Tuning Morphologies of Metal-Organic Framework-Derived Ni3P/Ni Carbon Nanocomposites for Water Oxidation.

The oxygen evolution reaction (OER) frequently acts as a kinetic bottleneck in various energy storage and conversion systems. Effective electrocatalysts for the OER play a crucial role in reducing the reaction barrier and expediting the reaction. Multicomponent transition metal phosphides (TMPs) have garnered an extensive amount of attention as a result of their exceptional performance in the OER. Here, we present a direct method for preparing two intrinsic morphologies of metal-organic frameworks (MOFs), barrel-like BMM-10 and pancake-like BMM-10(Ac), achieved by establishing a protonation/deprotonation equilibrium with varying NO3-/Ac- ratios. The BMM-10(Ac)-C catalyst was synthesized via heat treatment of the BMM-10(Ac) precursor, exhibiting superior OER performance. It realized an overpotential of 286 mV at a current density of 10 mA cm-2, with a Tafel slope of 111.17 mV decade-1 and a current retention of 98.03%. This improvement arises from the synergistic interaction between Ni3P/Ni nanoparticles and the partially graphitic carbon layer, augmenting the exposure of active sites. Furthermore, alterations in the morphological features of MOF-derived Ni3P/Ni carbon nanocomposites adjusted the active electrochemical surface area, thereby modulating the overall OER performance of the corresponding TMP carbon nanocomposites. This methodology can be extended to control the morphology of other MOFs and their derivatives, providing innovative avenues for the design and synthesis of new MOF-based TMP nanomaterials.

Ligand-induced hollow binary metal-organic framework derived Fe-doped cobalt-carbon nanomaterials for oxygen evolution.

There is significant anticipation for high-efficiency and cost-effective non-precious metal-based catalysts to advance the industrial application of the anodic oxygen evolution reaction (OER) for hydrogen production. This study introduces an efficient strategy that utilizes ligand-induced metal-organic framework (MOF) building blocks for the synthesis of hollow binary zeolitic imidazolate frameworks 67 (ZIF-67) and Prussian blue analogues (PBAs) (ZIF-67@PBA) heterostructures through a hybrid MOF-on-MOF approach. Manipulating the Co2+/Zn2+ ratio in the precursor ZIF-67 allows for the convenient synthesis of the final product, denoted as CoxFe-ZP, after pyrolysis, where the inclusion of Zn effectively modulates the distribution of Co in the catalyst. The resulting CoxFe-ZP catalysts exhibit a positive synergistic effect between hollow graphitic carbon nanomaterials and Fe-doped Co nanoparticles. The optimal Co0.3Fe-ZP catalyst demonstrates satisfactory OER performance, achieving an overpotential of 302 mV at 10 mA cm-2 and a small Tafel slope of 60.0 mV dec-1. Further analysis of the activation energy confirms that the enhanced OER activity of Co0.3Fe-ZP can be reasonably attributed to the combined influence of its morphology and composition. This study demonstrates a ligand-induced method for examining the morphology and electrochemical properties of grown binary MOF-on-MOF heterostructures for OER applications.

[Spatial Prediction Modeling for Soil pH Based on Multiscale Geographical Weighted Regression(MGWR) and Its Influencing Factors].

Anhui, Henan, Jiangsu, and Shandong provinces were selected as the study area. A total of 599 soil samples and nine environmental factors of soil pH were collected. The spatial distribution of soil pH was modeled based on multi-scale geographically weighted regression(MGWR), mixed geographically weighted regression(Mixed GWR), geographically weighted regression(GWR), and multiple linear regression(MLR) models. Then, the spatial difference in the effect of environmental factors on soil pH was revealed using MGWR and quantile regression models. The results showed that:① soil pH showed significant global and local spatial autocorrelation at different spatial distances, and the clustering characteristics were obvious. ② The MGWR model was the best among the four models, and the Radj2 of MGWR, Mixed GWR, GWR, and MLR were 0.64, 0.62, 0.59, and 0.48, respectively. The residual of MGWR had the strongest independent distribution and the weakest spatial autocorrelation with a global Moran's I of 0.07. ③ Three types of GWR predictions showed that the spatial distribution of soil pH decreased gradually from north to south in the study area, with the highest in northern Henan and the lowest in southern Anhui. ④ MGWR modeling results showed that there was strong spatial heterogeneity of mean annual precipitation(MAP), multi-resolution valley bottom flatness(MRVBF), and elevation affecting soil pH. MAP had a stronger effect on soil pH in northern Jiangsu and most parts of Shandong. The positive effect of MRVBF on soil pH was stronger in northern Jiangsu and western Shandong. The negative effect of elevation on soil pH was stronger in northern and central Jiangsu. ⑤ The quantile regression analysis showed that the mean annual precipitation had a significant negative effect on soil pH at different quantile levels of soil pH, and influence intensity decreased with the increase in pH quantile level. MRVBF had a significant negative effect on soil pH at a low quantile level(θ=0.1 to 0.4) but had no significant effect on soil pH at a high quantile level(θ=0.5 to 0.9). These results can provide an important reference for mapping soil properties and analyzing its influence factors based on the MGWR model in large regions.

