Gas-phase synthesis of Ti2CCl2 enables an efficient catalyst for lithium-sulfur batteries.

MXenes have aroused intensive enthusiasm because of their exotic properties and promising applications. However, to date, they are usually synthesized by etching technologies. Developing synthetic technologies provides more opportunities for innovation and may extend unexplored applications. Here, we report a bottom-up gas-phase synthesis of Cl-terminated MXene (Ti2CCl2). The gas-phase synthesis endows Ti2CCl2 with unique surface chemistry, high phase purity, and excellent metallic conductivity, which can be used to accelerate polysulfide conversion kinetics and dramatically prolong the cyclability of Li-S batteries. In-depth mechanistic analysis deciphers the origin of the formation of Ti2CCl2 and offers a paradigm for tuning MXene chemical vapor deposition. In brief, the gas-phase synthesis transforms the synthesis of MXenes and unlocks the hardly achieved potentials of MXenes.

Vanadium Intercalation into Niobium Disulfide to Enhance the Catalytic Activity for Lithium-Sulfur Batteries.

Despite their high specific energy and great promise for next-generation energy storage, lithium-sulfur (Li-S) batteries suffer from polysulfide shuttling, slow redox kinetics, and poor cyclability. Catalysts are needed to accelerate polysulfide conversion and suppress the shuttling effect. However, a lack of structure-activity relationships hinders the rational development of efficient catalysts. Herein, we studied the Nb-V-S system and proposed a V-intercalated NbS2 (Nb3VS6) catalyst for high-efficiency Li-S batteries. Structural analysis and modeling revealed that undercoordinated sulfur anions of [VS6] octahedra on the surface of Nb3VS6 may break the catalytic inertness of the basal planes, which are usually the primary exposed surfaces of many 2D layered disulfides. Using Nb3VS6 as the catalyst, the resultant Li-S batteries delivered high capacities of 1541 mAh g-1 at 0.1 C and 1037 mAh g-1 at 2 C and could retain 73.2% of the initial capacity after 1000 cycles. Such an intercalation-induced high activity offers an alternative approach to building better Li-S catalysts.

Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia.

Electrochemical conversion of nitrate to ammonia offers an efficient approach to reducing nitrate pollutants and a potential technology for low-temperature and low-pressure ammonia synthesis. However, the process is limited by multiple competing reactions and NO3- adsorption on cathode surfaces. Here, we report a Fe/Cu diatomic catalyst on holey nitrogen-doped graphene which exhibits high catalytic activities and selectivity for ammonia production. The catalyst enables a maximum ammonia Faradaic efficiency of 92.51% (-0.3 V(RHE)) and a high NH3 yield rate of 1.08 mmol h-1 mg-1 (at - 0.5 V(RHE)). Computational and theoretical analysis reveals that a relatively strong interaction between NO3- and Fe/Cu promotes the adsorption and discharge of NO3- anions. Nitrogen-oxygen bonds are also shown to be weakened due to the existence of hetero-atomic dual sites which lowers the overall reaction barriers. The dual-site and hetero-atom strategy in this work provides a flexible design for further catalyst development and expands the electrocatalytic techniques for nitrate reduction and ammonia synthesis.

Visible-Light-Responsive 2D Photocatalysts Assembled by Evans-Showell-Type POMs and Metalloviologen Frameworks for Sulfide-Sulfoxide Transformation.

Sulfide-sulfoxide aerobic photo-oxidation is of great interest in organic and medicinal chemistry; however, developing efficient and facile heterogeneous photocatalytic systems without additional additives remains challenging. Herein, we intentionally designed and synthesized two polyoxometalate (POM)-based metalloviologen frameworks, formulated as [MII(4-PBPY)2(H2O)][MII(H2O)4][CoIII2MoVI10H4O38]·nH2O (M = Cu, n = 10 for 1; M = Co, n = 11 for 2), prepared by the mild one-step synthesis strategy and characterized in detail. X-ray single-crystal diffraction analysis shows that they present a two-dimensional layered structure formed by two parallel metalloviologen layers pillared by dimeric Evans-Showell-type POMs. The connection of POM to the metalloviologen framework enables easier flow of electrons to the POM port, which can theoretically further induce O2 to generate reactive oxygen species (O2•-) to oxidize substrates to form target products. As expected, both 1 and 2 exhibit outstanding photocatalytic activity in the oxidation of sulfides. Within 6 h, methyl phenyl sulfide can be quantitatively converted into methyl phenyl sulfoxide. The in-depth mechanism reveals that there is also a synergistic energy-transfer pathway in the catalytic system in addition to the electron-transfer pathway. In addition, the corresponding catalytic activity and structure can be well maintained after at least 10 cycle experiments.

