Role of H2O Adsorption in CO Oxidation over Cerium-Oxide Cluster Anions (CeO2)nO- (n = 1-4).

Water (H2O) is ubiquitous in the environment and inevitably participates in many surface reactions, including CO oxidation. Acquiring a fundamental understanding of the roles of H2O molecules in CO oxidation poses a challenging but pivotal task in real-life catalysis. Herein, benefiting from state-of-the-art mass-spectrometric experiments and quantum chemical calculations, we identified that the dissociation of a H2O molecule on each of the cerium oxide cluster anions (CeO2)nO- (n = 1-4) at room temperature can create a new atomic oxygen radical (O•-) that then oxidizes a CO molecule. The size-dependent reactivity of H2O-mediated CO oxidation on (CeO2)nO- clusters was rationalized by the orbital compositions (O2p) and energies of the lowest unoccupied molecular orbitals of active O•- radicals modified by H2O dissociation. Our findings not only provide new insights into H2O-mediated CO oxidation but also demonstrate the importance of H2O in modulating the reactivity of the O•- radicals.

Effect of External Electric Field on Nitrogen Activation on a Trimetal Cluster.

Efficient nitrogen (N2) fixation and activation under mild conditions are crucial for modern society. External electric fields (Felectric) can significantly affect N2 activation. In this work, the effect of Felectric on N2 activation by Nb3 clusters supported in a sumanene bowl was studied by density functional theory calculations. Four typical systems at different stages of N-N activation were studied, including two intermediates and two transition states. The impact of Felectric on various properties related to N2 activation was investigated, including the N-N bond length, overlap population density of states (OPDOS), total energy of the system, adsorption energy of N2, decomposition of energy changes, and electron transfer. The sumanene not only functions as a support and protective substrate, but also serves as a donor or acceptor under different Felectric conditions. Negative Felectric is beneficial to N-N bond activation because it promotes electron transfer to the N-N region and improves the d-π* orbital hybridization between metals and N2 in the activation process. Positive Felectric improves d-π* orbital hybridization only when the N-N is nearly dissociated. The microscopic mechanism of Felectric's effects provides insight into N2 activation and theoretical guidance for the design of catalytic reaction conditions for nitrogen reduction reactions (NRR).

Catalysts with Trimetallic Sites on Graphene-like C2N for Electrocatalytic Nitrogen Reduction Reaction: A Theoretical Investigation.

Electrocatalytic nitrogen reduction reaction (NRR) is a green and highly efficient way to replace the industrial Haber-Bosch process. Herein, clusters consisting of three transition metal atoms loaded on C2N as NRR electrocatalysts are investigated using density functional theory (DFT). Meanwhile, Ca was introduced as a promoter and the role of Ca in NRR was investigated. It was found that Ca anchored to the catalyst can act as an electron donor and effectively promote the activation of N2 on M3. In both M3@C2N and M3Ca@C2N (M=Fe, Co, Ni), the limiting potential (UL) is less negative than that of the Ru(0001) surface and has the ability to suppress the competitive hydrogen evolution reaction (HER). Among them, Fe3@C2N is suggested to be the most promising candidate for NRR with high thermal stability, strong N2 adsorption ability, low limiting potential, and good NRR selectivity. The concepts of trimetallic sites and alkaline earth metal promoters in this work provide theoretical guidance for the rational design of atomically active sites in electrocatalytic NRR.

Exploring the stability and aromaticity of rare earth doped tin cluster MSn16- (M = Sc, Y, La).

Rare earth elements have high chemical reactivity, and doping them into semiconductor clusters can induce novel physicochemical properties. The study of the physicochemical mechanisms of interactions between rare earth and tin atoms will enhance our understanding of rare earth functional materials from a microscopic perspective. Hence, the structure, electronic characteristics, stability, and aromaticity of endohedral cages MSn16- (M = Sc, Y, La) have been investigated using a combination of the hybrid PBE0 functional, stochastic kicking, and artificial bee colony global search technology. By comparing the simulated results with experimental photoelectron spectra, it is determined that the most stable structure of these clusters is the Frank-Kasper polyhedron. The doping of atoms has a minimal influence on density of states of the pure tin system, except for causing a widening of the energy gap. Various methods such as ab initio molecular dynamics simulations, the spherical jellium model, adaptive natural density partitioning, localized orbital locator, and electron density difference are employed to analyze the stability of these clusters. The aromaticity of the clusters is examined using iso-chemical shielding surfaces and the gauge-including magnetically induced currents. This study demonstrates that the stability and aromaticity of a tin cage can be systematically adjusted through doping.