Understanding the Reaction Mechanism of Ni-Catalyzed Regio- and Enantioselective Hydroalkylation of Enamines: Chemoselectivity of (Bi-oxazoline)NiH.

This density functional theory study explores the detailed mechanism of nickel-catalyzed hydroalkylation of the C═C bond of N-Cbz-protected enamines (Cbz = benzyloxycarbonyl) with alkyl iodides to give chiral α-alkyl amines. The active catalyst (biOx)NiH, a chiral bioxazoline (biOx)-chelated Ni(I) hydride, exhibits chemoselectivity that favors single electron transfer to the alkyl iodide over C═C hydrometalation with the enamine. This generates an alkyl radical and a Ni(II) intermediate, which takes up the enamine substrate CbzNHCH═CH2CH3 via a regio- and enantioselective C═C insertion into the NiII-H bond. The resulting Ni(II) alkyl complex combines with the alkyl radical, forming a Ni(III) intermediate, from which the alkyl-alkyl reductive elimination delivers the chiral amine product. The regioselectivity arises from a combination of orbital and noncovalent interactions, both of which are induced by the Cbz group. Thus, Cbz plays an additional role in controlling regioselectivity. The enantioselectivity stems from the differing distortion energies of CbzNHCH═CH2CH3. The reductive elimination is the rate-determining step (ΔG⧧ = 18.7 kcal/mol). In addition, the calculations show a noninnocent behavior of the biOx ligand induced by the insertion of CbzNHCH═CH2CH3 into the Ni-H bond of (biOx)NiH. These computationally gained insights can have implications for developing new Ni(I)-catalyzed reactions.

Abundant Surface Defects in Cobalt Hydroxides/Oxyhydroxides Induced by Zinc Species Facilitate Water Oxidation.

The complex process of the anodic oxygen evolution reaction (OER) severely hinders overall water splitting, which further limits the large-scale production and application of hydrogen energy. In this work, one type of bimetallic coordination polymer of ZnCoBTC using the MOF-on-MOF strategy has been synthesized where both Co(II) and Zn(II) cations exhibit the same coordination environment. By applying an electric potential, the predesigned bimetallic MOF precursor can be conveniently degraded into CoOxHy as an active species for efficient OER. Owing to the dissolution of ZnOxHy species, in situ formed disordered defects on the external surface of the catalyst increase the specific surface area as well as expose abundant active materials. Therefore, the ZnCoOxHy nanosheet shows excellent OER performance and reaches an overpotential of only 334 mV at 10 mA cm-2 with a Tafel slope of 66.4 mV dec-1, indicating fast reaction kinetics. The results demonstrate that metals with the same coordination environment can undergo in situ replacement or secondary growth on the pristine MOF, and they can be electrochemically degraded into highly efficient catalysts for future energy applications.

Targeting the inward rectifier potassium channel 5.1 in thyroid cancer: artificial intelligence-facilitated molecular docking for drug discovery.