Tuning the Local Coordination of CoP1-xSx between NiAs- and MnP-Type Structures to Catalyze Lithium-Sulfur Batteries.

The slow conversion and rapid shuttling of polysulfides remain major challenges that hinder the practical application of lithium-sulfur (Li-S) batteries. Efficient catalysts are needed to accelerate the conversion and suppress the shuttling. However, the lack of a rational understanding of catalysis poses obstacles to the design of catalysts, thereby limiting the rapid development of Li-S batteries. Herein, we theoretically analyze the modulation of the electronic structure of CoP1-xSx caused by the NiAs-to-MnP-type transition and its influence on catalytic activity. We found that the interacting d-orbitals of the active metal sites play a determining role in adsorption and catalysis, and the optimal dz2-, dxz-, and dyz-orbitals in an appropriately distorted five-coordinate pyramid enable higher catalytic activity compared with their parent structures. Finally, rationally designed catalysts and S were electrospun into carbonized nanofibers to form nanoreactor chains for use as cathodes. The resultant Li-S batteries exhibited superior properties over 1000 cycles with only a decay rate of 0.031% per cycle and demonstrated a high capacity of 887.4 mAh g-1 at a high S loading of 10 mg cm-2. The structural modulation and bonding analyses in this study provide a powerful approach for the rational design of Li-S catalysts.

Continuous epitaxy of single-crystal graphite films by isothermal carbon diffusion through nickel.

Multilayer van der Waals (vdW) film materials have attracted extensive interest from the perspective of both fundamental research1-3 and technology4-7. However, the synthesis of large, thick, single-crystal vdW materials remains a great challenge because the lack of out-of-plane chemical bonds weakens the epitaxial relationship between neighbouring layers8-31. Here we report the continuous epitaxial growth of single-crystal graphite films with thickness up to 100,000 layers on high-index, single-crystal nickel (Ni) foils. Our epitaxial graphite films demonstrate high single crystallinity, including an ultra-flat surface, centimetre-size single-crystal domains and a perfect AB-stacking structure. The exfoliated graphene shows excellent physical properties, such as a high thermal conductivity of ~2,880 W m-1 K-1, intrinsic Young's modulus of ~1.0 TPa and low doping density of ~2.2 × 1010 cm-2. The growth of each single-crystal graphene layer is realized by step edge-guided epitaxy on a high-index Ni surface, and continuous growth is enabled by the isothermal dissolution-diffusion-precipitation of carbon atoms driven by a chemical potential gradient between the two Ni surfaces. The isothermal growth enables the layers to grow at optimal conditions, without stacking disorders or stress gradients in the final graphite. Our findings provide a facile and scalable avenue for the synthesis of high-quality, thick vdW films for various applications.

Visible-Light-Driven Oxidation of Amines to Imines in Air Catalyzed by Polyoxometalate-Tris(bipyridine)ruthenium Hybrid Compounds.

The development of visible-light photocatalysts for the selective oxidative coupling of amines to imines is an area of great interest. Herein, four hybrid compounds based on polyoxometalate anions and tris(bipyridine)ruthenium cations, Ru(bpy)3[M6O19] (M = Mo, W) 1-2, [Ru(bpy)3]2[Mo8O26] 3, [Ru(bpy)3]2[W10O32] 4, are prepared and characterized by X-ray diffraction (single-crystal and powder), elemental analysis, energy-dispersive X-ray spectroscopy (EDS) analysis, infrared (IR) spectroscopy, and solid diffuse reflective spectroscopy. Single-crystal structural analysis indicates that polyoxometalate anions and tris(bipyridine)ruthenium cations interact with each other through extensive hydrogen bonds in these compounds. These hybrid species with strong visible-light-harvesting abilities and suitable photocatalytic energy potentials show excellent photocatalytic activity and selectivity for the oxidation of amines to imines at room temperature in air as an oxidant. Among them, compound 1 with the [Mo6O19]2- anion has the highest catalytic activity, which can swiftly convert >99.0% of benzylamine into N-benzylidenebenzylamine with a selectivity of 98.0% in 25 min illumination by a 10 W 445 nm light-emitting diode (LED). Its turnover frequency reaches 392 h-1, which is not only better than the homogeneous catalyst [Ru(bpy)3]Cl2 but also much superior to those achieved over most of reported heterogeneous catalysts. Moreover, it shows a wide generality for various aromatic amines, accompanied by the advantages of good recyclability and stability. The photocatalytic oxidation mechanism of amines to the corresponding imines over polyoxometalate-based hybrid compounds was fully investigated.

