Engineering Internal and External Low-Coordination Atoms in Nickel-Organic Framework Nanoarrays to Promote the Electrochemical Oxygen Evolution Reaction.

Monometallic nickel-organic frameworks based on a carboxylated ligand [2,6-naphthalenedicarboxylic acid (Ni-NDC)] have abundant and uniformly distributed single-atom Ni sites, enabling superior oxygen evolution reaction (OER) activity. In theory, most of the Ni atoms inside Ni-NDC microcrystals are coordinatively saturated except for the surface. Therefore, there are no accessible low-coordination atoms (LCAs) as electrocatalytic sites for the OER. One effective way is to expose more LCAs by preparing self-supporting Ni-NDC nanoarrays (Ni-NDC NAs) with hierarchical secondary structural units. Another effective method is to create more internal LCAs by removing partial ligands or coordination atoms attached to the Ni atoms. Herein, by combining the two strategies, we engineered LCAs in the interior and exterior of Ni-NDC to synergistically accelerate the OER. In brief, ultrathick "brick-like" Ni-NDC NAs were first prepared with dissolution and coordination effects of NDC on self-sacrificial templates of "agaric-like" nickel hydroxide nanoarrays [Ni(OH)2 NAs]. Subsequently, dual-coordinated NDC was partially replaced by monocoordinated 2-naphthoic acid (NA). The Ni-NDC NAs were further tailed into ultrathin "liner leaf-like" nanoneedle arrays (LCAs-Ni-NDC NAs). As a consequence, the LCAs-Ni-NDC NAs have more internal and external LCAs, which can deliver an OER performance that is superior to that of Ni-NDC NAs.

Preoperative Frailty Assessment Predicts Postoperative Mortality, Delirium and Pneumonia in Elderly Lung Cancer Patients: A Retrospective Cohort Study.

BACKGROUND: The purpose of this study was to investigate the predictive value of the 5-factor modified frailty index (mFI-5) for postoperative mortality, delirium and pneumonia in patients over 65 years of age undergoing elective lung cancer surgery. METHODS: Data were collected from a single-center retrospective cohort study conducted in a general tertiary hospital from January 2017 to August 2019. In total, the study included 1372 elderly patients aged over 65 who underwent elective lung cancer surgery. They were divided into frail group (mFI-5, 2-5), prefrail group (mFI-5, 1) and robust group (mFI-5, 0) on the basis of mFI-5 classification. The primary outcome was postoperative 1-year all-cause mortality. Secondary outcomes were postoperative pneumonia and postoperative delirium. RESULTS: Frailty group had the highest incidence of postoperative delirium (frailty 31.2% versus prefrailty 1.6% versus robust 1.5%, p < 0.001), postoperative pneumonia (frailty 23.5% versus prefrailty 7.2% versus robust 7.7%, p < 0.001), and postoperative 1-year mortality (frailty 7.0% versus prefrailty 2.2% versus robust 1.9%. p < 0.001). Frail patients have significantly longer length of hospitalization than those in the robust group and prefrail patients (p < 0.001). Multivariate analysis showed a clear link between frailty and increased risk of postoperative delirium (aOR 2.775, 95% CI 1.776-5.417, p < 0.001), postoperative pneumonia (aOR 3.291, 95% CI 2.169-4.993, p < 0.001) and postoperative 1-year mortality (aOR 3.364, 95% CI, 1.516-7.464, p = 0.003). CONCLUSIONS: mFI-5 has potential clinical utility in predicting postoperative death, delirium and pneumonia incidence in elderly patients undergoing radical lung cancer surgery. Frailty screening of patients (mFI-5) may provide benefits in risk stratification, targeted intervention efforts, and assist physicians in clinical decision-making.

Accelerating Electrochemical Water Oxidation Activity by Tailoring Morphology and Electronic Structure of Nickel Organic Framework Nanoarrays with a Fe Etching Effect.

Fe-mediated nickel organic framework nanoarrays (NiFe-MOFs NAs) on carbon cloth were successfully constructed from ultrathin nanosheets via an etching effect. This strategy also combined the dissolution and coordination effect of acidic ligand (2,6-naphthalenedicarboxylic acid, NDC) to a self-sacrificial template of Ni(OH)2 NAs. Benefiting from the strong Fe etching effect, dense and thick brick-like Ni-NDC nanoplates were tailored into loose and ultrathin NiFe-NDC nanosheets with abundant squamous nanostructures, which were still tightly attached to carbon cloth. As a consequence, more coordinatively unsaturated metal sites (CUMSs) that served as active centers were exposed to accelerate oxygen production. Meanwhile, the electronic structure of active Ni centers was modulated by the incorporation of Fe atoms. The charge density redistribution between Ni and Fe ultimately optimized the energy barrier of the adsorption/desorption of oxygenated intermediates, promoting the kinetics for water oxidation.

Introducing a Synergistic Ligand Containing an Exotic Metal in Metal-Organic Framework Nanoarrays Enabling Superior Electrocatalytic Water Oxidation Performance.