BACKGROUND: Recurrent and metastatic thyroid cancer is more invasive and can transform to dedifferentiated thyroid cancer, thus leading to a severe decline in the 10-year survival. The thyroid-stimulating hormone receptor (TSHR) plays an important role in differentiation process. We aim to find a therapeutic target in redifferentiation strategies for thyroid cancer. METHODS: Our study integrated the differentially expressed genes acquired from the Gene Expression Omnibus database by comparing TSHR expression levels in the Cancer Genome Atlas database. We conducted functional enrichment analysis and verified the expression of these genes by RT-PCR in 68 pairs of thyroid tumor and paratumor tissues. Artificial intelligence-enabled virtual screening was combined with the VirtualFlow platform for deep docking. RESULTS: We identified five genes (KCNJ16, SLC26A4, TG, TPO, and SYT1) as potential cancer treatment targets. TSHR and KCNJ16 were downregulated in the thyroid tumor tissues, compared with paired normal tissues. In addition, KCNJ16 was lower in the vascular/capsular invasion group. Enrichment analyses revealed that KCNJ16 may play a significant role in cell growth and differentiation. The inward rectifier potassium channel 5.1 (Kir5.1, encoded by KCNJ16) emerged as an interesting target in thyroid cancer. Artificial intelligence-facilitated molecular docking identified Z2087256678_2, Z2211139111_1, Z2211139111_2, and PV-000592319198_1 (-7.3 kcal/mol) as the most potent commercially available molecular targeting Kir5.1. CONCLUSION: This study may provide greater insights into the differentiation features associated with TSHR expression in thyroid cancer, and Kir5.1 may be a potential therapeutic target in the redifferentiation strategies for recurrent and metastatic thyroid cancer.

Genetic diversity and natural selection of rif gene (PF3D7_1254800) in the Plasmodium falciparum global populations.

To reveal the genetic characteristics of one member of the Plasmodium falciparum repetitive interspersed family (rif), we sequenced the rif gene (PF3D7_1254800) in 53 field isolates collected from Ghana-imported cases into China and compared them with 350 publicly available P. falciparum rif sequences from global populations. In the Ghana-imported population, the nucleotide diversities were 0.05714 and 0.06616 for the full length and variable region of rif gene, respectively. Meanwhile, 22 and 20 haplotypes were identified for the full length and variable region of rif gene (Hd = 0.843 and 0.838, respectively). Diversity of rif gene in Ghana-imported population was higher than that observed in Cambodia, Thailand, Vietnam, Myanmar, Mali, Ghana, and Senegal populations. In this analysis, we found high genetic diversity of rif gene in global P. falciparum populations and identified 158 haplotypes. Tajima's D-test shows that there are large differences in the direction of selection between the conserved and variable region of rif gene. Tajima's D value for the variable region was 0.20074, indicating that balancing selection existed in this region. We found that the variable region was the main target of selection for positive diversification, and most mutation sites were located in this region. The population structure suggested optimized cluster values of K = 6. The five groups in Ghana-imported population included a unique subpopulation. Our results reveal the dynamics of the rif gene (PF3D7_1254800) in P. falciparum populations, which can aid in the rational design of P. falciparum rif-based vaccines.

Partially Oxidized Carbon Nanomaterials with Ni/NiO Heterostructures as Durable Glucose Sensors.

Conventional enzyme-based glucose biosensors have limited extensive applications in daily life because glucose oxidase is easily inactivated and is expensive. In this paper, we propose a strategy to prepare a new type of cost-effective, efficient, and robust nonenzymatic Ni-CNT-O for electrochemical glucose sensing. It is first followed by the pyrolysis of Ni-ABDC nanostrips using melamine to grow carbon nanotubes (CNTs) to give an intermediate product of Ni-CNT, which is further accompanied by partial oxidation to enable the facile formation of hierarchical carbon nanomaterials with improved hydrophilicity. A series of physicochemical characterizations have fully proved that Ni-CNT-O is a carbon-coated heterostructure of Ni and NiO nanoparticles embedded into coordination polymer-derived porous carbons. The obtained Ni-CNT-O exhibits a better electrocatalytic activity for glucose oxidation stemming from the synergistic effect of a metal element and a metal oxide than unoxidized Ni-CNT, which also shows high performance with a wide linear range from 1 to 3000 µM. It also offers a high sensitivity of 79.4 µA mM-1 cm-2, a low detection limit of 500 nM (S/N = 3), and a satisfactory long-term durability. Finally, this glucose sensor exhibits good reproducibility, high selectivity, as well as satisfactory results by comparing the current response of simulated serum within egg albumen.

Morphologically Controlled Metal-Organic Framework-Derived FeNi Oxides for Efficient Water Oxidation.

