Benchmarking boron cluster calculations: Establishing reliable geometrical and energetic references for Bn (n = 1-4).

Using full configuration interaction (FCI) and multi-reference configuration interaction methods (MRCI), reliable geometrical and energetic references for Bn (n = 1-4) clusters were established. The accuracy of the computed results was confirmed by comparison with available experimental data. Benchmark calculations indicated that B97D3, B97D, VSXC, HCTH407, BP86 and CCSD(T) methods provided reasonable results for structural parameters, with mean absolute error (MAEs) within 0.020 Å. Among the tested density functional theory (DFT) methods, the VSXC functional showed the best performance in predicting the relative energies of B1 B4 with a MAE of 12.8 kJ mol-1 . Besides, B1B95, B971, TPSS, B3LYP, and BLYP functionals exhibited reasonable performance with MAE values of less than 15.0 kJ mol-1 . T1 diagnostic values between 0.035 and 0.109 at the CCSD(T) level revealed strong correlations in B2 B4 clusters, highlighting the need for caution in using CCSD(T) as an energy reference for small boron clusters. The methods of CCSDT, CCSDT(Q) and CCSDT[Q], which incorporate three-electron and four-electron excitations, effectively improved the accuracy of the energy calculations.

Efficient Hydrogenation of N-Heterocycles Catalyzed by NNP-Manganese(I) Pincer Complexes at Ambient Temperature.

Manganese-catalyzed hydrogenation reactions have aroused widespread interest in recent years. Among the catalytic systems described, especially PNP- and NNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, ketones, nitriles, aldimines and esters. Furthermore, NNP-Mn pincer compounds are efficient catalysts for the hydrogenolysis of less reactive amides, ureas, carbonates, and carbamates. Herein, the synthesis and application of specific imidazolylaminophosphine ligands and the corresponding Mn pincer complexes are described. These new catalysts have been characterized and studied by a combination of experimental and theoretical investigations, and their catalytic activities have been tested in several hydrogenation reactions with good to excellent performance. Especially, the reduction of N-heterocycles can be performed under very mild conditions.

A Model of Basement Membrane-Associated Gene Signature Predicts Liver Hepatocellular Carcinoma Response to Immune Checkpoint Inhibitors.

Liver hepatocellular carcinoma (LIHC) is a highly lethal malignant tumor originating from the digestive system, which is a serious threat to human health. In recent years, immunotherapy has shown significant therapeutic effects in the treatment of LIHC, but only for a minority of patients. The basement membrane (BM) plays an important role in the occurrence and development of tumors, including LIHC. Therefore, this study is aimed at establishing a risk score model based on basement membrane-related genes (BMRGs) to predict patient prognosis and response to immunotherapy. First, we defined three patterns of BMRG modification (C1, C2, and C3) by consensus clustering of BMRG sets and LIHC transcriptome data obtained from public databases. Survival analysis showed that patients in the C2 group had a better prognosis, and Gene Set Variation Analysis (GSVA) revealed that the statistically significant pathways were mainly enriched in the C2 group. Moreover, we performed Weighted Correlation Network Analysis (WGCNA) on the above three subgroups and obtained 179 intersecting genes. We further applied function enrichment analyses, and the results demonstrated that they were mainly enriched in metabolism-related pathways. Furthermore, we conducted the LASSO regression analysis and obtained 4 BMRGs (MPV17, GNB1, DHX34, and MAFG) that were significantly related to the prognosis of LIHC patients. We further constructed a prognostic risk score model based on the above genes, which was verified to have good predictive performance for LIHC prognosis. In addition, we analyzed the correlation between the risk score and the tumor immune microenvironment (TIM), and the results showed that the high-risk scoring group tended to be in an immunosuppressed status. Finally, we investigated the relationship between the risk score and LIHC immune function. The results demonstrated that the risk score was closely related to the expression levels of multiple immune checkpoints. Patients in the low-risk group had significantly higher IPS scores, and patients in the high-risk group had lower immune escape and TIDE score. In conclusion, we established a novel risk model based on BMRGs, which may serve as a biomarker for prognosis and immunotherapy in LIHC.

Divergent Synthesis of Alcohols and Ketones via Cross-Coupling of Secondary Alcohols under Manganese Catalysis.