Expression level and clinical significance of NBAT-1 in human cancers: a systematic review and meta-analysis.

PURPOSE: There is an aberrant expression of NBAT-1 in various human cancers, which was proven to limit the proliferation, invasion, and metastasis of tumour cells via multiple approaches. Most existing research focuses on sample size and discrete outcomes. Thus, a quantitative meta-analysis was performed to elucidate the prognostic value of lncRNA NBAT-1 expression in cancer patients. MATERIALS AND METHODS: Using Web of Science and PubMed, two researchers independently identified relevant studies to explore the association between the pathological features of human cancers and NBAT-1 expression levels. Then two scholars conducted literature screening according to exclusion criteria and admission criteria, and finally conducted statistical analysis through data extraction with StataSE 12.0. RESULTS: A total of 12 eligible studies with 1600 patients were included in the meta-analysis eventually. It is indicated that the low expression level of lncRNA NBAT-1 was closely related to distant metastasis [RR = 0.50, 95% CI (0.33, 0.76), and P = 0.00], deep tumour invasion [RR = 0.62, 95% CI (0.49,0.80), and P = 0.00], poor histological grade [RR = 0.68, 95% CI (0.57, 0.81), and P = 0.00], advanced TNM stage [RR = 0.66, 95% CI (0.55, 0.79), and P = 0.00], large tumour volume[RR = 0.72, 95% CI (0.55, 0.93), and P = 0.01], and lymph node metastasis [RR = 0.62, 95% CI (0.46, 0.84), and P = 0.00], suggesting that it may serve as biomarkers for patients with poor prognosis. CONCLUSION: Reduced expression of NBAT-1 can predict poor prognosis in several cancers, as found in the meta-analysis, demonstrating that NBAT-1 can serve as a promising prognostic factor of human cancers.

Heteronuclear Trimetallic MFe2 and M2 Fe (M=V, Nb, and Ta) Clusters for Dinitrogen Activation.

Catalysts with heteronuclear metal active sites may have high performance in the nitrogen reduction reaction (NRR), and the in-depth understanding of the reaction mechanisms is crucial for the design of related catalysts. In this work, the dissociative adsorption of N2 on heteronuclear trimetallic MFe2 and M2 Fe (M=V, Nb, and Ta) clusters was studied with density functional theory calculations. For each cluster, two reaction paths were studied with N2 initially on M and Fe atoms, respectively. Mayer bond order analysis provides more information on the activation of N-N bonds. M2 Fe is generally more reactive than MFe2 . The coordination mode of N2 on three metal atoms can be end-on: end-on: side-on (EES) for both MFe2 and M2 Fe. In addition, a unique end-on: side-on: side-on (ESS) coordination mode was found for M2 Fe, which leads to a higher degree of N-N bond activation. Nb2 Fe has the highest reactivity towards N2 when both the transfer of N2 and the dissociation of N-N bonds are taken into account, while Ta-containing clusters have a superior ability to activate the N-N bond. These results indicate that it is possible to improve the performance of iron-based catalysts by doping with vanadium group metals.

