S2NS and BAC-C12 surfactants at 60 and 90 min, respectively, by applying 1.75 V applied potential vs RHE to the circuit, under 1 sun was achieved. An interesting competitive phenomenon for photohole utilization was observed between surfactants and adsorbed water. This led to the formation of H2O2 from water alongside surfactant degradation (anode) and hydrogen evolution (cathode). No byproducts were observed after the direct photohole mediated degradation of surfactants, implying its advantage over other AOPs and biological processes. In the cathode compartment, 82.51 µmol/cm2 and 71.81 µmol/cm2 of hydrogen gas were generated during the BAC-C12 and S2NS surfactant degradation process, respectively, at 1.75 V RHE applied potential.

Improving fragility hip fracture care through data: a multicentre experience from a country with an emerging economy during the COVID-19 pandemic.

INTRODUCTION: In low-to-middle-income countries (LMIC), the orthogeriatric model of care is still in its early stages of development. This study describes the initial results of the first online fragility hip fracture database to be setup in the Philippines using a modified minimum common dataset to generate outcomes data based on current hospital practices. METHODS: A multicentre prospective cohort study among 12 Philippine hospitals was conducted from June 2020 to February 2021. Thirty-day mortality, morbidity and mobility were measured. Significant factors associated with mortality were determined. RESULTS: 158 elderly patients with fragility hip fractures were included in the study. Nine patients (5.7%) were confirmed or suspected to have COVID-19 infection. Median time of injury to admission was at least 3 days (IQR: 1.0-13.7). Overall, 80% of patients underwent surgical intervention with a median time from admission to surgery of at least 5 days (IQR: 2.5-13.6). Thirty-day mortality and morbidity rates for acute fragility fractures were 3.7%. Factors significantly associated with early mortality were poor prefracture mobility, COVID-19 infection, radiograph of the abnormal chest and conservative treatment. Non-surgical patients had no functional mobility or were wheelchair users and had a significantly higher morbidity rate than surgically treated patients (13.6% vs 1.8%; p=0.031). CONCLUSION: Despite treatment delays unique to an LMIC, short-term outcomes remain favourable for non-COVID-19 fragility hip fracture patients treated with surgery. Prompt admission and multidisciplinary care for elderly hip fracture patients while maintaining protective measures for COVID-19 infection control are recommended. The quality of data collected illustrates how this online database can provide a framework for a sustainable audit or registry as well as provide a platform for the introduction of orthogeriatric concepts at a multiregional scale.

Augmenting the Performance of Hydrogenase for Aerobic Photocatalytic Hydrogen Evolution via Solvent Tuning.

This work showcases the performance of [NiFeSe] hydrogenase from Desulfomicrobium baculatum for solar-driven hydrogen generation in a variety of organic-based deep eutectic solvents. Despite its well-known sensitivity towards air and organic solvents, the hydrogenase shows remarkable performance under an aerobic atmosphere in these solvents when paired with a TiO2 photocatalyst. Tuning the water content further increases hydrogen evolution activity to a TOF of 60±3 s-1 and quantum yield to 2.3±0.4 % under aerobic conditions, compared to a TOF of 4 s-1 in a purely aqueous solvent. Contrary to common belief, this work therefore demonstrates that placing natural hydrogenases into non-natural environments can enhance their intrinsic activity beyond their natural performance, paving the way for full water splitting using hydrogenases.

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.

