Photosensitizing metal covalent organic framework with fast charge transfer dynamics for efficient CO2 photoreduction.

Designing artificial photocatalysts for CO2 reduction is challenging, mainly due to the intrinsic difficulty of making multiple functional units cooperate efficiently. Herein, three-dimensional metal covalent organic frameworks (3D MCOFs) were employed as an innovative platform to integrate a strong Ru(ii) light-harvesting unit, an active Re(i) catalytic center, and an efficient charge separation configuration for photocatalysis. The photosensitive moiety was precisely stabilized into the covalent skeleton by using a rational-designed Ru(ii) complex as one of the building units, while the Re(i) center was linked via a shared bridging ligand with an Ru(ii) center, opening an effective pathway for their electronic interaction. Remarkably, the as-synthesized MCOF exhibited impressive CO2 photoreduction activity with a CO generation rate as high as 1840 µmol g-1 h-1 and 97.7% selectivity. The femtosecond transient absorption spectroscopy combined with theoretical calculations uncovered the fast charge-transfer dynamics occurring between the photoactive and catalytic centers, providing a comprehensive understanding of the photocatalytic mechanism. This work offers in-depth insight into the design of MCOF-based photocatalysts for solar energy utilization.

Panchromatic Light-Harvesting Three-Dimensional Metal Covalent Organic Frameworks for Boosting Photocatalysis.

Constructing artificial photocatalysts with panchromatic solar energy utilization remains an appealing challenge. Herein, two complementary photosensitizers, [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) and porphyrin dyes, have been cosensitized in metal covalent organic frameworks (MCOFs), resulting in the MCOFs with strong light absorption covering the full visible spectrum. Under panchromatic light irradiation, the cosensitized MCOFs exhibited remarkable photocatalytic H2 evolution with an optimum rate of up to 33.02 mmol g-1 h-1. Even when exposed to deep-red light (λ = 700 ± 10 nm), a commendable H2 production (0.79 mmol g-1 h-1) was still obtained. Theoretical calculation demonstrated that the [Ru(bpy)3]2+ and porphyrin modules in our MCOFs have a synergistic effect to trigger an interesting dual-channel photosensitization pathway for efficient light-harvesting and energy conversion. This work highlights the potential of combining multiple PSs in MCOFs for panchromatic photocatalysis.

A prediction model for osteonecrosis of femoral head after internal fixation with multiple cannulated compression screws for adult femoral neck fractures.

OBJECTIVES: This study aims to investigate the high-risk factors for osteonecrosis of the femoral head (ONFH) after internal fixation with multiple cannulated compression screws for adult femoral neck fractures and to construct a prediction model. PATIENTS AND METHODS: Between from January 2012 and December 2020, a total of 268 patients (138 males, 130 females; mean age: 53±10 years; range, 23 to 70 years) with ONFH who had complete follow-up data were included. Closed reduction in combination with open reduction were performed. All patients received internal fixation with multiple cannulated compression screws and were assigned to ONFH and non-ONFH groups. Logistic regression model was utilized to identify independent risk factors for postoperative ONFH, followed by constructing a nomogram prediction model. The predictive ability of the model was evaluated by receiver operating characteristic curve, Hosmer-Lemeshow test, and calibration curve. RESULTS: Multivariate analysis revealed that older age (odds ratio [OR]: 2.307, 95% confidence interval [CI]: 1.295-4.108], Charlson Comorbidity Index (CCI) ≥2 (OR: 2.214, 95% CI: 1.035-4.739), fracture displacement (OR: 2.426, 95% CI: 1.122-5.247), unsatisfactory reduction (OR: 2.629, 95% CI: 1.275-5.423), postoperative removal of internal fixation implant (OR: 2.200, 95% CI: 1.051-4.604) were independent risk factors for postoperative ONFH (p<0.05). The nomogram prediction model constructed based on these clinical characteristics showed high predictive value (AUC=0.807) and consistency (p>0.05). CONCLUSION: Age, comorbidity index, fracture type, reduction quality and postoperative removal of internal fixation implant are of utmost importance for postoperative ONFH in patients with femoral neck fractures. The established nomogram prediction model can accurately predict the occurrence of postoperative ONFH.

