Spin-state regulating of cobalt assisted by iron doping and coordination for enhanced oxygen evolution reaction

Customizing catalysts from the electronic structure, such as spin state, is an effective but challenging strategy for oxygen evolution reaction (OER). Herein, an ultrafine Co–Fe material highly dispersed on nitrogen carbide matrix is fabricated by coordination polymer and self-templating method to scrutinize the impact of spin state of Co on OER through Fe doping. The optimized catalyst shows boosted OER performance, which only requires overpotential of 333 mV at 10 mA cm^?2, outperforming other control samples and commercial RuO₂. The elevated local spin states of Co by Fe doping lead to charge transfer acceleration and fast generation of oxygenated intermediates, which is proved to account for the OER elevation. In addition, the long-term stability of Co–Fe material is guaranteed by the strong coordination of Co/Fe to the melamine-formaldehyde resin, which is used to adsorb metal ions, contributing to the high dispersion of active sites during the OER process.     

Cytotoxic Potential of a-Azepano- and 3-Amino-3,4-SeCo-Triterpenoids

Semi-synthetic triterpenoids, holding an amino substituted seven-membered A-ring (azepano-ring), which could be synthesized from triterpenic oximes through a Beckmann type rearrangement followed by a reduction of lactame fragment, are considered to be novel promising agents exhibiting anti-microbial, alpha-glucosidase, and butyrylcholinesterase inhibitory activities. In this study, in an attempt to develop new antitumor candidates, a series of A-ring azepano- and 3-amino-3,4-seco-derivatives of betulin, oleanolic, ursolic, and glycyrrhetinic acids were evaluated for their cytotoxic activity against five human cancer cell lines and non-malignant mouse fibroblasts by means of a colorimetric sulforhodamine assay. Azepanoallobetulinic acid amide derivative 11 was the most cytotoxic compound of this series but showed little selectivity between the different human tumor cell lines. Flow cytometry experiments showed compound 11 to act mainly by apoptosis (44.3%) and late apoptosis (21.4%). The compounds were further screened at the National Cancer Institute towards a panel of 60 cancer cell lines. It was found that compounds 3, 4, 7, 8, 9, 11, 15, 16, 19, and 20 showed growth inhibitory (GI₅₀) against the most sensitive cell lines at submicromolar concentrations (0.20–0.94 μM), and their cytotoxic activity (LC₅₀) was also high (1–6 μM). Derivatives 3, 8, 11, 15, and 16 demonstrated a certain selectivity profile at GI₅₀ level from 5.16 to 9.56 towards K-562, CCRF-CEM, HL-60(TB), and RPMI-8226 (Leukemia), HT29 (Colon cancer), and OVCAR-4 (Ovarian cancer) cell lines. Selectivity indexes of azepanoerythrodiol 3 at TGI level ranged from 5.93 (CNS cancer cell lines SF-539, SNB-19 and SNB-75) to 14.89 for HCT-116 (colon cancer) with SI 9.56 at GI₅₀ level for the leukemia cell line K-562. The present study highlighted the importance of A-azepano-ring in the triterpenic core for the development of novel antitumor agents, and a future aim to increase the selectivity profile will thus lie in the area of modifications of azepano-triterpenic acids at their carboxyl group.     

Hit to Leads with Cytotoxic Effect in Leukemic Cells: Total Synthesis Intermediates as a Molecule Treasure Chest

A previously designed and developed 12-step total synthesis that includes [1,1′-biphenyl]-2-amine and carbazole intermediates and that ultimately produces the carbazole alkaloid carbazomycin G was exploited as a screening compound library with the goal of identifying potential lead compound(s) with cytotoxic effect. These compounds were investigated by using in-vitro tests involving the two human cell lines HL-60 and MOLM-13, which both model acute myeloid leukaemia (AML). The in-vitro biological test results were used together with the molecular structures of the various intermediates in a concise SAR analysis. Several of the intermediates revealed cytotoxicity (IC₅₀<10⁻⁴ M), although the final natural product carbazomycin G did not reveal cytotoxicity versus the two said human cell lines.     

