Ionic Liquid-Accelerated Growth of Covalent Organic Frameworks with Tunable Layer-Stacking.

Layer-stacking behaviors are crucial for two-dimensional covalent organic frameworks (2D COFs) to define their pore structure, physicochemical properties, and functional output. So far, fine control over the stacking mode without complex procedures remains a grand challenge. Herein, we proposed a "key-cylinder lock mimic" strategy to synthesize 2D COFs with a tunable layer-stacking mode by taking advantage of ionic liquids (ILs). The staggered (AB) stacking (unlocked) COFs were exclusively obtained by incorporating ILs of symmetric polarity and matching molecular size; otherwise, commonly reported eclipsed (AA) stacking (locked) COFs were observed instead. Mechanistic study revealed that AB stacking was induced by a confined interlocking effect (CIE) brought by anions and bulky cations of the ILs inside pores ("key" and "cylinder", respectively). Excitingly, this strategy can speed up production rate of crystalline powders (e.g., COF-TAPT-Tf@BmimTf2N in merely 30 minutes) under mild reaction conditions. This work highlights the enabling role of ILs to tailor the layer stacking of 2D COFs and promotes further exploration of their stacking mode-dependant applications.

Reprocessible Triketoenamine-Based Vitrimers with Closed-Loop Recyclability.

Development of thermosets that can be repeatedly recycled via both chemical route (closed-loop) and thermo-mechanical process is attractive and remains an imperative task. In this work, we reported a triketoenamine based dynamic covalent network derived from 2,4,6-triformylphloroglucinol and secondary amines. The resulting triketoenamine based network does not have intramolecular hydrogen bonds, thus reducing its π-electron delocalization, lowering the stability of the tautomer structure, and enabling its dynamic feature. By virtue of the highly reversible bond exchange, this novel dynamic covalent bond enables the easy construction of highly crosslinked and chemically reprocessable networks from commercially available monomers. The as-made polymer monoliths exhibit high mechanical properties (tensile strength of 79.4 MPa and Young's modulus of 571.4 MPa) and can undergo a monomer-network-monomer (yields up to 90 %) recycling mediated by an aqueous solution, with the new-generation polymer capable of restoring the material strength to its original state. In addition, owing to its dynamic nature, a catalyst-free and low-temperature reprogrammable covalent adaptable network (vitrimer) was achieved. The design concept reported herein can be applied to the development of other novel vitrimers with high repressibility and recyclability, and sheds light on future design of sustainable polymers with minimal environmental impact.

Development and validation of a nomogram for prognosis of sinonasal adenocarcinoma (a nomogram for sinonasal adenocarcinoma).

BACKGROUND: The incidence of sinonasal adenocarcinoma is low, and there are few studies on survival and prognosis. Therefore, we aim to develop and validate a prognostic model for predicting the overall survival of sinonasal adenocarcinoma and provide guidance for clinical management. METHODS: Patients who were diagnosed as sinonasal adenocarcinoma through Surveillance, Epidemiology, and End Results database between 1975 and 2015 were randomly divided into a training group and validation group. Univariate, multivariate survival analysis was performed to screen independent survival factors. A nomogram was established to predict the overall survival rate of sinonasal adenocarcinoma. Receiver operating characteristic curve and calibration plot were performed to verify the discrimination and accuracy of the model. A decision curve analysis was performed to verify the clinical applicability of the model. RESULTS: A total of 423 patients with sinonasal adenocarcinoma were randomly divided into training group (n = 299) and verification group (n = 124). We established and verified the Nomo map including age, marriage, grade, surgery and tumour size. The c-index of Surveillance, Epidemiology, and End Results stage, T stage and this model are 0.635, 0.626 and 0.803, respectively. The survival rate of the high-risk group scored by this model was lower than that of the low-risk group (P < 0.001). Decision curve analysis shows that the model has advantages in predicting survival rates. CONCLUSION: Our model is considered to be a useful tool for predicting the overall survival of sinonasal adenocarcinoma, with good discrimination and clinical applicability. We hope that this model will help rhinologists to make clinical decisions and manage patients diagnosed with sinonasal adenocarcinoma.

Relation between endothelial nitric oxide synthase genetic polymorphisms and pulmonary arterial hypertension in newborns with congenital heart disease.