CT enterography for predicting necessity of enterectomy in ovarian cancer patients for achieving optimal debulking surgery / 中国医学影像技术

Objective To observe the value of preoperative CT enterography(CTE)for predicting the necessity of enterectomy in ovarian cancer(OC)patients for achieving optimal debulking surgery(ODS).Methods Preoperative CTE data of 49 patients with pathologically confirmed OC were retrospectively analyzed,including 13 cases received neoadjuvant chemotherapy(NACT)and 36 cases did not.The length(L)and circumference(C)of muscular involvement shown on CTE were taken as criteria for judging the necessity of enterectomy in OC patients([degree 0:no muscular involvement,degree 1:L＜3.0 cm and C＜1/3,degree 2:L≥3.0 cm[A]or C≥1/3[B]).The patients were followed up for at least 1 year after surgery,and the actual operation results were recorded to estimate the ideal surgical strategy.The consistency of CTE evaluated necessity of enterectomy and the ideal surgical strategy was analyzed.Results For patients not undergoing NACT,according to degree 2 A or B showed on CTE,predicted results had excellent agreement with the ideal surgical strategy(Kappa=0.852,P＜0.001),while those according to degree 1 or 2,2 A,2 B were all in good agreement with the ideal surgical strategy(Kappa=0.684-0.771,all P＜0.001).For patients undergoing NACT,the predicted results of degree 2 muscular involvement showed on CTE before NACT had excellent consistencies with the ideal surgical strategy(all Kappa=0.806,all P=0.003).The predicted results of degree 2 muscular involvement showed on CTE after NACT had moderate consistencies with the ideal surgical strategy(all Kappa=0.581,all P=0.021).Conclusion Preoperative CTE could be used to predict the necessity of enterectomy in OC patients for achieving ODS.

Management of menopausal syndrome in women with dyslipidemia / 中华预防医学杂志

The prevalence of dyslipidemia is increased in postmenopausal women due to dysregulation of lipid metabolism and deficiency of estrogen levels. At the same time, some postmenopausal women also have menopausal syndromes such as vasomotor symptoms, physical physiology, mental psychology, and urogenital tract atrophy. Menopausal hormone therapy is the most effective measure to alleviate menopausal syndrome. And initiating MHT in early menopause can reduce cardiovascular damage. However, menopausal hormone therapy can also bring the risk of thromboembolic diseases such as venous embolism, myocardial infarction and stroke. Different drug regimens have different effects on lipid metabolism. Women with menopausal syndrome should take individualized treatment plans for different types of dyslipidemia. Therefore, this article reviews the management and treatment of menopausal syndrome in women with dyslipidemia, so as to provide a reference for personalized management of dyslipidemia in postmenopausal women.

Management of menopausal syndrome in women with dyslipidemia / 中华预防医学杂志

The prevalence of dyslipidemia is increased in postmenopausal women due to dysregulation of lipid metabolism and deficiency of estrogen levels. At the same time, some postmenopausal women also have menopausal syndromes such as vasomotor symptoms, physical physiology, mental psychology, and urogenital tract atrophy. Menopausal hormone therapy is the most effective measure to alleviate menopausal syndrome. And initiating MHT in early menopause can reduce cardiovascular damage. However, menopausal hormone therapy can also bring the risk of thromboembolic diseases such as venous embolism, myocardial infarction and stroke. Different drug regimens have different effects on lipid metabolism. Women with menopausal syndrome should take individualized treatment plans for different types of dyslipidemia. Therefore, this article reviews the management and treatment of menopausal syndrome in women with dyslipidemia, so as to provide a reference for personalized management of dyslipidemia in postmenopausal women.

Trimetallic clusters in the sumanene bowl for dinitrogen activation.

It is of great importance to find catalysts for the nitrogen reduction reaction (NRR) with high stability and reactivity. A series of M3 clusters (M = Ti, Zr, V, and Nb) supported on sumanene (C21H12) were designed as potential catalysts for the NRR by taking advantage of the high reactivity of trimetallic clusters and the unique geometric and electronic properties of sumanene, a bowl-like organic molecule. Detailed mechanisms of NN bond cleavage on C21H12-M3 were investigated by DFT calculations and compared with those on bare M3 clusters. M3 in the sumanene bowl is very stable with large binding energies, which prohibits the cohesion of M3 into M6. In the bowl, M3 has a (quasi-) equilateral triangle structure with lengthened M-M bonds, which is particularly beneficial to the N2 transfer process on Ti3 and V3 clusters. The N-N bond can be dissociated by both M3 and C21H12-M3 clusters without the overall energy barriers. A blurring effect is found in which some geometric and electronic properties of different metal types become similar when M3 is supported on the substrate. Our work demonstrates that sumanene is a suitable substrate to support M3 in the activation of N2 with enhanced stability and maintained a high level of reactivity compared to bare M3.