Chlorination behaviors for green and efficient vanadium recovery from tailing of refining crude titanium tetrachloride.

The refined tailing, generated from refining of titanium tetrachloride (TiCl4) for vanadium (V) removal, is a hazardous material to environment due to the high content of V. Aiming at effective and selective extraction of V from the refined tailing, a fluidized chlorination process was proposed in present work. The chlorination behaviors of the refined tailing which determine the efficiency and selectivity of V extraction were emphatically investigated. A resultant 96.36% of V and 4.23% of Ti can be synchronously extracted from the tailing at the optimum conditions of 800 °C for 60 min, with the pressure fraction of chlorine [P(Cl2)/P(Cl2 +N2)] = 0.5 and the mass fraction of petroleum coke in raw materials for chlorination at 10 wt%. High purity vanadium oxytrichloride (VOCl3, higher than 99.99 wt%) can be finally obtained via further simple purification of the collected chloride product. Moreover, the chlorination residue containing concentrated TiO2 has the potential to be further utilized for Ti extraction. Thus the process provides a new prospect for effective, clean and comprehensive utilization of the refined tailing, which can solve the hazardous waste recycle and environmental concerns simultaneously.

Highly Efficient Synthesis of p-Benzoquinones Catalyzed by Robust Two-Dimensional POM-Based Coordination Polymers.

Selective oxidation of alkyl-substituted phenols offers efficient access to p-benzoquinones (BQs) that serve as key components for synthesizing biologically active compounds, but rational manufacture of efficient recyclable catalysts for such a reaction remains a severe challenge. Herein, two crystalline 2D polyoxometalate-based coordination polymers (POMCPs), formulated as H3[CuI3(L)3]2[PM12O40]·xH2O (M = Mo, x = 4 for 1; M = W, x = 6 for 2; and HL = 4-(1H-tetazol-5-yl)pyridine), are prepared by a mineralizer-assisted one-step synthesis strategy and explored as heterogeneous catalysts for p-BQs synthesis. Both compounds have been characterized through elemental analysis, EDS analysis, infrared spectroscopy, UV-vis diffuse reflectance spectrum, EPR, XPS, BET, single-crystal, and powder X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that both 1 and 2 exhibit an interesting 2D sheet structure composed of 2-connected Keggin type anions [PM12O40]3- and hexa-nuclear {CuI6(HL)6} cluster-based metal-organic chains via Cu···O interactions. When used as catalysts, POMCPs 1 and 2 have excellent catalytic activities in the selective oxidation of substituted phenols to p-BQs with H2O2. Notedly, in the model reaction from 2,3,6-trimethylphenol (TMP) to the vitamin E key intermediate trimethyl-p-benzoquinone (TMBQ), the catalytic activities expressed by turnover frequency (TOF) of 1 and 2 can reach an unprecedented 2400 and 2000 h-1, respectively, at close to 100% TMBQ yield. The truly heterogeneous nature, stability, and structural integrity of both catalysts were ascertained by FTIR, PXRD techniques, and the following cycles. Mechanism studies reveal that both catalysts can involve a dual reaction pathway through a heterolytic oxygen atom transfer mechanism and homolytic radical mechanism. Moreover, the 2D POMCPs with highly accessible bilateral active sites and efficient mass transfer efficiency possess superior catalytic performance to their analogous 3D species.

Analysis of Nonlinear Transient Energy Effect on Thermoelectric Energy Storage Structure.