Positional Isomers of Covalent Organic Frameworks for Indoor Humidity Regulation.

Humidity is one of the most important indicators affecting human health. Here, a pair of covalent organic frameworks (COFs) of positional isomers (p-COF and o-COF) for indoor humidity regulation is reported. Although p-COF and o-COF have the same sql topology and pore size, they exhibit different water adsorption behaviors due to the subtle differences in water adsorption sites. Particularly, o-COF exhibits a steep adsorption isotherm in the range of 45-65% RH with a hysteresis loop, which is perfectly suitable for indoor humidity regulation. In the laboratory experiment, when the humidity of the external environment is 20-75% RH, o-COF can control the humidity of the room in the range of 45-60% RH. o-COF has shown great potential as a dual humidification/dehumidification adsorbent for indoor humidity regulation.

A high-resolution nutrient emission inventory for hotspot identification in the Yangtze River Basin.

A high-resolution nutrient emission inventory can provide reliable and accurate identification of priority control areas, which is crucial for efficient decisions on water quality restoration. However, the inventories widely used in large-scale modeling are usually based on provincial inputs, which induce the challenges of lacking localized parameters and missing localized characteristic when provincial scale inputs are converted to finer scales with the down-scale methods. Based on elaborate investigations and statistical data at the county scale with multi-scale data conversion, the China Emission Inventory of Nutrients (CEIN) was developed with a spatial resolution of a 0.1° grid and sub-basin scales. The Yangtze River Basin was used as a case study to illustrate the potential applications of CEIN. The emissions of total nitrogen (TN) and total phosphorus (TP) of Yangtze River Basin is 0.43 Mt and 0.04 Mt for point sources, 11.09 Mt and 4.64 Mt for diffuse sources in 2017. The hotspot analysis for 2606 sub-basins indicated that cropland is the key source of nutrient emissions, accounting for 58.88% and 79.15% of TN and TP, respectively. Industrial sewage and freshwater aquaculture accounted for 27.39% (TN) and 21.98% (TP) of the point sources, which is substantial due to their direct discharge into surface waters. The current results also reveal that, in contrast to CEIN, the previously used common emission factors based on GDP per capita produced considerable overestimations of 2.37 and 2.65 times the actual TN and TP emissions, respectively. Additional advantages of the CEIN have been demonstrated in identifying priority control areas more accurately with reduced bias and quantifying the effects of policies at much smaller scales. For example, the CEIN helps to distinguish hotspots, which was neglected when identifying sources at the level-III sub-basin scale, and indicates that the management of fractional areas (TN: 16.97%; TP: 13.44%) provides the highest nutrient emissions control (TN: 44.34%; TP: 48.65%) for the entire basin. The evaluation of China's toilet revolution policy demonstrates that achieving equitable access to safe sanitation has resulted in a reduction of 7240 t of TN and 833 t of TP, which is extremely critical for rural water quality and health.

Single-atom sites on perovskite chips for record-high sensitivity and quantification in SERS.

Surface enhanced Raman scattering (SERS) is a rapid and nondestructive technique that is capable of detecting and identifying chemical or biological compounds. Sensitive SERS quantification is vital for practical applications, particularly for portable detection of biomolecules such as amino acids and nucleotides. However, few approaches can achieve sensitive and quantitative Raman detection of these most fundamental components in biology. Herein, a noble-metal-free single-atom site on a chip strategy was applied to modify single tungsten atom oxide on a lead halide perovskite, which provides sensitive SERS quantification for various analytes, including rhodamine, tyrosine and cytosine. The single-atom site on a chip can enable quantitative linear SERS responses of rhodamine (10-6-1 mmol L-1), tyrosine (0.06-1 mmol L-1) and cytosine (0.2-45 mmol L-1), respectively, which all achieve record-high enhancement factors among plasmonic-free semiconductors. The experimental test and theoretical simulation both reveal that the enhanced mechanism can be ascribed to the controllable single-atom site, which can not only trap photoinduced electrons from the perovskite substrate but also enhance the highly efficient and quantitative charge transfer to analytes. Furthermore, the label-free strategy of single-atom sites on a chip can be applied in a portable Raman platform to obtain a sensitivity similar to that on a benchtop instrument, which can be readily extended to various biomolecules for low-cost, widely demanded and more precise point-of-care testing or in-vitro detection. Electronic Supplementary Material: Supplementary material is available for this article at 10.1007/s40843-022-1968-5 and is accessible for authorized users.