Designing and fabricating well-aligned metal-organic framework nanoarrays (MOF NAs) with high electrocatalytic activity and durability for water oxidation at large current density remain huge challenges. Here the vertical NiFc-MOF NAs constructed from agaric-like nanosheets were fabricated by introducing a ligand containing an exotic Fe atom to coordinate with Ni ion using Ni(OH)2 NAs as a self-sacrificing template. The NiFc-MOF NAs exhibited superior water oxidation performance with a very low overpotential of 161 mV at the current density of 10 mA cm-2. Chronoamperometry was tested at an overpotential of 250 mV, which delivered an initial industrial-grade current density of 702 mA cm-2 and still remained at 694 mA cm-2 after 24 h. Furthermore, it possessed fast reaction kinetics with a small Tafel slope of 29.5 mV dec-1. The superior electrocatalytic performance can be ascribed to the structural advantage of vertically grown agaric-like NAs and the synergistic electron coupling between Ni and Fe atoms, namely, electron transfer from Ni to Fe atoms in NiFc-MOF NAs. The exposed density and valence state of active Ni sites were synchronously increased. Furthermore, the energy barrier for the adsorption/desorption of oxygenated intermediates was ultimately optimized for water oxidation. This work provides a novelty orientation to accelerate electrocatalytic performance of MOF NAs by introducing self-sacrificing templates containing one metal and synergistic ligand containing dissimilar metal.

Efficient extraction of trace organochlorine pesticides from environmental samples by a polyacrylonitrile electrospun nanofiber membrane modified with covalent organic framework.

Detecting and analyzing of the trace organochlorine pesticides (OCPs) in the real water has become a big challenge. In this work, a novel functional electrospun nanofiber membrane (PAN@COFs) was synthesized through the in situ growth of covalent organic frameworks (COFs) on a polyacrylonitrile electrospun nanofiber membranes under room temperature and used in the solid-phase micro-extraction (SPME) to enrich trace organochlorine pesticides (OCPs) in water. The resulted PAN@COFs composite consisted of numerous nanofibers coated ample porous COFs spheres (~ 500 nm) and owned stable crystal structure, abundant functional groups, good stability. In addition, the enrichment experiments clearly revealed that PAN@COFs exhibited rather outstanding performance on adsorbing the trace OCPs (as low as 10 ng L-1) with the enrichment of 482-2686 times. Besides, PAN@COFs displayed good reusability and could be reused 100 times. Notably, in the real water samples (sea water and river water), the high enrichment factors and recovery rates strongly confirmed the feasibility of PAN@COFs for detecting the trace OCPs. Furthermore, due to the synergy of π-π stacking interaction and hydrophobic interaction between the OCPs molecules and PAN@COFs, the OCPs could be efficiently adsorbed on PAN@COFs, even under the extremely low driving force.

Surfactant-Free Approach for Engineering an Ultrathin Ti-Doped Ni(OH)2 Nanosheet on Carbon Cloth: Experimental and Theoretical Insight into Boosted Alkaline Water Oxidation Activity.

Ti-based layered double hydroxides (LDHs) have enormous potential in photocatalysis, electrocatalysis, and photoelectrocatalysis. However, Ti-based LDHs are rarely reported because of the difficulties of the preparation process, in which the Ti precursors are more prone to hydrolysis into titanium hydroxide. In this work, toward robust, efficient, and earth-abundant electrocatalysts for water oxidation in alkaline environments, we have engineered Ti-doped Ni(OH)2 nanosheet arrays on carbon cloth [Ti-Ni(OH)2/CC] with a facile solvothermal and surfactant-free method. The experimental tests show that the activity of Ti-Ni(OH)2-1/CC (∼12.5 atom % Ti substitution) is optimal among these materials. In addition, the activity is correlated with the Ti substitution ratio and reversed with higher Ti doping level (≥25 atom % Ti substitution). Therein, η10 of Ti-Ni(OH)2-1/CC is as low as 196 mV, and it is still maintained at 210 mV after a long-term chronopotentiometry (CP) test at a constant current density of 10 mA cm-2 for 32 h, demonstrating superior activity and long-term durability. Density functional theory calculations further reveal that dilute Ti substitution produces extra active sites and promotes more optimal OH* adsorption to the surface of the electrocatalyst.

Development and validation of a prognostic nomogram for patients with intravesical recurrence after radical nephroureterectomy for non-metastatic upper tract urothelial carcinoma.