A homogeneous manganese-catalyzed cross-coupling of two secondary alcohols for the divergent synthesis of γ-disubstituted alcohols and ß-disubstituted ketones is reported. Employing the well-defined Mn-MACHOPh as the catalyst, this novel protocol has a broad substrate scope with good functional group tolerance and affords a diverse library of valuable disubstituted alcohols and ketones in moderate to good yields. The strong influence of the reaction temperature on the selective formation of alcohol products was theorized in preliminary DFT studies. Studies have shown that the Gibbs free energy of the formation of alcohols is thermodynamically more favourable than corresponding ketones at a lower temperature.

Benefits of successful percutaneous coronary intervention in chronic total occlusion patients with diabetes.

BACKGROUND: Diabetes was commonly seen in chronic total occlusion (CTO) patients but data regarding the impact of successful percutaneous coronary intervention (PCI) on clinical outcome of CTO patients with diabetes was controversial. And importantly, no studies have compared quality of life (QOL) after CTO-PCI in patients with and without diabetes. METHODS: Consecutive patients undergoing elective CTO-PCI were prospectively enrolled from Apr. 2018 to May 2021. Patients were subdivided into 2 groups: Diabetes and No Diabetes. Detailed baseline characteristics, assessment of symptoms and QOL, angiographic and procedural details, in-hospital complications, and 1 month and 1 year follow-up data were collected. These data were analyzed accordingly for risk predictors of clinical outcome in patients who have diabetes and received successful CTO-PCI. RESULTS: A total of 1076 patients underwent CTO-PCI attempts. Diabetes was present in 374 (34.76%) patients, who had more hypertension, previous PCI and stroke. Regarding the coronary lesions, diabetic patients suffered more LCX lesion, multivessel disease, number of lesions per patient, blunt stump, calcification and higher J-CTO score (p < 0.05). In-hospital major adverse cardiac event (MACE) (4.13% vs. 5.35%; p = 0.362) was similar in the two groups. At 1 month and 1 year follow-up after successful CTO-PCI, the incidence of MACE and all-cause mortality were also similar in the two groups (p > 0.05). Number of lesions per patient was an independent risk factor of MACE and all-cause mortality (p < 0.001) 1 year after successful CTO-PCI. Symptom and QOL were markedly improved regardless of diabetes both at 1 month and 1 year follow-up, and importantly, patients with diabetes showed similar degrees of improvement to those without diabetes (P > 0.05). CONCLUSIONS: Successful CTO-PCI could represent an effective strategy improving clinical outcome, symptoms and QOL in CTO patients with diabetes.

A General and Highly Selective Palladium-Catalyzed Hydroamidation of 1,3-Diynes.

A chemo-, regio-, and stereoselective mono-hydroamidation of (un)symmetrical 1,3-diynes is described. Key for the success of this novel transformation is the utilization of an advanced palladium catalyst system with the specific ligand Neolephos. The synthetic value of this general approach to synthetically useful α-alkynyl-α, ß-unsaturated amides is showcased by diversification of several structurally complex molecules and marketed drugs. Control experiments and density-functional theory (M06L-SMD) computations also suggest the crucial role of the substrate in controlling the regioselectivity of unsymmetrical 1,3-diynes.

Cobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid.

Among the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3. Compared to related ruthenium and manganese complexes 7 and 8, this optimal cobalt complex showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on the triplet state potential energy surface.

Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts.

[Fe(PNP)(CO)HCl] (PNP=di-(2-diisopropylphosphanyl-ethyl)amine), activated in situ with KOtBu, is a highly active catalyst for the isomerization of allylic alcohols to ketones without an external hydrogen supply. High reaction rates were obtained at 80 °C, but the catalyst is also sufficiently active at room temperature with most substrates. The reaction follows a self-hydrogen-borrowing mechanism, as verified by DFT calculations. An alternative isomerization through alkene insertion and ß-hydride elimination could be excluded on the basis of a much higher barrier. In alcoholic solvents, the ketone product is further reduced to the saturated alcohol.

Selective Base-free Transfer Hydrogenation of α,ß-Unsaturated Carbonyl Compounds using iPrOH or EtOH as Hydrogen Source.