In complex flight conditions, due to the large amount of unusable heat generated by aerodynamic heating, the thermal protection system of an aircraft needs to withstand a large temperature shock, which brings great challenges to the design of the structure. In order to effectively utilize the irregular aerodynamic heat, and improve structural heat conduction, a composite structure is formed by using phase change energy storage materials on the basis of the thermoelectric structure, which transforms the aerodynamic waste heat into stable electric energy for the internal system. Through the study of the response of nonlinear transient energy, it is found that the thermoelectric and mechanical properties of the new structure can be improved by adding phase change energy storage materials. Under actual flight conditions, the new structure can reduce the maximum temperature by 180 K and the maximum thermal stress by 110 Mpa. The mechanical properties of the structure are effectively improved, the service life of the structure is prolonged, and the waste heat can be converted into stable electrical energy output to improve the thermoelectric output performance. On the premise of ensuring conversion efficiency, the output power of the new structure has been improved by 64.8% through structural optimization under actual flight conditions.

2D Hybrid Architectures Constructed from Two Kinds of Polyoxovanadates as Efficient Heterogeneous Catalysts for Cyanosilylation and Knoevenagel Condensation.

The design of heterogeneous catalysts for highly efficient catalysis for cyanosilylation reactions and Knoevenagel condensations is greatly significant, due to the important application of their products in industry. Herein, five hybrid compounds constructed from two types of polyoxovanadates, [MV12O38]12- (M = Ni, Mn) and [V10O28]6-, were successfully synthesized as heterogeneous catalysts for both reactions, which are {(dpdo)[Ln2(H2O)9(dpdo)][Ln(H2O)5]2[Ln(H2O)4]2[V10O28][NiV12O38]·nH2O} (1, Ln = La, n = 23; 2, Ln = Ce, n = 27; 3, Ln = Pr, n = 27; dpdo = 4,4'-bipyridine N,N'-dioxide) and {(dpdo)[Ln2(H2O)9(dpdo)][Ln(H2O)5]2[Ln(H2O)4]2[V10O28][MnV12O38]·27H2O} (4, Ln = La; 5, Ln = Pr). These compounds were characterized by IR spectroscopy, elemental analysis, TG analysis and X-ray diffraction (single crystal and powder) etc. Compounds 1-5 have similar 2D hybrid structures, in which isopolyvanadate [V10O28]6- and heteropolyvanadate [MV12O38]12- are linked together by hydrated Ln3+ cations and Ln-dpdo coordination complexes. Polyoxovanadates [V10O28]6- and [MV12O38]12- both originate from the transformation of the [MV13O38]7- raw material. This kind of extended structure containing isopolyvanadate and heteropolyvanadate has never been reported hitherto. Because of the Lewis acidity of the Ln3+ cation and the Lewis basicity of the polyoxovanadates, all five compounds exhibit excellent catalytic performance in cyanosilylation and Knoevengel condensation reactions. Especially, compound 3, with a Pr3+ cation, displayed the best catalytic results. Furthermore, these catalysts exhibit a truly heterogeneous nature and good recyclability.

The Association Between the Incidence Risk of Peripheral Neuropathy and PD-1/PD-L1 Inhibitors in the Treatment for Solid Tumor Patients: A Systematic Review and Meta-Analysis.

Purpose: We conducted this study to determine the relationship between PD-1/PD-L1 inhibitors and the incidence risk of peripheral neuropathy in patients with solid tumors. Method: The process of the meta-analysis was performed by us according to the Preferred Reporting Items for Systematic Reviews and Meta-analyses (PRISMA) guidelines. Incidence of all-grade and grade 3-5 treatment-related peripheral neuropathy in patients with solid tumors were taken into account. Results: After screening and eligibility assessment, a total of 17 clinical trials involving 10,500 patients were selected for the final meta-analysis. The incidence risk of peripheral neuropathy for all grade was significantly lower in the PD-1/PD-L1 inhibitor group than that of the control group, either monotherapy (OR = 0.08, 95%CI:[0.03, 0.19]) or chemotherapy (OR = 0.05, 95%CI:[0.03, 0.11]). Similar incidence trend could also be seen for the incidence risk of grade 3-5 peripheral neuropathy. When PD-1/PD-L1 inhibitors were used in combination with chemotherapy, the incidence risk of peripheral neuropathy was higher than in the control chemotherapy group, whether it was all-grade (OR = 1.22, 95%CI:[1.00, 1.49]) or grade 3-5 degree (OR = 1.74, 95%CI:[1.03, 2.92]). Conclusion: Compared with chemotherapy, incidence risk of peripheral neuropathy related to PD-1/PD-L1 inhibitor was significantly lower than that of the chemotherapy group, while PD-1/PD-L1 inhibitor increased the incidence risk of peripheral neuropathy when it was combined with chemotherapy.