OBJECTIVE: To investigate whether endothelial nitric oxide synthase (eNOS) rs1799983, rs2070744, and rs61722009 gene polymorphisms are associated with pulmonary arterial hypertension (PAH) in South Fujian newborns with congenital heart disease (CHD). METHODS: Genotyping for the eNOS rs1799983, rs2070744, and rs61722009 polymorphisms was performed using Sanger sequencing in 50 newborns with PAH secondary to CHD [CHD PAH (+)], 52 newborns with CHD without PAH [CHD PAH (-)], and 60 healthy controls. RESULTS: The genotype and allele frequency distributions of eNOS rs1799983, rs2070744, and rs61722009 were similar between CHD and healthy controls (P > .05). The frequencies of the eNOS rs1799983 G/T allele were 85% and 15% in the CHD PAH (+) group and 96.15% and 3.85% in the CHD PAH (-) group, the frequency of the T allele was higher in the CHD PAH (+) group than in the CHD PAH (-) group(P< .05), and patients with the GT/TT genotypes of eNOS rs1799983 may present higher PAH (OR = 4.412, 95%CI:1.411-13.797, P= .011). Newborns with the GT/TT genotypes had decreased plasma NO production compared to newborns with the GG genotype (P< .01), and NO levels in the CHD PAH (+) group were significantly lower than those in the CHD PAH (-) group (P < .05). CONCLUSION: The T allele could be a risk factor for PAH in newborns with CHD in South Fujian through decreased levels of nitric oxide production by the endothelium.

Effect of vanadium and tungsten loading order on the denitration performance of F-doped V2O5-WO3/TiO2 catalysts.

F-doped V2O5-WO3/TiO2 catalyst has been confirmed to have excellent denitration activity at low temperatures. Since the V2O5-WO3/TiO2 catalyst is a structure-sensitive catalyst, the loading order of V2O5 and WO3 may affect its denitration performance. In this paper, a series of F-doped V2O5-WO3/TiO2 catalysts with different V2O5 and WO3 loading orders were synthesized to investigate the effect of denitration performance at low temperatures. It was found that the loading orders led to significant gaps in denitration performance in the range of 120-240 °C. The results indicated loading WO3 first better utilized the oxygen vacancies on the TiF carrier promoting the generation of reduced vanadium species. In addition, loading WO3 first facilitated the dispersion of V2O5 thus enhanced the NH3 adsorption capacity of VWTiF. In situ DRIFT verified the rapid reaction between NO2, nitrate, and nitrite species and adsorbed NH3 over the VWTiF, confirming that the NH3 selective catalytic reduction (NH3-SCR) reaction over VWTiF at 240 °C proceeded by the Langmuir-Hinshelwood (L-H) mechanism. This research established the constitutive relationship between the loading order of V2O5 and WO3 and the denitration performance of the F-doped VWTi catalyst providing insights into the catalyst design process.

Thiol-grafted covalent organic framework-based electrochemical platforms for sensitive detection of Hg(II) ions.

Triazine-based covalent organic frameworks functionalized by thiol and thioether (COFS-CH3/COFS-SH) were designed and served as a platform that could bind with mercury ions specifically based on Hard-Soft-Acid-Base theory. As such, when employing COFs as a modifier in a carbon paste electrode (CPE), the COFS-CH3-modified CPE revealed an extraordinary performance (detection limit of 0.01 ppb; linear range of 0.1 to 1.0 ppb) and repeatability for electrochemical detection of trace mercury, even in real samples collected from tap or lake water. This innovative approach leverages the inherent properties of covalent organic frameworks (COFs) to enable highly sensitive and selective detection of target analytes.

Dietary fats and serum lipids in relation to the risk of ovarian cancer: a meta-analysis of observational studies.

Although numerous epidemiological studies investigated the association between dietary fat intakes or serum lipid levels and ovarian cancer risk, a consistent and explicit conclusion for specific dietary fats or serum lipids that increase the risk of ovarian cancer is not available. In this study, a systematic review and meta-analysis were conducted to assess the key dietary fats and serum lipids that increased the risk of ovarian cancer. Databases such as PubMed, Web of Science, and EMBASE were searched for observational studies. A total of 41 studies met the inclusion criteria, including 18 cohort and 23 case-control studies (109,507 patients with ovarian cancer and 2,558,182 control/non-ovarian cancer participants). Higher dietary intakes of total fat (RR = 1.19, 95% CI = 1.06-1.33, I2 = 60.3%), cholesterol (RR = 1.14, 95% CI = 1.03-1.26, I2 = 19.4%), saturated fat (RR = 1.13, 95% CI = 1.04-1.22, I2 = 13.4%), and animal fat (RR = 1.21, 95% CI = 1.01-1.43, I2 = 70.5%) were significantly associated with a higher risk of ovarian cancer. A higher level of serum triglycerides was accompanied by a higher risk of ovarian cancer (RR = 1.33, 95% CI = 1.02-1.72, I2 = 89.3%). This meta-analysis indicated that a higher daily intake of total fat, saturated fat, animal fat, and cholesterol and higher levels of serum triglycerides were significantly associated with an increased risk of ovarian cancer.