Commercially available Ru-MACHOTM -BH is an active catalyst for the hydrogenation of several functional groups and for the dehydrogenation of alcohols. Herein, we report on the new application of this catalyst to the base-free transfer hydrogenation of carbonyl compounds. Ru-MACHOTM -BH proved to be highly active and selective in this transformation, even with α,ß-unsaturated carbonyl compounds as substrates. The corresponding aliphatic, aromatic and allylic alcohols were obtained in excellent yields with catalyst loadings as low as 0.1-0.5 mol % at mild temperatures after very short reaction times. This protocol tolerates iPrOH and EtOH as hydrogen sources. Additionally, scale up to multi-gram amounts was performed without any loss of activity or selectivity. An outer-sphere mechanism has been proposed and the computed kinetics and thermodynamics of crotonaldehyde and 1-phenyl-but-2-en-one are in perfect agreement with the experiment.

Cobalt Pincer Complexes for Catalytic Reduction of Carboxylic Acid Esters.

A selection of cobalt(I) and cobalt(II) pincer type complexes with different substitution patterns was tested in the catalytic reduction of carboxylic acid esters to alcohols. The cobalt pincer type complex 4 is suitable for the hydrogenation of aromatic as well as aliphatic and cyclic esters. Mechanistic investigation indicated a metal ligand cooperated reaction pathway.

Reaction Mechanism for Direct Cyclization of Linear C5 , C6 , and C7 Alkenes over H-ITQ-13 Zeolite Investigated Using Density Functional Theory.

Although dienes or trienes have been shown to be possible precursors for cyclization, direct cyclization of alkenes or alkoxides has not been systematically studied yet. Thus, the reaction mechanism of cyclization of linear alkenes over H-ITQ-13 was investigated here by density functional theory considering dispersive interactions (DFT-D). The similar free energy of different linear alkoxides of the same carbon number suggests that they can co-exist in the H-ITQ-13 intersection at 673.15 K during the methanol to olefins (MTO) process. The formation of linear alkenes by olefins methylation with methoxyl groups (ZOCH3 ), trimethyloxonium ions (TMO+ ), and methanol are kinetically more favorable than by dimerization of olefins. Linear alkoxides or alkenes prefer direct cyclization to cycloalkanes rather than hydride transfer to diene. This study provides new insight into the alkene cyclization and aromatization mechanisms in MTO process.

Ligand- and Solvent-Tuned Chemoselective Carbonylation of Bromoaryl Triflates.

The palladium-catalyzed chemoselective carbonylation of bromoaryl triflates is reported. The selective C-Br bond versus C-OTf (OTf=triflate) bond functionalization can be remarkably tuned by the combination of the ligand [4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) vs. 1,1'-bis(diphenylphosphino)ferrocene (DPPF)] and the solvent (toluene vs. DMSO). The respective ligand and solvent effects are rationalized by DFT calculations. In contrast, the monodentate ligands BuPAd2 and tBu3 P prefer the selective C-Br bond activation and are solvent insensitive.

Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand.

A new chiral manganese PNP pincer complex is described. The asymmetric hydrogenation of several prochiral ketones with molecular hydrogen in the presence of this complex proceeds under mild conditions (30-40 °C, 4 h, 30 bar H2 ). Besides high catalytic activity for aromatic substrates, aliphatic ketones are hydrogenated with remarkable selectivity (e.r. up to 92:8). DFT calculations support an outer sphere hydrogenation mechanism as well as the experimentally determined stereochemistry.

Theoretical insights into the mechanism of olefin elimination in the methanol-to-olefin process over HZSM-5, HMOR, HBEA, and HMCM-22 zeolites.

The mechanism of olefin elimination in the process of methanol-to-olefins (MTO) over a series of zeolites like HZSM-5, HMOR, HBEA, and HMCM-22 was investigated by DFT-D calculations, which is a crucial step that controls the MTO product distribution. The results demonstrate that the manners of olefin elimination are related to the pore structure of zeolite catalyst and the interaction between proton transfer reagent (water or methanol) and zeolite acidic framework. The indirect spiro mechanism is preferable to the direct mechanism over HMOR, HBEA, and HMCM-22 zeolites with large pores, as suggested by the energy barrier of rate-determining step and the potential energy surface (PES), but is unfavorable over HZSM-5 with medium-sized pores due to the steric hindrance of spiro intermediates. Over various zeolites, water and methanol perform differently in proton transfer to form the spiro intermediates; over HMOR and HBEA with strong acidity, water is superior to methanol in promoting propene elimination, whereas over HMCM-22 with relatively weaker acidity, methanol is more favorable as a proton transfer reagent.