Multiunit Catalysts with Synergistic Reactivity: Three-Dimensional Polyoxometalate-Based Coordination Polymers for Highly Efficient Synthesis of Functionalized p-Benzoquinones.

The rational design of highly efficient catalysts for the synthesis of functionalized p-benzoquinones (p-BQs) is of great significance for the manufacture of bioactive compounds. Herein, two 3D crystalline polyoxometalate-based coordination polymers (POMCPs) are used as heterogeneous catalysts for the synthesis of p-BQs, which are H[CuII(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O (1) (Httb = 1-(tetrazol-5-yl)-4-(triazol-1-yl)benzene) and [ClCu6I(trz)4][ClCu5I(trz)4]2[CuII(H2O)][PW12O40] (2) (trz = 1,2,4-triazole). Both compounds were characterized by elemental analysis, IR, XPS, solid diffuse reflective spectroscopy, TG analysis, and single-crystal X-ray diffraction. In 1, Keggin anions [PW12O40]3- locate in 1D square channels constructed from wave-like Cu-ttb layers to form a 3D POMCP by coordinating to Cu ions, and in 2, [PW12O40]3- anions situate in eight-membered Cu-trz channels via Cu···O interactions to yield a 3D POMCP structure. The catalytic activities of 1 and 2 have been evaluated in the selective oxidation of alkylphenols/alkoxybenzenes/methylnaphthalene, especially in the oxidation reaction of 2,3,6-trimethylphenol (TMP) to 2,3,5-trimethyl-p-benzoquinone (TMBQ, vitamin E key intermediate), with H2O2 as oxidant. By using catalysts 1 and 2 under optimal conditions, the yield of TMBQ can reach 99% and 96% within 10-20 min, respectively. Both catalysts demonstrated high turnover frequencies (300 h-1 for 1 and 600 h-1 for 2) and the truly heterogeneous nature. 1 and 2 catalyzed the synthesis of p-BQs on the basis of effective cooperative catalytic activities by POMs and metal nodes.

The overall safety evaluation of programmed cell death/programmed cell death ligand 1 (PD-1/PD-L1) treatment for lung cancer patients: An updated systematic review and meta-analysis.

BACKGROUND: We performed the meta-analysis to evaluate the overall safety of programmed cell death-1 (PD-1) or ligand 1 (PD-L1) inhibitor treatment for lung cancer patients. METHOD: Randomized controlled trials were collected according to the Preferred Reporting Items for Systematic Reviews and Meta-analyses (PRISMA) guidelines. Risk ratio (RR) of PD-1/PD-L1 inhibitor treatment-related death, treatment-related adverse events, any serious events, and any events leading to discontinuation were all taken into account for the final evaluation. RESULTS: Fourteen studies were collected for the meta-analysis. The RR of treatment-related death for PD-1/PD-L1 was significantly lower than that of the control group (RR = 0.37, 95% confidence interval, CI: [0.21, 0.66]). Similar analysis results could also be seen for the RR of treatment-related adverse events and adverse events leading to discontinuation. When PD-1/PD-L1 was combined with chemotherapy, it increased the RR of adverse events leading to discontinuation (RR = 1.68, 95% CI: [1.22, 3.32]). The RR of overall treatment-related adverse events was lower in nivolumab (PD-1) than that of the control group (nivolumab + ipilimumab) (RR = 0.77, 95% CI: [0.65, 0.90]). Similar analysis results could also be seen in the RR of treatment-related adverse events for grade 3 to 5 and adverse events leading to discontinuation. CONCLUSION: Compared with chemotherapy, RR of the treatment-related deaths associated with PD-1/PD-L1 inhibitor was significantly lower than that of the chemotherapy group, while it did not increase the RR when they were combined with chemotherapy or other drugs. When PD-1/PD-L1 was combined with chemotherapy, it increased the RR of adverse events leading to discontinuation.

Methotrexate, doxorubicin, and cisplatinum regimen is still the preferred option for osteosarcoma chemotherapy: A meta-analysis and clinical observation.