The complex oxygen evolution reaction (OER) is recognized as the most studied and explored electrochemical conversion, which plays a crucial role in energy-related applications. In this work, a series of metal-organic framework (MOF)-derived FeNi oxides from a barrel-shaped Ni-based BMM-10 precursor are conveniently obtained to show an excellent OER performance. Under mild Fe(III) etching, a type of core-shell Fe0.5-BMM-10 can be well preserved and the coordination bond of the middle frame structure is decomposed. Furthermore, the Fex-BMM-10-T series is successfully synthesized with a well-preserved morphology compared to precursors after direct oxidation. Finally, followed by initial electrochemical activation, the decomposition of FeNi oxides generates active Fe-doped nickel oxyhydroxides for efficient water oxidation. The improved OER performance stems from the high specific surface area and abundant exposed active centers, as well as the significant synergistic effect between iron and nickel, which is further verified by the theoretical calculation. This approach can be extended to precisely adjust the morphology of MOFs and their derivatives that can result in superior electrocatalytic properties in terms of energy conversion and storage applications.

Higher FT4 level within the normal range predicts the outcome of cryoballoon ablation in paroxysmal atrial fibrillation patients without structural heart disease.

BACKGROUND: Accumulated evidence has indicated that a high-normal FT4 level is an independent risk factor for the clinical progression of AF. However, the association between elevated FT4 concentration within the normal range and AF recurrence after cryoballoon ablation in China is unknown. METHODS: This retrospective and observational study included 453 AF patients who underwent cryoballoon ablation from January 2016 to August 2018. Patients were classified into quartiles based on preprocedural serum FT4 concentration. The clinical characteristics of the patients and the long-term rate of AF recurrence after ablation were assessed. RESULTS: After a mean follow-up period of 17.4 ± 9.0 months, 91 (20.1%) patients suffered from AF recurrence. The AF recurrence rate by FT4 quartile was 17.7%, 19.0%, 21.4%, and 22.3% for participants with FT4 in quartile 1, 2, 3, and 4, respectively (p < .001). On multivariate Cox regression, FT4 concentration (HR: 1.187, 95% CI: 1.093-1.290, p < .001) and left atrial diameter (HR: 1.052, 95% CI: 1.014-1.092, p = .007) were significant predictors of AF recurrence. When stratifying for AF type, the rate of postoperative recurrence was independently increased as FT4 concentration increased in paroxysmal AF, but not in persistent AF (p < .001 in paroxysmal AF and p = .977 in persistent AF). CONCLUSION: Higher FT4 level within the normal range predicted the outcome of cryoballoon ablation in Chinese paroxysmal AF patients without structural heart disease.

Serum Uric Acid Revealed a U-Shaped Relationship With All-Cause Mortality and Cardiovascular Mortality in High Atherosclerosis Risk Patients: The ASSURE Study.

Background: Previous studies have demonstrated an association between hyperuricemia and cardiovascular disease (CVD). The Framingham study confirmed that patients with high atherosclerotic risks (HARs) had worse prognoses. However, after adjusting for confounding factors, the association between serum uric acid (SUA) and all-cause mortality and cardiovascular mortality remains unclear, especially for HAR patients. Objective: The aim of this study was to reveal the relationship of SUA with all-cause and cardiovascular mortality in HAR patients. Methods: This multicenter cohort study enrolled 3,047 participants, and the follow-up was 68.85 ± 11.37 months. Factors related to cardiovascular and all-cause mortality were tested by multivariate Cox regression analysis. Restricted cubic splines (RCSs) with knots were used to explore the shape of the dose-response relationship with SUA and the hazard ratio (HR) of all-cause and CVD mortality. SUA transformed by RCS was added to the Cox regression model as an independent variable, and all-cause and CVD mortality scores were calculated. Survival receiver operating characteristic curves were produced using a regression model predicting the score. Results: SUA demonstrated a "U-shaped" relationship with all-cause and cardiovascular mortality. SUA predicted all-cause and CVD mortality, with cutoff values of values of >370.5 µmol/L for males and >327.65 µmol/L for females and <180.5 µmol/L for males and <165.7 µmol/L for females, respectively. The survival ROC curve indicated that SUA is able to predict all-cause and CVD mortality, with areas under the curve of 0.702 and 0.711, respectively. The HRs of all-cause mortality (male and female) with hyperuricemia and hypouricemia were 2.08 and 2.01 and 2.04 and 1.98, respectively, and the HRs of CVD mortality (male and female) were 2.09 and 1.79, and 2.02 and 1.89, respectively. Conclusion: Abnormal SUA levels were significant and independent risk factors for all-cause and CVD mortality. Hyperuricemia and hypouricemia increased mortality in both males and females. Routine SUA evaluation and intensive management are needed for HAR patients. Clinical Trial Registration: www.ClinicalTrials.gov, identifier: NCT03616769.