The efficacy of intra-articular fentanyl supplementation for knee arthroscopy: A meta-analysis of randomized controlled studies.

INTRODUCTION: The efficacy of intra-articular fentanyl supplementation for pain control after knee arthroscopy remains controversial. We conduct a systematic review and meta-analysis to explore the influence of intra-articular fentanyl supplementation for pain intensity after arthroscopic knee surgery. METHODS: We searched PubMed, EMbase, Web of Science, EBSCO, and Cochrane Library databases through May 2019 for randomized controlled trials (RCTs) assessing the efficacy and safety of intra-articular fentanyl supplementation for arthroscopic knee surgery. This meta-analysis is performed using the random-effects model. RESULTS: Four RCTs are included in the meta-analysis. Overall, compared with control group after knee arthroscopy, intra-articular fentanyl supplementation is associated with reduced pain scores at 1 h (standard mean difference (Std MD) = -3.50; 95% confidence interval (CI) = -5.68 to -1.32; p = 0.002), 2 h (Std MD = -4.73; 95% CI = -8.75 to -0.71; p = 0.02), and 8 h (Std MD = -5.02; 95% CI = -9.73 to -0.30; p = 0.04) but shows no substantial impact on pain scores at 4 h (Std MD = -3.94; 95% CI = -7.93 to 0.05; p = 0.05) or the supplementary analgesia (risk ratio = 0.56; 95% CI = 0.09-3.59; p = 0.54). CONCLUSIONS: Intra-articular fentanyl supplementation does benefit in pain control after knee arthroscopy.

Effect of selenium antagonist lead-induced damage on Th1/Th2 imbalance in the peripheral blood lymphocytes of chickens.

Lead (Pb) is a type of toxic metal that can hurt the immune system. Selenium (Se) can reduce the damage caused by heavy metals. To investigate the effects of Se against Pb on bird immune cells, as well as the immunotoxin mechanism of Pb, Se supplementation and/or Pb poisoning chicken models were established. One hundred eighty 1-year-old broiler chickens were randomly divided into four groups (n = 6). The four groups were the control group, the selenium-rich group (Se group), the Pb supplementation group (Pb group) and the Se and Pb compound group (Se + Pb group). The peripheral blood lymphocytes of chickens were collected to test the selenoproteins and cytokine mRNA levels at 30 and 60 d. Determination of the content of Se and Pb in the serum, principal component analysis and ingenuity pathway analysis were performed at the two time points. As a result, Pb exposure increased the content of Pb, activating the Th1/Th2 pathway in peripheral blood lymphocytes. Additionally, this experiment showed that Se supplementation and Pb exposure could influence the mRNA levels of selenoproteins and cytokines in the peripheral blood lymphocytes of chickens. However, all of the parameters that we detected in the experiment indicated that Se supplementation could alleviate the increase of selenoproteins and cytokine mRNA levels and the Th1/Th2 imbalance induced by Pb in peripheral blood lymphocytes. In summary, Se can alleviate the toxic effects caused by Pb in the peripheral blood lymphocytes of chickens, suggesting the antagonism between Se and Pb.

[Case-control study on a new Kirschner wire tension band with hole in the treatment of adult olecranon fractures in adults].