Comparison of Nitrogen Activation on Trinuclear Niobium and Tungsten Sulfide Clusters Nb3 Sn and W3 Sn (n=0-3): A DFT Study.

The front cover artwork is provided by Prof. Xun-Lei Ding's group at North China Electric Power University (NCEPU). The image shows the cleavage of the triple bond of a dinitrogen molecule on trinuclear metal clusters with sulfide ligands, which is the critical step in nitrogen reduction reactions (NRR). Read the full text of the Research Article at 10.1002/cphc.202200124.

Comparison of Nitrogen Activation on Trinuclear Niobium and Tungsten Sulfide Clusters Nb3 Sn and W3 Sn (n=0-3): A DFT Study.

The reaction of N2 with trinuclear niobium and tungsten sulfide clusters Nb3 Sn and W3 Sn (n=0-3) was systematically studied by density functional theory calculations with TPSS functional and Def2-TZVP basis sets. Dissociations of N-N bonds on these clusters are all thermodynamically allowed but with different reactivity in kinetics. The reactivity of Nb3 Sn is generally higher than that of W3 Sn . In the favorite reaction pathways, the adsorbed N2 changes the adsorption sites from one metal atom to the bridge site of two metal atoms, then on the hollow site of three metal atoms, and at that place, the N-N bond dissociates. As the number of ligand S atoms increases, the reactivity of Nb3 Sn decreases because of the hindering effect of S atoms, while W3 S and W3 S2 have the highest reactivity among four W3 Sn clusters. The Mayer bond order, bond length, vibrational frequency, and electronic charges of the adsorbed N2 are analyzed along the reaction pathways to show the activation process of the N-N bond in reactions. The charge transfer from the clusters to the N2 antibonding orbitals plays an essential role in N-N bond activation, which is more significant in Nb3 Sn than in W3 Sn , leading to the higher reactivity of Nb3 Sn . The reaction mechanisms found in this work may provide important theoretical guidance for the further rational design of related catalytic systems for nitrogen reduction reactions (NRR).

Facile N≡N Bond Cleavage by Anionic Trimetallic Clusters V3-x Tax C4- (x=0-3): A DFT Study.

Activation of N2 on anionic trimetallic V3-x Tax C4- (x=0-3) clusters was theoretically studied employing density functional theory. For all studied clusters, initial adsorption of N2 (end-on) on one of the metal atoms (denoted as Site 1) is transferred to an of end-on: side-on: side-on coordination on three metal atoms, prior to N2 dissociation. The whole reaction is exothermic and has no global energy barriers, indicating that the dissociation of N2 is facile under mild conditions. The reaction process can be divided into two processes: N2 transfer (TRF) and N-N dissociation (DIS). For V-series clusters, which has a V atom on Site 1, the rate-determining step is DIS, while for Ta-series clusters with a Ta on Site 1, TRF may be the rate-determining step or has energy barriers similar to those of DIS. The overall energy barriers for heteronuclear V2 TaC4- and VTa2 C4- clusters are lower than those for homonuclear V3 C4- and Ta3 C4- , showing that the doping effect is beneficial for the activation and dissociation of N2 . In particular, V-Ta2 C4- has low energy barriers in both TRF and DIS, and it has the highest N2 adsorption energy and a high reaction heat release. Therefore, a trimetallic heteronuclear V-series cluster, V-Ta2 C4- , is suggested to have high reactivity to N2 activation, and may serve as a prototype for designing related catalysts at a molecular level.