Decreased plasma musclin levels are associated with potential atrial fibrillation in non-diabetic patients.

BACKGROUND: Musclin is involved in the regulation of natriuretic peptide (NP) clearance and may affect the concentration of atrial natriuretic peptide (ANP). It has also been found to play an important role in several diseases, such as diabetes mellitus and hypertension. Both abnormalities in ANP and associated medical history are involved in the pathogenesis of atrial fibrillation (AF). However, plasma concentration of musclin as a biomarker for risk stratification in patients with AF has not been fully investigated. METHODS: Plasma musclin levels were measured in 290 patients with AF (including 199 paroxysmal AF patients and 91 persistent AF patients) and 120 control subjects. The association between plasma musclin levels and AF onset, as well as its predictive effects on clinical outcomes after cryoballoon ablation were analyzed. RESULTS: AF patients were found to have a lower concentration of plasma musclin than healthy controls. Moreover, in the non-diabetic group and normal N-terminal pro-brain natriuretic peptide (NT-proBNP) level group, the association between lower plasma concentration of musclin and AF remained significant. According to receiver operating characteristic (ROC) curve analysis, the optimal cut-off point of musclin for predicting AF onset was 54.94 ng/mL, which had a sensitivity of 81.67% and a specificity of 31.47% [area under the ROC curve (AUC) =60.71%]. In follow-up studies, both diabetes and left atrial size were independent predictors of AF recurrence after ablation, while musclin showed only a modest relationship with the outcome of cryoballoon ablation. CONCLUSIONS: Our data indicated that decreased musclin was associated with the onset of AF. Moreover, lower plasma levels of musclin were an independent risk factor of AF in non-diabetic patients. Our studies suggest that musclin could be a predictive factor for the onset of AF.

Rs4968309 in Myosin Light Chain 4 (MYL4) Associated With Atrial Fibrillation Onset and Predicts Clinical Outcomes After Catheter Ablation in Atrial Fibrillation Patients Without Structural Heart Disease.

BACKGROUND: Atrial fibrillation (AF) is the most common arrhythmia with serious complications and a high rate of recurrence after catheter ablation. Recently, mutation ofMYL4was reported as responsible for familial atrial cardiomyopathy and AF. This study aimed to determine the association between polymorphism inMYL4with the onset and recurrence of AF.Methods and Results:A total of 7 single-nucleotide polymorphisms were selected by linkage disequilibrium and genotyped in 510 consecutive AF patients and 192 controls without structural heart disease. A total of 246 AF patients who underwent cryoballoon ablation had a 1-year scheduled follow-up study for AF recurrence. C allele and CC genotype of rs4968309 and A allele of rs1515751were associated with AF onset both before and after adjustment of covariation (age, sex, hypertension, and diabetes). AF type and left atrial size were different among the genotypes of rs4968309. Moreover, CC genotype of rs4968309 increased susceptibly of AF recurrence after cryoballoon ablation. The prevalence of hypertension was associated with rs1515752, and left atrial size was associated with the genotype of rs2071438. CONCLUSIONS: C allele and CC genotype of rs4968309 inMYL4were associated with AF onset and recurrence. Moreover, the A allele of rs1515751 had a significant association with AF onset. The polymorphisms ofMYL4can predict AF onset and prognosis after ablation in AF patients without structural heart disease.

Network propagation with dual flow for gene prioritization.

Based on the hypothesis that the neighbors of disease genes trend to cause similar diseases, network-based methods for disease prediction have received increasing attention. Taking full advantage of network structure, the performance of global distance measurements is generally superior to local distance measurements. However, some problems exist in the global distance measurements. For example, global distance measurements may mistake non-disease hub proteins that have dense interactions with known disease proteins for potential disease proteins. To find a new method to avoid the aforementioned problem, we analyzed the differences between disease proteins and other proteins by using essential proteins (proteins encoded by essential genes) as references. We find that disease proteins are not well connected with essential proteins in the protein interaction networks. Based on this new finding, we proposed a novel strategy for gene prioritization based on protein interaction networks. We allocated positive flow to disease genes and negative flow to essential genes, and adopted network propagation for gene prioritization. Experimental results on 110 diseases verified the effectiveness and potential of the proposed method.