Development of a validated stability-indicating HPLC- DAD method for dasabuvir and the characterization of its degradation products using LC-QToF-MS/MS

Abstract A stability-indicating HPLC-DAD method was developed and validated for the simultaneous determination of dasabuvir and its degradation products in the pharmaceutical formulation. The proposed method utilized a Symmetry® C18 (4.6 x 75 mm, 3.5 µm) column, and the mobile phase consisted of an isocratic elution of formic acid (0.1%) and acetonitrile (55:45, v/v), at a flow of 1 mL min-1; analytes were detected at 244 nm. Dasabuvir was submitted to different stress degradation conditions, such as acidic, alkaline, neutral, thermal, oxidative and photolytic, and the structural elucidation of degradation products was performed using LC-QToF-MS/MS. The HPLC-DAD stability-indicating method was validated for selectivity, linearity, limit of detection and quantification, accuracy, precision and robustness, according to ICH guidelines. Dasabuvir produced two degradation products (DP1 and DP2) from the alkaline stress conditions, which were characterized in negative ion mode. Dasabuvir was linear in the range 9.78 to 136.92 µg mL-1, and DP and DP were linear in the range 2.9 to 20.2 µg mL-1 and 1.3 to 14.9 µg mL-1, respectively. The 1 2 recovery ranged between 99.16 and 100.86%, while precision ranged from 1.02 to 2.89%. As the method can effectively separate the dasabuvir from its degradation products and quantitate them, it may be employed as a stability-indicating method for the pharmaceutical formulation.

Molecularly profiled trials: toward a framework of actions for the "nil actionables".

The sequencing of tumour or blood samples is increasingly used to stratify patients into clinical trials of molecularly targeted agents, and this approach has frequently demonstrated clinical benefit for those who are deemed eligible. But what of those who have no clear and evident molecular driver? What of those deemed to have "nil actionable" mutations? How might we deliver better therapeutic opportunities for those left behind in the clamour toward stratified therapeutics? And what significant learnings lie hidden in the data we amass but do not interrogate and understand? This Perspective article suggests a holistic approach to the future treatment of such patients, and sets a framework through which significant additional patient benefit might be achieved. In order to deliver upon this framework, it encourages and invites the clinical community to engage more enthusiastically and share learnings with colleagues in the early drug discovery community, in order to deliver a step change in patient care.

Local Surveillance and Control of Raccoon Rabies Virus in Striped Skunks (Mephitis mephitis) in Southwestern New Brunswick, Canada.

Targeted surveillance for raccoon rabies virus was conducted between February and May 2017, near Waweig, New Brunswick, Canada, in response to detection of a rabid striped skunk (Mephitis mephitis) on 8 February 2017. A total of six skunks, 11 raccoons (Procyon lotor), and two porcupines (Erethizon dorsatum) were live-trapped, euthanized, and tested for rabies virus antigens using the direct rapid immunohistochemical test. Of these, only two skunks tested positive for rabies. All three rabid skunks came from the same location, an abandoned barn used as a denning site. Four of five skunks removed from this barn were males. Feeding, aggression, extreme response to noise and light stimuli, and exposure to porcupine quills were observed in two rabid skunks. No additional cases of rabies in wildlife were detected in the area since 8 March 2017. A targeted surveillance approach that removed potentially infected wildlife followed by localized oral rabies vaccine distribution was implemented in this locality.

Ce=O Terminated CeO2.

Multiply bonded lanthanide oxo groups are rare in coordination compounds and have not previously been reported for a surface termination of a lanthanide oxide. Here we report the observation of a Ce=O terminated ceria surface in a CeO2 (111)-( 3 × 3 )R30° reconstruction of ≈3 nm thick ceria islands prepared on Pt(111). This is evidenced by scanning tunnelling microscopy (STM), low energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS) measurements in conjunction with density functional theory (DFT) calculations. A Ce=O stretching frequency of 775 cm-1 is observed in HREELS, compared with 766 cm-1 calculated by DFT. The calculations also predict that the Ce=O bond is weak, with an oxygen vacancy formation energy of 0.85 eV. This could play an important role in the facile removal of lattice oxygen from CeO2 , accompanied by the reduction of CeIV to CeIII , which is a key attribute of ceria-based systems in connection with their unique catalytic properties.

Genome-based local dynamics of canine rabies virus epidemiology, transmission, and evolution in Davao City, Philippines, 2018-2019.