Effects of perimenopausal one-day outpatient multidisciplinary model on the cognition of women to menopause hormone therapy / 中国药房

OBJECTIVE To evalu ate the effects of perimenopausal one-day outpatient multidisciplinary model on the cognition of women to menopause hormone therapy （MHT）. METHODS The perimenopausal one-day outpatient service opened by the Third Affiliated Hospital of Chongqing Medical University in 2017 was introduced ，which was participated by doctors ，pharmacists， nutritionists，music psychotherapists ，nurses and other multidisciplinary members to provide systematic ，all-round，humanistic and face-to-face group science popularization and education ，practical experience and Q&A for women in perimenopause or about to enter perimenopause （called“students”）. The students who participated in one-day outpatient service in 2020 were selected as the survey object ， and the questionnaire was CMEI2020KPYJ（ZAMM）00206] designed to analyze the understanding of perimenopausal syndrome，awareness rate of MHT ，willingness to use and concerns. RESULTS A total of 295 students completed the questionnaire. Compared with before participation ， after participated in one-day outpatient service ，the cognition level of the students were all improved significantly ，including perimenopausal age （96.61％ vs. 99.32％，P＝0.037），the importance of perimenopausal health care knowledge （91.19％ vs. 96.95％，P＜0.001），whether the perimenopausal syndrome needs treatment （88.47％ vs. 99.32％，P＜0.001），willingness to use MHT （70.59％ vs. 94.48％ ，P＜0.001），MHT treatment timing （60.50％ vs. 95.17％ ，P＜0.001），reducing the risk of cardiovascular disease （51.68％ vs. 96.55％ ，P＜0.001），delaying aging （69.75％ vs. 97.59％ ，P＜0.001），preventing osteoporosis（65.13％ vs. 97.59％），P＜0.001）；the medical staff were higher than the non-medical staff （P＜0.05）. Totally 90％ of the students said they had gained knowledge about the prevention and treatment of common diseases ，nutrition and guidance， psychological regulation guidance hormone therapy related knowledges and exercise methods ；the proportion of the students who were willing to use MHT for 1 to 5 years（31.09％ vs. 47.93％）increased significantly. The proportion of the students who concerned about the risk of thrombosis （60.24％ vs. 36.81％），weight gain （59.64％ vs. 14.84％）and life-long dependence （52.41％ vs. 18.13％）was significantly reduced ，but that of the students who concerned about cancer risk was not diminished. From 2017 to 2020，the utilization rate of MHT was increased from 2.22％ to 62.16％ in non-medical staff among the students. CONCLUSIONS The multidisciplinary model of perimenopausal one-day outpatient service can improve the awareness of MHT among perimenopausal women ，eliminate misunderstandings ，and increase the utilization rate of MHT.

Downregulation of promoter methylation gene PRDM5 contributes to the development of tumor proliferation and predicts poor prognosis in gastric cancer.

Background: Epigenetic aberrations of tumor suppressor genes (TSGs), particularly DNA methylation, are frequently involved in the pathogenesis of gastric cancer (GC). Previous studies have shown that PRDM5 is methylated and silenced in GC. However, the role of PRDM5 in GC progression has not been explored. Methods: The expression and epigenetic alterations of PRDM5 in GC were analyzed in public datasets. The mRNA and protein expression of PRDM5 in fresh tissues were detected by semi-quantitative PCR and Western blot. And expression of PRDM5 in gastric paracarcinoma and carcinoma tissues from 162 patients was detected by immunohistochemistry (IHC) and assessed the association with different clinicopathological features. The prognostic value of PRDM5 in GC patients was evaluated using Kaplan-Meier plotter. We also studied promoter region methylation of PRDM5 in GC by methylation-specific PCR (MSP). The effects of PRDM5 on cell proliferation and migration were conducted by functional experiments in vitro. Results: The expression of PRDM5 was downregulated in GC, and that was associated with poor survival and tumor progression. And PRDM5 expression was found to be an independent prognostic factor for GC. We also found that the methylation of PRDM5 promoter was closely related to the histopathological types and the progression of tumors through the public relations database. In vitro, ectopical expression of PRDM5 inhibited the growth of tumor cells, while knockdown of PRDM5 increased the proliferation and migration of tumor cells. Conclusion: These results suggest that PRDM5 may be a novel TSG methylated in GC that plays important roles in GC development. And we found PRDM5 as a potential survival biomarker for GC, especially in well differentiated GC. PRDM5 expression was significantly correlated with tumor stage and histological type.

Non-Dissociative Activation of Chemisorbed Dinitrogen on One or Two Vanadium Atoms Supported by a Mo6 S8 Cluster.