BACKGROUND: We designed the study to investigate whether methotrexate, doxorubicin, and cisplatinum (MAP) chemotherapy strategy was still the preferred option for the survival of osteosarcoma patients. METHOD: We collected some trials of osteosarcoma to make a meta-analysis first. Then, we retrospectively collected data from 115 patients with osteosarcoma and performed further analysis to verify the impact of MAP regimen on the survival of patients. RESULTS: Seven studies including 3433 participants met the preliminary inclusion criteria. Meta-analysis of the 3-year disease-free survival (odds ratio [OR] = 1.06, 95% confidence interval [CI]: 0.88-1.28; P = .52) and overall survival (OR = 1.21, 95% CI: 0.70-2.11; P = .54), 5-year disease-free survival (OR = 1.07, 95% CI: 0.87-1.30; P = .54) and overall survival (OR = 0.86, 95% CI: 0.65-1.12; P = .26), and mortality rate (OR = 0.90, 95% CI: 0.70-1.17; P = .44), showed no statistically significant differences. The most common grade 3/4 adverse events were neutropenia (498 [85.9%] patients in MAP vs 533 [93.3%] in MAP plus ifosfamide and etoposide, or other adjuvant therapy drugs [MAP]). MAP was associated with less frequent toxicities than MAP group with statistical significance in thrombocytopenia, febrile neutropenia, anemia, and hypophosphatemia. The same phenomenon could also be seen in the analysis of clinical data. CONCLUSION: MAP regimen remains the preferred option for osteosarcoma chemotherapy.

Incidence risk of PD-1/PD-L1 related diarrhea in non-small cell lung cancer (NSCLC) patients: a systematic review and meta-analysis.

Purpose: We designed the study to illustrate the OR of programmed cell death-1 (PD-1) or ligand 1 (PD-L1) inhibitor-related diarrhea in patients with non-small cell lung cancer. Method: This systematic review and meta-analysis were put into practice according to the Preferred Reporting Items for Systematic Reviews and Meta-analyses (PRISMA) guidelines. Incidence of all grades for PD-1/PD-L1 inhibitor-related diarrhea in NSCLC was taken into account. Results: After screening and eligibility assessment of 57 articles, a total of 12 clinical trials involving 6,659 participants were collected for the final meta-analysis. The incidence risk of diarrhea for all grades was lower in PD-1 inhibitor monotherapy compared to monochemotherapy of docetaxel (OR=0.31, 95% CI [0.24, 0.41]; I2=0%, Z=8.23 (p<0.00001)), while a similar result could also be seen in PD-L1 inhibitor monotherapy group (OR=0.41, 95% CI [0.27, 0.64]; I2=59%, Z=3.92 [p<0.00001]). The opposite result can be seen when PD-1/PD-L1 inhibitor combined chemotherapy was compared to chemotherapy alone (OR=1.51, 95% CI [1.22, 1.87]; I2=0%, Z=3.77 [p<0.00001]). Similar incidence trend could also be seen in the meta-analysis of diarrhea for grade 1-2 and grade 3-5. Conclusion: The incidence risk of diarrhea associated with PD-1/-PD-L1 inhibitor monotherapy was significantly lower than that of docetaxel monotherapy group. However it was higher in PD-1/PD-L1 inhibitor combined with chemotherapy group compared with the chemotherapy alone group.

Hydrogen Diffusion Guided Design of Pt-Based Alloys for Inhibition of Butadiene Over-Hydrogenation.

Alloying Pt with other metals is an effective strategy to tune its performance towards selective hydrogenation reactions. Herein, we have demonstrated a process to screen Pt-based alloys for inhibition of butadiene over-hydrogenation with a model comprising isolated single atoms (ISA) embedded into Pt(111). DFT calculations reveal that the diffusion energy barrier of H co-adsorbed with 1-butene is a key parameter for the screening. The output from the ISA model was validated by testing several typical Pt-based alloys towards butadiene hydrogenation. Furthermore, an unexpected higher selectivity to cis-2-butene compared to the trans isomer and 1-butene over the PtZn alloy was explored employing the ISA model.

Hyper expression of MTBP may be an adverse signal for the survival of some malignant tumors: A data-based analysis and clinical observation.