PURPOSE: To develop and validate a prognostic nomogram for patients with intravesical recurrence (IVR) after radical nephroureterectomy (RNU) for non-metastatic upper tract urothelial carcinoma (UTUC). METHODS: The clinical data of 468 patients registered in the surveillance, epidemiology and end results database between 2010 and 2015 were retrospectively analyzed. Multivariate analysis using the Cox proportional hazard model was used to determine independent prognostic factors for the development of a nomogram to predict the 1-, 3-, and 5-year probability of individual cancer-specific survival (CSS). Moreover, the nomogram was internally validated using receiver operating characteristic curves and calibration plots. RESULTS: Age at IVR > 80 years, UTUC stage ≥ T3, bladder cancer (BC) stage T1, and muscle-invasive BC (stage ≥ T2) were identified as independent risk factors for CSS in patients with IVR after RNU, whereas a time interval of > 24 months between UTUC and BC was an independent protective factor. The 1-, 3-, and 5-year predictive accuracies of our nomogram were 0.74, 0.70, and 0.71, respectively. Additionally, 1-, 3-, and 5-year calibration curves demonstrated perfect agreement between the nomogram-predicted and the actual CSS. CONCLUSIONS: This study developed and internally validated the first nomogram to date to predict individual prognosis in patients with IVR after RUN for UTUC. This nomogram can be used for patient counseling and for designing clinical trials.

Development and validation of a SEER-based prognostic nomogram for patients with bone metastatic prostate cancer.

Controversies exist between the previous two prognostic nomograms for patients with bone metastatic prostate cancer (PCa), and a nomogram applied to western patients has yet to be established. Thus, we aimed to build a reliable and generic nomogram to individualize prognosis.The independent prognostic factors were identified in a retrospective study of 1556 patients with bone metastatic PCa registered in the Surveillance, Epidemiology and End Results (SEER) database. Besides, the prognostic nomogram was developed using R software according to the result of multivariable Cox regression analysis. Then, the discriminative ability of the nomogram was assessed by analyses of receiver operating characteristic curves (ROC curves). We also performed 1-, 2-, and 3-year calibrations of the nomogram by comparing the predicted survival to the observed survival. Furthermore, the model was externally validated using the data of 711 patients diagnosed at different times enrolled in the SEER database.Age ≥70 years, Gleason score ≥8, PSA value of 201 to 900 ng/ml, stage T4, stage N1, with liver metastases, and Asian/Pacific ethnicity were identified as independent prognostic factors. In the primary cohort, 1-, 2-, and 3-year area under the ROC curve (AUC) of the nomogram for predicting cancer-specific survival (CSS) were 0.71, 0.70, and 0.70, respectively. Besides 1-, 2-, and 3-year AUC were 0.70, 0.68, and 0.69, respectively, in the external validation cohort. Moreover, calibration curves presented perfect agreements between the nomogram-predicted and actual 1-, 2-, and 3-year CSS rate in both the primary and external validation cohorts. In other words, our nomogram has great predictive accuracy and reliability in predicting 1-, 2-, and 3-year CSS for patients with bone metastatic prostate cancer.This study established and validated a prognostic nomogram applied to not only Asian patients but western patients with bone metastatic PCa, which will be useful for patients' counseling and clinical trial designing.

Synthesis of Double-Layer Nitrogen-Doped Microporous Hollow Carbon@MoS2/MoO2 Nanospheres for Supercapacitors.

In this work, a double-layer nitrogen-doped microporous hollow carbon@MoS2/MoO2 nanosphere (NCs@MoS2/MoO2) is prepared via a facile method utilizing Mo-mediated in situ growth on polyaniline-coated polystyrene spheres and carbonization process. Because of its unique structure, the as-obtained NCs@MoS2/MoO2 exhibits a high specific capacitance (569 F g-1 at 1 A g-1) and excellent rate performance (54.8% capacitance retention) from 1 A g-1 (569 F g-1) to 20 A g-1 (312 F g-1) when directly used as a supercapacitor electrode. In a two-electrode system, it exhibits 81% capacitance retention and 91.4% Coulombic efficiency even after 5000 cycles at 5 A g-1. Therefore, the prepared NCs@MoS2/MoO2 shows to be an outstanding material for supercapacitor electrodes.

Hypoxia upregulates HIG2 expression and contributes to bevacizumab resistance in glioblastoma.

Hypoxia contributes to the maintenance of stem-like cells in glioblastoma (GBM), and activates vascular mimicry and tumor resistance to anti-angiogenesis treatments. The present study examined the expression patterns and biological significance of hypoxia-inducible protein 2 (HIG2, also known as HILPDA) in GBM. HIG2 was highly expressed in gliomas and was correlated with tumor grade, and high HIG2 expression independently predicted poor GBM patient prognosis. HIG2 was upregulated during hypoxia and by hypoxia mimics, and HIG2 knockdown in GBM cells inhibited cell proliferation and invasion. HIF1α bound to the HIG2 promoter and increased its expression in GBM cells, and HIG2 upregulated HIF1α expression. Reconstruction of a HIG2-related molecular network using bioinformatics methods revealed that HIG2 is closely correlated with angiogenesis genes, such as VEGFA, in GBM. HIG2 levels positively correlated with VEGFA in GBM samples. In addition, treatment of transplanted xenograft nude mice with bevacizumab (anti-angiogenesis therapy) resulted in HIG2 upregulation at late stages. We conclude that HIG2 is overexpressed in GBM and upregulated by hypoxia, and is a potential novel therapeutic target. HIG2 overexpression is an independent prognostic indicator and may promote tumor resistance to anti-angiogenesis treatments.