Rabies is a fatal zoonotic and neglected tropical disease caused by the rabies virus (RABV) and is associated with neuronal dysfunction and death, with dogs as the predominant carrier. The Philippines plans to eradicate rabies by 2022, but this is challenged with sub-optimal coverage of vaccination programs coupled with sustained transmission chains, making it unable to eradicate the disease. We investigated the dynamics of canine rabies in the highly urbanized Davao City of the Philippines and its neighboring localities by assessing genetic relationships, transmission patterns, selection pressure, and recombination events using the whole genome sequence of 49 RABV cases from June 2018 to May 2019, majority of which (46%) were from the district of Talomo, Davao City. Although phylogeographic clustering was observed, local variants also exhibited genetic sub-lineages. Phylogenetic and spatial transmission analysis provided evidence for intra- and inter-city transmission predominantly through the Talomo district of Davao City. Around 84% of the cases were owned dogs, but the genetic similiarity of RABVs from stray and owned dogs further alluded to the role of the former as transmission vectors. The high rate of improper vaccination among the affected dogs (80%) was also a likely contributor to transmission. The RABV population under Investigation is generally under strong purifying selection with no evidence of vaccine evasion due to the genetic homogeneity of viruses from vaccinated and improperly vaccinated dogs. However, some homologous recombination (HR) events were identified along the G and L genes, also predominantly associated with viruses from Talomo. The complementary findings on epidemiology, transmission, and recombination for Talomo suggest that high incidence areas can be seeds for virus dispersal and evolution. We recommend further Investigations on the possibility of HR in future large-scale genome studies. Finally, districts associated with these phenomena can be targeted for evidence-based local strategies that can help break RABV transmission chains and prevent emergence of novel strains in Davao City.

FaceGuard: A Wearable System To Avoid Face Touching.

Most people touch their faces unconsciously, for instance to scratch an itch or to rest one's chin in their hands. To reduce the spread of the novel coronavirus (COVID-19), public health officials recommend against touching one's face, as the virus is transmitted through mucous membranes in the mouth, nose and eyes. Students, office workers, medical personnel and people on trains were found to touch their faces between 9 and 23 times per hour. This paper introduces FaceGuard, a system that utilizes deep learning to predict hand movements that result in touching the face, and provides sensory feedback to stop the user from touching the face. The system utilizes an inertial measurement unit (IMU) to obtain features that characterize hand movement involving face touching. Time-series data can be efficiently classified using 1D-Convolutional Neural Network (CNN) with minimal feature engineering; 1D-CNN filters automatically extract temporal features in IMU data. Thus, a 1D-CNN based prediction model is developed and trained with data from 4,800 trials recorded from 40 participants. Training data are collected for hand movements involving face touching during various everyday activities such as sitting, standing, or walking. Results showed that while the average time needed to touch the face is 1,200 ms, a prediction accuracy of more than 92% is achieved with less than 550 ms of IMU data. As for the sensory response, the paper presents a psychophysical experiment to compare the response time for three sensory feedback modalities, namely visual, auditory, and vibrotactile. Results demonstrate that the response time is significantly smaller for vibrotactile feedback (427.3 ms) compared to visual (561.70 ms) and auditory (520.97 ms). Furthermore, the success rate (to avoid face touching) is also statistically higher for vibrotactile and auditory feedback compared to visual feedback. These results demonstrate the feasibility of predicting a hand movement and providing timely sensory feedback within less than a second in order to avoid face touching.

LC-QToF-MS method for quantification of ethambutol, isoniazid, pyrazinamide and rifampicin in human plasma and its application.

