Nitrogen Doping-Roused Synergistic Active Sites in Perovskite Enabling Highly Selective CO2 Photoreduction into CH4.

The intricate protonation process in carbon dioxide reduction usually makes the product unpredictable. Thus, it is significant to control the reactive intermediates to manipulate the reaction steps. Here, we propose that the synergistic La-Ti active sites in the N-La2Ti2O7 nanosheets enable the highly selective carbon dioxide photoreduction into methane. In the photoreduction of CO2 over N-La2Ti2O7 nanosheets, in situ Fourier transform infrared spectra are utilized to monitor the *CH3O intermediate, pivotal for methane production, whereas such monitoring is not conducted for La2Ti2O7 nanosheets. Also, theoretical calculations testify to the increased charge densities on the Ti and La atoms and the regulated formation energy barrier of *CO and *CH3O intermediates by the constructed synergistic active sites. Accordingly, the methane formation rate of 7.97 µL h-1 exhibited by the N-La2Ti2O7 nanosheets, along with an electron selectivity of 96.6%, exceeds that of most previously reported catalysts under similar conditions.

Selective Photoreduction of CO2 to CH4 Triggered by Metal-Vacancy Pair Sites.

Selectively achieving the photoreduction of carbon dioxide (CO2) to methane (CH4) remains a significant challenge, which primarily arises from the complexity of the protonation process. In this work, we designed metal-vacancy pair sites in defective metal oxide semiconductors, which anchor the reactive intermediates with a bridged linkage for the selective protonation to produce CH4. As an example, oxygen-deficient Nb2O5 nanosheets are synthesized, in which the niobium-oxygen vacancy pair sites are demonstrated by X-ray photoelectron spectroscopy and electron paramagnetic resonance spectra. In situ Fourier transform infrared spectroscopy monitors the *CH3O intermediate, a key intermediate for CH4 production, during the CO2 photoreduction in oxygen-deficient Nb2O5 nanosheets. Importantly, the built metal-vacancy pair sites regulate the *CH3O formation step as a spontaneous process, making the reduction of CO2 to CH4 the preferred method. Therefore, the oxygen-deficient Nb2O5 nanosheets exhibit a CH4 formation rate of 19.14 µmol g-1 h-1, with an electron selectivity of ∼94.1%.

Fundamentals and Challenges of Engineering Charge Polarized Active Sites for CO2 Photoreduction toward C2 Products.

ConspectusGlobal warming and climatic deterioration are partly caused by carbon dioxide (CO2) emission. Given this, CO2 reduction into valuable carbonaceous fuels is a win-win route to simultaneously alleviate the greenhouse effect and the energy crisis, where CO2 reduction into hydrocarbon fuels by solar energy may be a potential strategy. Up to now, most of the current photocatalysts photoconvert CO2 to C1 products. It is extremely difficult to achieve production of C2 products, which have higher economic value and energy density, due to the kinetic challenge of C-C coupling of the C1 intermediates. Therefore, to realize CO2 photoreduction to C2 fuels, design of high-activity photocatalysts to expedite the C-C coupling is significant. Besides, the current mechanism for CO2 photoreduction toward C2 fuels is usually uncertain, which is possibly attributed to the following two reasons: (1) It is arduous to determine the actual catalytic sites for the C-C coupling step. (2) It is hard to monitor the low-concentration active intermediates during the multielectron transfer step.Most traditional metal-based photocatalysts usually possess charge balanced active sites that have the same charge density. In this aspect, the neighboring C1 intermediates may also show the same charge distribution, which would lead to dipole-dipole repulsion, thus preventing C-C coupling for producing C2 fuels. By contrast, photocatalysts with charge polarized active sites possess obviously different charge distributions in the adjacent C1 intermediates, which can effectively suppress the electrostatic repulsion to steer the C-C coupling. Based on this analysis, higher asymmetric charge density on the active sites would be more beneficial to anchoring between the adjacent intermediates and active atoms in catalysts, which can boost C-C coupling.In this Account, we summarize various strategies, including vacancy engineering, doping engineering, loading engineering, and heterojunction engineering, for tailoring charge polarized active sites to boost the C-C coupling for the first time. Also, we overview diverse in situ characterization technologies, such as in situ X-ray photoelectron spectroscopy, in situ Raman spectroscopy, and in situ Fourier transform infrared spectroscopy, for determining charge polarized active sites and monitoring reaction intermediates, helping to reveal the internal catalytic mechanism of CO2 photoreduction toward C2 products. We hope this Account may help readers to understand the crucial function of charge polarized active sites during CO2 photoreduction toward C2 products and provide guidance for designing and preparing highly active catalysts for photocatalytic CO2 reduction.