To explore the relationship between mouse double minute 2 binding protein (MTBP) and the prognosis of cancer patients, a databank-based reanalysis was conducted and a clinical observation about lung adenocarcinoma was taken to verify the result of data analysis.We reanalyzed all the downloaded data in order to make a conclusion about the relationship between MTBP and the prognosis of cancer patients. At last, we collected 112 lung cancer patients with MTBP information to verify the results of data analysis (GSE30219).The overall Kaplan-Meier curve results of 6 eligible data groups were shown in Fig. 1. The Kaplan-Meier curve result of GSE16011 was shown in Fig. 1A (concordance index = 59.48, Log-Rank Equal Curves [P = 5.942e-05], R = 0.045/1, risk groups hazard ratio = 1.69 [conf. int. 1.3-2.9], P = 7.344e-05), while the stratification results were displayed independently in Figs. 2 and 3. The similar results could be seen in other 5 data groups. The tissue sections of 112 patients with lung adenocarcinoma were collected and immunohistochemically stained. The hyper expression rate of MTBP in adenocarcinoma was 23.21% (26/112). The results showed that patients with hyper expression of MTBP had significantly worse prognosis than the control group, and the survival curves were clearly separated from each other (Fig. 4B, P = .000).Hyper expression of MTBP maybe an adverse event for the survival of some cancer patients, especially in glioblastoma, kidney cancer, and lung cancer patients, which has been verified in 112 lung cancer patients with MTBP status.

A novel fractional crystallization route to porous TiO2-Fe2O3 composites: large scale preparation and high performances as a photocatalyst and Li-ion battery anode.

Meso/macroporous TiO2-Fe2O3 composite particles are prepared using naturally abundant ilmenite via a novel heat treatment induced fractional crystallization strategy in a fluidized bed. Fluid-bed roasting in oxidizing and reducing environments is carried out in order to realize the fractional crystallization of ilmenite. Subsequently, acid leaching is employed to remove most of the ferrous phase and form porous TiO2-Fe2O3 composites. The influences of the reaction parameters on the composition, structure and properties of the products are studied. It is found that the pore structure and composition of the porous TiO2-Fe2O3 composite particles can be controlled simply by controlling some parameters, such as the roasting time, temperature, precursor particle size, and post-roasting treatment. Photocatalytic and electrochemical cycling measurements show that the synergism of porous structures and the controlled doping of α-Fe2O3 endow the as-obtained products with excellent visible light photocatalytic activity and provide enhanced performance in lithium ion batteries. The composite porous particles thus obtained may have some promising applications in the fields of photocatalysts, electrode materials, absorbers, pigments etc. This work opens a new avenue for reasonable combination of cost-effective raw materials, a large scale fabricating process and fine control over the structure and composition in the design and preparation of functional materials.

DFT calculations on the electronic structures of BiOX (X = F, Cl, Br, I) photocatalysts with and without semicore Bi 5d states.

The electronic structures of BiOX (X = F, Cl, Br, I) photocatalysts have been calculated with and without Bi 5d states using the experimental lattice parameters, via the plane-wave pseudopotential method based on density functional theory (DFT). BiOF exhibits a direct band gap of 3.22 or 3.12 eV corresponding to the adoption of Bi 5d states or not. The indirect band gaps of BiOCl, BiOBr, and BiOI are 2.80, 2.36, and 1.75 eV, respectively, if calculated with Bi 5d states, whereas the absence of Bi 5d states reduces them to 2.59, 2.13, and 1.53 eV successively. The calculated gap characteristics and the falling trend of gap width with the increasing X atomic number agree with the experimental results, despite the common DFT underestimation of gap values. The shapes of valence-band tops and conduction-band bottoms are almost independent of the involvement of Bi 5d states. The indirect characteristic becomes more remarkable, and the conduction-band bottom flattens in the sequence of BiOCl, BiOBr, and BiOI. Both O 2p and X np (n = 2, 3, 4, and 5 for X = F, Cl, Br, and I, respectively) states dominate the valence bands, whereas Bi 6p states contribute the most to the conduction bands. With the growing X atomic number, the localized X np states shift closer toward the valence-band tops, and the valence and conduction bandwidths evolve in opposite trends. Atomic and bond populations have also been explored to elucidate the atomic interactions, along with the spatial distribution of orbital density.