In this research, we developed and validated a liquid chromatography coupled to mass spectrometry (LC-QToF-MS) method for simultaneous quantification of the anti-tuberculosis drugs ethambutol, isoniazid, pyrazinamide and rifampicin in human plasma. Plasma samples spiked with cimetidine (internal standard) were extracted using protein precipitation with acetonitrile containing 1% formic acid. Separation was performed using a C18 column under flow gradient conditions with water and acetonitrile, both containing 5 mm ammonium formate and 0.1% formic acid. The method was validated according to the ANVISA and US Food and Drug Administration guidelines for bioanalytical method validation. The calibration curve was linear over a concentration range of 0.2-5 µg ml-1 for ethambutol, 0.2-7.5 µg ml-1 for isoniazid, 1-40 µg ml-1 for pyrazinamide and 0.25-2 µg ml-1 for rifampicin, all with adequate precision and accuracy. The method was reproducible, selective and free of carryover and matrix effects. The validated LC-QToF-MS method was successfully applied to real samples and shown to be applicable to future therapeutic and pharmacokinetic monitoring studies.

"Experience Isn't Everything": How Emotion Affects the Relationship Between Experience and Cue Utilization.

OBJECTIVE: This research examined whether negative and positive arousal emotions modify the relationship between experience level and cue utilization among anesthetists. BACKGROUND: The capacity of a practitioner to form precise associations between clusters of features (e.g., symptoms) and events (e.g., diagnosis) and then act on them is known as cue utilization. A common assumption is that practice experience allows opportunities for cue acquisition and cue utilization. However, this relationship is often not borne out in research findings. This study investigates the role of emotional state in this relationship. METHOD: An online tool (EXPERTise 2.0) was used to assess practitioner cue utilization for tasks relevant to anesthesia. The experience of positive and negative arousal emotions in the previous three days was measured, and emotion clusters were generated. Experience was measured as the composite of practice years and hours of practice experience. The moderating role of emotion on the relationship between experience and cue utilization was examined. RESULTS: Data on 125 anesthetists (36% female) were included in the analysis. The predicted interaction between arousal emotions and the experience level emerged. In particular, post hoc analyses revealed that anxiety-related emotions facilitated the likelihood of high cue utilization in less experienced practitioners. CONCLUSION: The findings suggest a role for emotions in cue use and suggest a functional role for normal range anxiety emotions in a simulated work-relevant task. APPLICATION: This research illustrates the importance of understanding the potentially functional effects common negative arousal emotions may have on clinical performance, particularly for those with less experience.

Shape and Core-Excited Resonances in Thiophene.

We present a comprehensive study of resonance formation in electron collisions with thiophene. Detailed calculations have been performed using the ab initio R-matrix method. Absolute differential cross sections for electron impact excitation up to 18 eV and for two scattering angles, 90 and 135°, have been measured. Agreement between the calculated and measured experimental cross sections is very good. Three shape resonances previously described, two of π* character and one σ*, as well as a number of resonances of core-excited or mixed character are identified and characterized in the calculations. The measured cross sections provide experimental confirmation for a number of the core-excited resonances. The link between these resonances and prior DEA experiments is discussed.

Variation of SMSI with the Au:Pd Ratio of Bimetallic Nanoparticles on TiO2(110).

Au/Pd nanoparticles are important in a number of catalytic processes. Here we investigate the formation of Au-Pd bimetallic nanoparticles on TiO2(110) and their susceptibility to encapsulation using scanning tunneling microscopy, as well as Auger spectroscopy and low energy electron diffraction. Sequentially depositing 5 MLE Pd and 1 MLE Au at 298 K followed by annealing to 573 K results in a bimetallic core and Pd shell, with TiOx encapsulation on annealing to ~ 800 K. Further deposition of Au on the pinwheel type TiOx layer results in a template-assisted nucleation of Au nanoclusters, while on the zigzag type TiOx layer no preferential adsorption site of Au was observed. Increasing the Au:Pd ratio to 3 MLE Pd and 2 MLE Au results in nanoparticles that are enriched in Au at their surface, which exhibit a strong resistance towards encapsulation. Hence the degree of encapsulation of the nanoparticles during sintering can be controlled by tuning the Au:Pd ratio.