Use of failure mode and effect analysis to reduce patient safety risks in purchasing prescription drugs from online pharmacies in China.

Background: Online pharmacies have gradually penetrated the market, but pose risks to patients' health. Failure Mode and Effect Analysis (FMEA) is an effective and reliable method for reducing pharmacy and medication risks. The purpose of this study was to conduct a prospective risk analysis of the process of purchasing prescription drugs from online pharmacies in China to guarantee drug quality and patient safety. Methods: The FMEA was performed at Sichuan University, China. A multidisciplinary team was assembled comprising a leader, four regulators, four pharmacists, two experts, etc. The process was composed of eight subprocesses: searching for prescription drugs, submitting medication requirements, completing patient information forms, dispensing, delivering, etc. Brainstorming was used to identify and prioritize failure modes, propose corrective actions, and reduce risks. Risk priority numbers were the main criterion and were obtained by multiplying three scores: severity, occurrence and detectability, which were scored by the team The team proposed corrective actions for each selected failure mode. Results: A total of forty-one potential failure modes were identified, and the causes, effects, and corrective actions of the 30 top failure modes were analyzed. The highest risk value was assigned to "photocopies of paper prescriptions uploaded were reused by patients." Three failure modes for the S value of 5 were: "drugs are eroded and polluted by moisture or insects in the process of transportation," "the qualification information of the pharmacies were absent or fake," and "pharmacists fail to check prescriptions in accordance with Prescription Administrative Regulation." Of the top failure modes, 36.67% were from Step 5, delivering the drug. After taking corrective measures to control risks, the risks reduced by 69.26%. Conclusion: The results of this study proves that the FMEA is a valuable tool for identifying and prioritizing the risks inherent in online pharmacies. This study shows that there are many potential risks in the process of purchasing prescription drugs from online pharmacies, especially in the drug delivery stage. Enhanced training and the introduction of smart devices may minimize risks. Online pharmacies and Chinese regulators should consider these findings for risk mitigation and the improvement of regulations pertaining to online pharmacies.

Visual Impairments Are Associated With Retinal Microvascular Density in Patients With Parkinson's Disease.

OBJECTIVE: This study aimed to evaluate retinal microvascular density in patients with Parkinson's disease (PD) and its correlation with visual impairment. METHODS: This cross-sectional study included 24 eyes of 24 patients with PD and 23 eyes of 23 healthy controls. All participants underwent ophthalmic examination, visual evoked potential (VEP) test, 25-item National Eye Institute Visual Function Questionnaire (NEI VFQ-25), and optical coherence tomography angiography (OCTA) examination. The correlation between retinal microvascular density and visual parameter was evaluated using Spearman correlation analysis, and the area under receiver operating characteristic curve (AUROC) was calculated. RESULTS: Parkinson's disease patients had prolonged P100 latency (P = 0.041), worse vision-related quality of life (composite score and 3 of 12 subscales in NEI VFQ-25), and decreased vessel density (VD) in all sectors of 3-mm-diameter region (all P < 0.05) compared with healthy controls. There were no statistical differences in the ganglion cell-inner plexiform layer (GCIPL) thickness and retinal nerve fiber layer (RNFL) thickness between the two groups. A negative correlation was found between P100 latency and nasal and superior sectors of macular VD in a 3-mm-diameter region (r = -0.328, P = 0.030; r = -0.302, and P = 0.047, respectively). Macular VD in a 3-mm-diameter region showed diagnostic capacities to distinguish PD patients from healthy controls (AUROCs, ranging from 0.655 to 0.723). CONCLUSION: This study demonstrated that decreased retinal microvascular density was correlated with visual impairment in PD patients. Retinal microvasculature change may occur earlier than visual decline and retinal structure change and has the potential to be a promising diagnostic marker for early PD.

The Role of Elastase in Corneal Epithelial Barrier Dysfunction Caused by Pseudomonas aeruginosa Exoproteins.