ZK60镁合金表面滚压强化试验研究

试验研究了ZK60镁合金表面滚压加工中工艺参数对试件表面粗糙度、表面形貌、表面残余应力和表层显微硬度的影响,结果表明滚压力和重复滚压次数对试件的表面粗糙度、表面形貌以及表面残余应力和表层硬度影响程度较大,滚压速度影响较小。对精车ZK60镁合金试件进行滚压加工,试件表面粗糙度R a、R z最大减小了50.3%和48.1%;残余压应力最大可达-54.55 MPa;显微硬度从试件表层到内部基体材料逐渐降低,表层硬度值最大为92.83 HV 0.25,比基体材料硬度提高了15.32%。     

Effect of Co addition on microstructural and mechanical properties of WC–B4C–SiC composites

In this study, the effect of Co addition on microstructural and mechanical properties of WC-B₄C–SiC composites sintered by spark plasma sintering (SPS) method was investigated. For this purpose, three batches of WC-B₄C–SiC with different contents of Co (10 vol%, 15 vol%, and 20 Vol %) were sintered at 1400 °C. The results of X-ray diffraction (XRD) analysis of the samples indicated the formation of W₂B₅, W₃CoB₃ as well as the remained C phases and unreacted SiC phase. It was observed that by increasing the Co content, the amount of W₂B₅ phase reduces and W₃CoB₃ and C contents increase. Therefore, W₂B₅ peaks were not detected in the sample containing 20vol% Co. Relative density values above 97% were obtained for all the composites. However, a decrease was observed in relative density by increasing the Co content in the composites. The highest flexural strength (510 ± 42 MPa), fracture toughness (10.34 ± 0.82 MPa m^1/2), and hardness (20.63 ± 0.75 GPa) were also obtained for the sample containing 10vol% Co compared to the other samples. In addition, Transgranular fracture of SiC as well as pulling out of W₃CoB₃ and W₂B₅ particles were observed in the fracture surface micrographs of the samples. The presence of micro-cracks in the SiC grains, fracture of W₃CoB₃ grains, and crack deflection was reported as dominant toughening mechanisms.     

Synthesis and characterization of transition metal mixed oxide doped graphene embedded durable electrocatalyst for hydrogen evolution reaction

A promising electrocatalyst containing variable percentage of V₂O₅–TiO₂ mixed oxide in graphene oxide support was prepared by embedding the catalyst on Cu substrate through facile electroless Ni–Co–P plating for hydrogen evolution reaction. The solvothermal decomposition method was opted for tuning the crystalline characteristics of prepared material. The optimized mixed oxide was well characterized, active sites centres were identified and explained by X-ray diffraction, high resolution tunnelling electron microscopy, scanning electron microscopy coupled with energy dispersive X-ray and X-ray photon spectroscopy analysis. The structural and electronic characteristics of material was done by fourier transform infrared spectroscopy and the electrochemical behaviour of the prepared material was evaluated by using Tafel plot, electrochemical impedance analysis, linear sweep voltammetry, open circuit analysis and chronoamperometry measurements. The results show the enhanced catalytic activity of Ni–Co–P than pure Ni–P plate, due to synergic effect. Moreover, the prepared mixed oxide incorporated Ni–Co–P plate has a high activity towards HER with low over potential of 101 mV, low Tafel slope of 36 mVdec^?1, high exchange current density of 9.90 × 10^?2 Acm^?2.     

Kinetics and mechanistic studies of methane dry reforming over Ca promoted 1Co–1Ce/AC-N catalyst

The mechanism and kinetic features of dry reforming with methane (DRM) over Ca promoted 1Co–1Ce/AC-N catalyst was investigated. The mechanistic pathway studies have conducted by FTIR and XPS analysis, structure-activity correlations demonstrated the CH₄ and CO₂ could adsorb on catalyst active sites and generate intermediate CH_x, OH and CH_xO, continue to generate CO and H₂ and then desorbed from active sites. Moreover, CH₄ could also oxidized by Ce⁴⁺ and CO₂ reduced by Ce³⁺, the same content of Ce⁴⁺ and Ce³⁺ on promoted catalyst greatly improved the reaction rate. The kinetic of dry reforming with methane was examined for temperature between 650 and 850 at 800 °C. The research was carried out by changing the CH₄/CO₂ ratios between 0.3 and 3.0. The obtained experiment data were fitted by three typical kinetic models (Power Law, Eley-Rideal and Langmuir-Hinshelwood), the fitting results demonstrated that the best prediction of reforming rates can provided by Langmuir-Hinshelwood model for the reaction temperatures between 650 and 800 °C. Moreover, activation energies of methane and carbon dioxide consumption were ?117 and ?47 kJ/mol, indicating that much higher energy barrier is needed for methane activation compared to carbon dioxide.     