Associations between body mass index and all-cause mortality among individuals with psoriasis: results from the NHANES database retrospective cohort study.

Background: Previous findings imply a potential positive association between BMI and all-cause mortality in individuals with psoriasis, yet direct evidence remains absent. This study aimed to fill this gap. Methods: We utilized data from the National Health and Nutrition Examination Survey (NHANES) for the periods 2003-2006 and 2009-2014. Participants' BMI was categorized as lean (<25), overweight (25 ≤ BMI < 30), and obese (BMI ≥ 30). Psoriasis status was determined through self-reporting. The main outcome measured was all-cause mortality up to December 2019. We accounted for multiple covariates, such as sociodemographic factors and histories of smoking and alcohol consumption. Our statistical analyses mainly included Kaplan-Meier survival analysis, Restricted Cubic Spline (RCS) and Multivariate Cox Regression (MCR). We also applied propensity score matching (PSM) to verify the robustness of our findings. Results: Among 22,876 participants, 618 (2.70%) reported a history of psoriasis. An overall effect from the MCR analysis showed that, among individuals with psoriasis, a higher baseline BMI was independently associated with an increased risk of all-cause mortality, noting a 5.5% rise in mortality risk per BMI unit [hazard ratio (HR) = 1.055, 95% CI: 1.004-1.110, p = 0.035]. This significant relationship persisted after PSM. A statistically significant positive correlation was consistent among males, smokers, and individuals younger than 60. However, no such association was found in individuals without a history of psoriasis. Additionally, no significant difference in mortality risk was found between lean and overweight groups with psoriasis, according to the RCS regression and stratified analysis. Conclusion: Our findings indicated a trend that, higher BMIs significantly correlated with increased risks of all-cause mortality in people with psoriasis, particularly among obese ones. However, the impact of being overweight on this relationship remains underexplored. Moreover, the necessity to employ alternative metrics beyond BMI for body fat assessment to further investigate these associations is critical.

Deprotonated 2-thiolimidazole serves as a metal-free electrocatalyst for selective acetylene hydrogenation.

Metal-free catalysts offer a desirable alternative to traditional metal-based electrocatalysts. However, metal-free catalysts, featuring defined active sites, rarely show activities as promising as metal-based materials. Here we report 2-thiolimidazole as an efficient metal-free catalyst for selective electrocatalytic hydrogenation of acetylene into ethylene. Under alkaline conditions, the sulfhydryl and imino groups of 2-thiolimidazole are spontaneously deprotonated into dianions. Deprotonation thus enriches the negative charges of pyridinic N sites in 2-thiolimidazole to enhance the adsorption of electrophilic acetylene through the σ-configuration. Ethylene partial current densities show a volcano relationship with the negative charges of the pyridinic N sites in various imidazole derivatives. Consequently, the deprotonated 2-thiolimidazole exhibits an ethylene partial current density and faradaic efficiency competitive with metal-based catalysts like Cu and Pd. This work highlights the tunability and promising potential of metal-free molecules in electrocatalysis.

BZW2, CDT1 and IVD Act As Biomarkers for Predicting Hepatocellular Carcinoma.

BACKGROUND: Hepatocellular carcinoma (HCC) is the leading cause of cancer-related deaths globally. This study aimed to provide a comprehensive investigation to screen and identify biomarkers for predicting HCC. METHODS: Firstly, the bioinformatics technique was applied to screen potential HCC-related genes, and the relationships between BZW2, CDT1, IVD expression and survival rate and clinicopathological factors were assessed. Afterward, qRT-PCR, western blot and immunohistochemistry were employed to validate the expression of BZW2, CDT1, and IVD in clinical resected cancer specimens. Furthermore, in vitro assays, cell cycle, apoptosis, colony formation and scratch experiments were performed to detect the effects of si-BZW2, si-CDT1 and oe-IVD in HCC cells. In vivo experiments, tumor volume and weight were measured to assess the anti-tumor effect of si-BZW2, si-CDT1 and oe-IVD in HCCtumor- bearing mice. RESULTS: Bioinformatics analysis indicated that HCC patients with high expression of BZW2, CDT1 and low expression of IVD have a poor prognosis and unfavorable clinicopathological factors. Similarly, clinical sample analysis revealed that BZW2 and CDT1 expression were increased while IVD expression was decreased in HCC tissues. Meanwhile, in vitro experiments found that si-BZW2, si- CDT1 and oe-IVD promoted apoptosis and inhibited the colony formation and migration of HCC cells. As expected, in vivo experiments demonstrated that si-BZW2, si-CDT1 and oe-IVD could inhibit tumor growth. CONCLUSION: Increased BZW2, CDT1 levels, and decreased IVD levels could act as biomarkers for predicting HCC. Furthermore, targeting BZW2, CDT1, and IVD may offer a new approach to treat HCC.