Prediction of Clinical Outcome in Endometrial Carcinoma Based on a 3-lncRNA Signature.

Endometrial carcinoma (EC) is one of the common gynecological cancers with increasing incidence and revived mortality recently. Given the heterogeneity of tumors and the complexity of lncRNAs, a panel of lncRNA biomarkers might be more precise and stable for prognosis. In the present study, we developed a new lncRNA model to predict the prognosis of patients with EC. EC-associated differentially expressed long noncoding RNAs (lncRNAs) were identified from The Cancer Genome Atlas (TCGA). Univariate COX regression and least absolute shrinkage and selection operator (LASSO) model were selected to find the 8-independent prognostic lncRNAs of EC patient. Furthermore, the risk score of the 3-lncRNA signature for overall survival (OS) was identified as CTD-2377D24.6 expression × 0.206 + RP4-616B8.5 × 0.341 + RP11-389G6.3 × 0.343 by multivariate Cox regression analysis. According to the median cutoff value of this prognostic signature, the EC samples were divided into two groups, high-risk set (3-lncRNAs at high levels) and low-risk set (3-lncRNAs at low levels), and the Kaplan-Meier survival curves demonstrated that the low-risk set had a higher survival rate than the high-risk set. In addition, the 3-lncRNA signature was closely linked with histological subtype (p = 0.0001), advanced clinical stage (p = 0.011), and clinical grade (p < 0.0001) in EC patients. Our clinical samples also confirmed that RP4-616B8.5, RP11-389G6.3, and CTD-2377D24.6 levels were increased in tumor tissues by qRT-PCR and in situ hybridization. Intriguingly, the p-value of combined 3-lncRNAs was lower than that of each lncRNA, indicating that the 3-lncRNA signature also showed higher performance in EC tissue than paracancerous. Functional analysis revealed that cortactin might be involved in the mechanism of 3-lncRNA signatures. These findings provide the first hint that a panel of lncRNAs may play a critical role in the initiation and metastasis of EC, indicating a new signature for early diagnosis and therapeutic strategy of uterine corpus endometrial carcinoma.

Bimetallic PtCu Nanocrystal Sensitization WO3 Hollow Spheres for Highly Efficient 3-Hydroxy-2-butanone Biomarker Detection.

As a foodborne bacterium, Listeria monocytogenes (LM) can cause serious diseases and even death to weak people. 3-Hydroxy-2-butanone (3H-2B) has been proven to be a biomarker for exhalation of LM. Detection of 3H-2B is a fast and effective method for determining whether the food is infected. Herein, we present an excellent 3H-2B gas sensor based on bimetallic PtCu nanocrystal modified WO3 hollow spheres. The structure and morphology of the PtCu/WO3 were characterized, and their gas sensitivities were measured by a static testing method. The results showed that the sensor response of WO3 hollow spheres was enhanced by about 15 times after modification with bimetallic PtCu nanocrystal. The maximum response value of the PtCu/WO3 sensor to 10 ppm 3H-2B is as high as 221.2 at 110 °C. In addition, the PtCu/WO3 sensor also exhibited good selectivity to 3H-2B, fast response/recovery time (9 s/28 s), and low limit of detection (LOD < 0.5 ppm). Furthermore, the sensitivity mechanism was studied by monitoring the reaction products by gas chromatography-mass spectrometry. The excellent gas-sensing performance can be attributed to the synergy between PtCu and WO3, including the unique spillover effect of O2 on PtCu nanoparticles, the regulated depletion layer by p-type CuxO to n-type WO3, and their selective catalysis to 3H-2B. Hence, this work offers the rational design and synthesis of highly efficient sensitive materials for the detection of LM for food security.