海水中134Cs、137Cs和60Co的联合分析

建立了小体积海水中¹³⁴Cs、¹³⁷Cs和⁶⁰Co的联合分析方法，确定了最佳实验条件。采用磷钼酸铵富集法对海水中放射性铯进行浓集后，其上清液利用氢氧化钴沉淀载带海水中的⁶⁰Co，用γ能谱仪进行测量。结果表明：该法对海水中放射性¹³⁴Cs、¹³⁷Cs和⁶⁰Co的回收率分别为87%~95%、87%~95%和89%~93%，检测限分别为0.048、0.051、0.046 Bq/L。另外，对2017年IAEA国际比对（IAEA-RML-2017-01）海水样品中的¹³⁴Cs、¹³⁷Cs和⁶⁰Co进行分析测量，核素分析结果的最终评价均为“通过”，验证了本实验室采用的¹³⁴Cs、¹³⁷Cs和⁶⁰Co联合分析方法的可行性和可靠性，为今后该方法在常规海洋环境放射性监测中的应用推广奠定了基础。     

γ射线和电子束辐照对风味豆干杀菌效果及品质的影响

为探究γ射线和电子束辐照对风味豆干微生物和理化指标影响的差异性，分别采用不同剂量的γ射线（0、3.1、5.9、8.6、11.4 kGy）和电子束（0、2.7、5.5、8.2、10.8 kGy）辐照风味豆干，研究其对风味豆干中微生物存活数、营养成分、理化指标及质构特性的影响。结果表明，γ射线和电子束辐照均能有效控制风味豆干菌落总数、霉菌及大肠菌群数，γ射线辐照杂菌和霉菌的D₁₀值分别为1.82 kGy和1.72 kGy，电子束辐照的D₁₀值分别为2.44 kGy和1.79 kGy，γ射线对风味豆干的杀菌效果强于电子束。两种辐照方式对风味豆干水分、蛋白和灰分的含量没有明显影响，但辐照后脂肪含量均显著降低。γ射线辐照后风味豆干氨基酸的含量无明显变化，但5.5 kGy剂量条件下，电子束辐照会对缬氨酸、苯丙氨酸、脯氨酸、甘氨酸、丙氨酸、酪氨酸等6种氨基酸的含量产生显著影响。γ射线辐照对风味豆干过氧化值有显著的影响，与酸价无明显的相关性；而电子束辐照与风味豆干过氧化值没有明显的相关性，但会引起其酸价显著上升。γ射线辐照不会对风味豆干硬度、内聚性、胶着性、咀嚼性和弹性产生显著影响，电子束辐照对其硬度、内聚性和胶着性的影响不显著，但5.5 kGy以上剂量辐照会对其咀嚼性和弹性产生显著的影响。综上所述，γ射线和电子束对风味豆干的辐照效应在某些方面存在一定的差异性，但均具有在豆干加工中应用的潜力，研究结果可为γ射线和电子束辐照技术在豆干加工中的应用提供理论依据。     

Super-oleophilicity Co-doping Co2+/F-/TiO2 one-dimensional nanotubes for photocatalytic denitrification of light oil

In this study, a simple hydrothermal synthesis method was adapted for the preparation of Co-doping Co²⁺/F^-/TiO₂ nanotubes photocatalyst, and the micro-nano structure of catalysts prepared by biomimetic technology which makes the catalyst have super-oleophilicity property. Co²⁺/F^-/TiO₂ revealed improved photocatalytic performance for denitrification of light oil compared to single TiO₂ photocatalysts. The enhance of photocatalytic activity can be attributed to narrowing the band gap, increasing the light response wavelength and exposing more highly active crystal surfaces due to synergistic effects of Co²⁺ and F^? in the photocatalyst.