Comparative effects of acupuncture and metformin on insulin sensitivity in overweight/obese and lean women with polycystic ovary syndrome and insulin resistance: a post hoc analysis of a randomized trial.

Objective: This study explored the efficacy of acupuncture and metformin in enhancing insulin sensitivity among women with polycystic ovary syndrome (PCOS) and insulin resistance (IR), distinguishing between overweight/obese and lean groups. Methods: A post-hoc analysis of a randomized trial (NCT02491333) was undertaken. Participants were women aged 18-40 with PCOS and IR. They were randomized to receive true acupuncture with a placebo, metformin with sham acupuncture, or sham acupuncture with a placebo for 4 months, with follow-up visits over 3 months. Our study, involving 339 women, assessed the differential impact of acupuncture and metformin on insulin sensitivity in overweight/obese [body mass index (BMI) ≥ 24] versus lean women (BMI < 24). Primary outcomes measured changes in the Homeostatic Model Assessment of Insulin Resistance (HOMA-IR) at 4 and 7 months. Secondary outcomes assessed changes in glucose area under the curve (glucoseAUC) during the oral glucose tolerance test (OGTT) and BMI changes at 4 months. Results: Overweight/obese participants were generally older with higher measurements in various health metrics, but lower levels in specific hormonal metrics compared to lean women (p < 0.05). Among overweight/obese women, metformin outperformed acupuncture in reducing HOMA-IR levels (p = 0.004) and showed a significant drop from the baseline after 4 months (p < 0.05). In contrast, acupuncture's effect on HOMA-IR did not significantly differ from sham acupuncture at 4 and 7 months. For lean women, metformin and acupuncture showed comparable improvements in HOMA-IR, with notable declines at 4 and 7 months (p < 0.05). Acupuncture proved more beneficial for lean women than their overweight/obese counterparts after 4 months (p = 0.021). Conclusion: In overweight/obese women with PCOS and IR, acupuncture was less effective than metformin in enhancing insulin sensitivity. However, in lean women, acupuncture's efficacy was comparable to metformin. Further studies are required to validate these observations.

Nomogram Based on Platelet-Albumin-Bilirubin for Predicting Tumor Recurrence After Surgery in Alpha-Fetoprotein-Negative Hepatocellular Carcinoma Patients.

Purpose: In this study, we developed a nomogram based on the platelet-albumin-bilirubin (PALBI) score to predict recurrence-free survival (RFS) after curative resection in alpha-fetoprotein (AFP)-negative (≤20 ng/mL) hepatocellular carcinoma (HCC) patients. Patients and Methods: A total of 194 pathologically confirmed AFP-negative HCC patients were retrospectively analyzed. Univariate and multivariate Cox regression analyses were performed to screen the independent risk factors associated with RFS, and a nomogram prediction model for RFS was established according to the independent risk factors. The receiver operating characteristic (ROC) curve and the C-index were used to evaluate the accuracy and the efficacy of the model prediction. The correction curve was used to assess the calibration of the prediction model, and decision curve analysis was performed to evaluate the clinical application value of the prediction model. Results: PALBI score, MVI, and tumor size were independent risk factors for postoperative tumor recurrence (P < 0.05). A nomogram prediction model based on the independent predictive factors was developed to predict RFS, and it achieved a good C-index of 0.704 with an area under the ROC curve of 0.661 and the sensitivity was 73.2%. Patients with AFP-negative HCC could be divided into the high-risk group or the low-risk group by the risk score calculated by the nomogram, and there was a significant difference in RFS between the two groups (P < 0.05). Decision curve analysis (DCA) showed that the nomogram increased the net benefit in predicting the recurrence of AFP-negative HCC and exhibited a wider range of threshold probabilities than the independent risk factors (PALBI score, MVI, and tumor size) by risk stratification. Conclusion: The nomogram based on the PALBI score can predict RFS after curative resection in AFP-negative HCC patients and can help clinicians to screen out high-risk patients for early intervention.