OBJECTIVE: To compare the efficacy of Kirschner wire tension band with hole and common Kirschner wire tension band in the treatment of olecranon fractures in adults, so as to guide the selection of clinical surgical procedures. METHODS: From July 2011 to October 2015, a total of 49 patients with olecranon fractures underwent open reduction and fixation with Kirschner wire tension band, which were retrospectively analyzed. Of the 49 patients, 21 patients(group A) were treated with Kirschner wire tension band with hole, including 12 males and 9 females, with an average age of(37.6 ±8.2) years old;28 patients(group B) were treated with common Kirschner wire, including 18 males and 10 females, with an average age of(38.9±7.3) years old. There were no statistically significant differences between the two groups in general data. The differences of operative duration, frequency of radiation, fracture healing time, complications and postoperative elbow function scores between the two groups were observed and analyzed by parallel statistical analysis. RESULTS: In group A, the operative duration was(60.4±10.7) min, the average number of radiation times was (12.5±2.9); in group B, the operative duration was (62.3±11.8) min, and the average radiation times was(13.7±3.8); there was no significant difference in operative time and radiation times between the two groups (P >0.05). In group A, the fracture healing time was (13.2±2.6) weeks without K-wire migration, skin irritation and other complications; and fracture healing time in group B was(14.6±1.8) weeks with complications(K-wire migration in 6 cases, skin irritation in 7 cases, internal fixation failure in 2 cases);the fracture healing time of group A was shorter than that in group B. Evaluation of elbow joint function in two groups of patients after operation showed that in group A, pain score was 41.0±3.5, movement function score was 18.0±2.1, stability score was 9.0±0.8, daily activities score was 18.0±4.3, the total average score was 87.0±7.8; and in group B, the pain score was 39.0±5.6, movement function score was 17.0±3.2, the stability score was 8.0±2.4, daily activities score was 16.0±5.2, the total average score was 83.0±10.7. There were no statistically significant in the scores between the two groups. CONCLUSIONS: Compared with ordinary Kirschner wire, the treatment of olecranon fracture with Kirschner tension band with hole can shorten the time of fracture healing, significantly reduce the occurrence of complications, and do not affect the recovery of postoperative function, which is suitable for clinical use.

Postoperative plasma 8-iso-prostaglandin F2α levels are associated with delirium and cognitive dysfunction in elderly patients after hip fracture surgery.

BACKGROUND: Oxidative stress may be involved in occurrence of postoperative delirium (POD) and cognitive dysfunction (POCD). 8-iso-Prostaglandin F2α (8-iso-PGF2α), an isoprostane derived from arachidonic acid via lipid peroxidation, is considered a gold standard for measuring oxidative stress. The present study aimed to investigate the ability of postoperative plasma 8-iso-PGF2α levels to predict POD and POCD in elderly patients undergoing hip fracture surgery. METHODS: Postoperative plasma 8-iso-PGF2α levels of 182 patients were measured by an enzyme-linked immunosorbent assay. We assessed the relationships between plasma 8-iso-PGF2α levels and the risk of POD and POCD using a multivariate analysis. RESULTS: Plasma 8-iso-PGF2α levels and age were identified as the independent predictors for POD and POCD. Based on areas under receiver operating characteristic curve, the predictive values of 8-iso-PGF2α were obviously higher than those of age for POD and POCD. In a combined logistic-regression model, 8-iso-PGF2α significantly enhanced the areas under curve of age for prediction of POD and POCD. CONCLUSIONS: Postoperative plasma 8-iso-PGF2α levels may have the potential to predict POD and POCD in elder patients undergoing hip fracture surgery.

Chicken 15-kDa selenoprotein plays important antioxidative function in splenocytes.

The 15-kDa selenoprotein (Sep15) is a thioredoxin-like protein. The expression of Sep15 is regulated by dietary selenium (Se) and plays important roles in mammals. However, the structure and function of chicken Sep15 and its response to Se are still unclear. In the present study, we replicated the chicken Se deficiency models and Sep15 deficiency models in splenocytes. Then, the homology, structure analysis, and levels of Sep15 were analyzed. In addition, the oxidative stress levels were examined in Sep15 deficiency splenocytes. The results indicated that chicken Sep15 preserved high similarity with that of other 14 animals in the coding nucleotide sequences (CDS) and deduced amino acid sequence, which suggested that chicken Sep15 may be derived from the same ancestor with other animals. The predicted structure and function showed that chicken Sep15 preserved the conserved thioredoxin-like fold CxU, which suggested an antioxidative function. Chicken Sep15 was also decreased by Se deficiency in immune organs (P < 0.05). In addition, Sep15 deficiency induced the occurrence of higher oxidative stress and enhanced the sensitivity of cells to H2O2 (P < 0.05). So the in vitro study further verified its antioxidative function. Thus, similar to its mammal homolog, chicken Sep15 preserves the typical characteristic of selenoprotein and may play some roles in the redox regulation.