Adsorption of N2 on Mo6 S8 q _Vx clusters (x=0, 1, 2; q=0, ±1) were systematically studied by density functional theory calculations with dispersion corrections. It was found that the N2 can be chemisorbed and undergo non-dissociative activation on single or double metal atoms. The adsorption and activation are influenced by metal types (V or Mo), N2 coordination modes and charge states of the clusters. Particularly, anionic Mo6 S8 - _V2 clusters have remarkable ability to fix and activate N2 . In Mo6 S8 - _V2 , two V atoms prefer to adsorb on two adjacent S-Mo-S hollow sites, leading to the formation of a supported V…V unit. The N2 is bridged side-on coordinated with these two V atoms with high adsorption energy and significant charge transfer. The bond order, bond length and vibration frequency of the adsorbed N2 are close to those of a N-N single bond.

Prognostic Significance of the Preoperative Controlled Nutritional Status Score in Lung Cancer Patients Undergoing Surgical Resection.

Several studies have reported the preoperative control nutritional status (CONUT) score as an independent prognostic factor for the prognosis of lung cancer patients. Patients with severe chronic obstructive pulmonary disease usually have high cholesterol levels, cachexia, and muscle atrophy. Abnormal nutritional status and lymphopenia were also related to poor prognosis. We explored the relationship between the preoperative CONUT score and patient prognosis and predicted the efficacy of pembrolizumab in lung cancer treatment. A systematic literature search was performed to identify qualified articles reporting the prognostic prediction potential of CONUT scores in lung cancer patients. A meta-analysis was performed for the association between CONUT scores and survival outcomes and clinic-pathological parameters. Overall, eight articles and 1,220 cases were included. Abnormal preoperative CONUT scores were a poor prognostic factor for elderly lung cancer patients. Finally, higher CONUT scores of pembrolizumab were associated with poor survival. CONUT was an independent prognostic indicator of lung cancer, successfully predicting the efficacy and prognosis of pembrolizumab in lung cancer treatment.

Non-stoichiometric molybdenum sulfide clusters and their reactions with the hydrogen molecule.

Structures of non-stoichiometric MoxSy clusters (x = 2-4; y = 2-10) were studied by density functional calculations with global optimization. Besides 1T phase like structures, a novel regular grid structure in which Mo atoms are well separated by S atoms was found, which might be used as a building-block to construct a new type of two-dimensional molybdenum sulfide monolayer. The hydrogen molecule prefers to be adsorbed onto Mo atoms rather than S atoms, and Mo atoms with less S coordination have a higher ability to adsorb H2. In addition, the reaction pathways for H2 dissociation were studied on two clusters with the highest H2 adsorption energy (Mo2S4 and Mo3S3). The vacant bridge site of Mo-Mo in S-deficient clusters, which corresponds to the sulfur vacancy in the bulk phase MoS2, is favored by H atom adsorption and plays an important role in the H atom transfer on MoxSy clusters. Our results provide a new aspect to understand the reason why S defect in MoS2 and MoS2 with an Mo-edge could enhance the catalytic performance in the hydrogen evolution reaction.

Methane activation by heteronuclear diatomic AuRh+ cation: comparison with homonuclear Au2+ and Rh2.

The ability to activate methane differs appreciably for different transition metals, and it is attractive to find the most suitable metal for the direct conversion of methane to value-added chemicals. Herein, we performed a comparative study on the reactions of CH4 with Au2+, AuRh+ and Rh2+ cations by mass-spectrometry based experiments and DFT-based theoretical analysis. Different reactivity has been found for these cations: Au2+ has the lowest reactivity, and it can activate methane but only produce H-Au2-CH3+ without H2 release; Rh2+ has the highest reactivity, and it can produce both carbene-type Rh2-CH2+ and carbyne-type H-Rh2-CH+ with H2 release; AuRh+ also has high reactivity to produce only AuRh-CH2+ with H2, avoiding the excessive dehydrogenation of CH4. Our theoretical results demonstrate that Rh is responsible for the high reactivity, while Au leads to selectivity, which may be caused by the unique intrinsic bonding properties of the metals.