Purpose: To investigate the role of elastase in corneal epithelial barrier dysfunction caused by the exoproteins secreted by Pseudomonas aeruginosa. Methods: Exoproteins obtained from Pseudomonas aeruginosa culture supernatant were analyzed by shotgun proteomics approach. In vitro multilayered rabbit corneal epithelial barrier model prepared by air-liquid interface technique (CECs-ALI) were treated with 2 µg/ml exoproteins and/or 8 mM elastase inhibitor. Then the epithelial barrier function was evaluated by transepithelial electrical resistance (TEER) assay and tight junction proteins immunofluorescence. Cell viability and the apoptosis rate were examined by CCK8 assay and flow cytometry. TNF-α, IL-6, IL-8, and IL-1ß levels were measured by ELISA. Mice cornea treated with exoproteins and/or elastase inhibitor were evaluated in vivo and in vitro. Results: Elastase (24.2%) is one of the major components of exoproteins. After 2 µg/ml exoproteins were applied to CECs-ALI for two hours, TEER decreased from 323.2 ± 2.7 to 104 ± 6.8 Ω/cm2 (P < 0.001). The immunofluorescence results showed a distinct separation in tight junction and significant degradation of ZO-1 and occludin (P < 0.05). Elastase inhibitor (8 mM) alleviated the decrease in TEER value (234 ± 6.8 Ω cm2) induced by exoproteins. Inhibition of elastase decreased the apoptosis rate of CECs treated with exoproteins from 30.2 ± 3.8% to 7.26 ± 1.3% and the levels of inflammatory factors (P < 0.05). Mice corneal epithelium defect could be induced by exoproteins and protected by elastase inhibitor. Conclusions: Elastase plays a critical role in corneal epithelial barrier dysfunction caused by Pseudomonas aeruginosa exoproteins via damaging tight junctions. The inhibition of elastase could protect the corneal epithelial barrier via reducing virulence and inflammation.

Patient Preferences For Specialty Pharmacy Services: A Stated Preference Discrete-Choice Experiment in China.

Objectives: To survey, analyze, and ascertain the preferences for specialty pharmacy services among patients requiring complex care and to provide evidence to support specialty pharmacy service decision-making in China. Methods: To identify essential service attributes and levels, a review of the literature, discussions with specialty pharmacy managers and a pilot questionnaire were conducted. A D-efficient fractional factorial design was used to generate the discrete-choice experiment (DCE) questionnaire. A face-to-face survey of patients with chronic illness and their families or friends was conducted at three specialty pharmacies in Chengdu and Qingdao, China. A mixed logit model was used for estimation. Results: Six relevant attributes were identified and incorporated into the DCE questionnaire. A total of 417 participants completed the survey (mean age 43 years, 45.1% males), and 32.1% had lung cancer. The conditional relative importance showed that the most critical attribute was "frequency of telephone follow-up to monitor adverse drug reactions (ADRs), "followed by "mode of drug delivery," "provider of medication guidance services," and "availability of medical insurance consultation"; the least important attribute was "business hours." A 1 min increase in time spent led to a 0.73% decrease in the probability that a service profile would be chosen. Negative preferences were noted for ADR monitoring by telephone follow-up once a year (ß = -0.23, p < 0.001) and business hours [8:30-20:00 (Monday to Friday), 8:30-17:30 (weekend)] (ß = -0.12, p < 0.001). Compared with women, men had a higher preference for service monitoring ADRs once every 3 months. Conclusions: Preference measurements showed that "frequency of telephone follow-up to monitor ADRs" had the most critical impact on decisions, followed by "mode of drug delivery." Specialty pharmacies in China need to take these findings into account to improve their design to increase uptake and patient loyalty.

Comparison of infection eradication rate of using articulating spacers containing bio-inert materials versus all-cement articulating spacers in revision of infected TKA: a systematic review and meta-analysis.

PURPOSE: To assess the infection eradication rate when using two types of articulating spacers (prosthetic articulating spacers and all-cement articulating spacers) in two-stage revision of infected total knee arthroplasty (TKA). METHODS: We comprehensively searched PubMed, Embase, and the Cochrane Library databases and performed a systematic review and meta-analysis of retrospective comparative studies assessing two types of articulating spacers. A quality assessment of the included studies was performed following the STROBE statement. RESULTS: Thirty retrospective studies, including a total of 821 knees, were identified. The pooled infection control rates in stage I were as follows: 0.98 (95% confidence interval [CI], 0.97 to 1.00) and 0.98 (95% CI, 0.96 to 0.99) for the prosthetic articulating spacer group and all-cement articulating spacer group, respectively. The pooled postoperative reinfection rate was 0.05 (95% CI, 0.03 to 0.08) for the prosthetic spacer group and 0.03 (95% CI, 0.01 to 0.06) for the all-cement spacer group. Results of the subgroup analyses showed that the weight of the antibiotic cement, antibiotic type, mean period of spacers in situ, postoperative antibiotic treatment period, and postoperative antibiotic treatment approach had no effect on the reinfection rates (p < 0.05). CONCLUSIONS: Compared to all-cement articulating spacers, articulating spacers containing bio-inert materials have a similar infection control rate but a higher postoperative reinfection rate. Although the 95% CIs of reinfection rates in the two groups overlapped, our results indicate that articulating spacers containing bio-inert materials may be associated with higher reinfection rates and poorer clinical outcomes than all-cement articulating spacers.