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Science China-Materials · 2023 ·Vol. 66 ·期 8 ·3213-3222 · IF 8.1

Non-equimolar (Hf,Zr,Ta,W)B2 high-entropy diborides enable superior oxidation resistance

Wen Zihao,Meng Hong,Jiang Shengda,Tang Zhongyu,Liu Yiwen,Chu Yanhui

Developing superior oxidation resistance of high-entropy diborides is critical for extending their potential applications in harsh environments. Herein, we developed non-equimolar (Hf,Zr,Ta,W)B 2 high-entropy diborides with superior oxidation resistance by adjusting W contents for the first time. The as-fabricated (Hf 0.28 Zr 0.28 Ta 0.28 W 0.15 )B 2 samples are predicted to possess superior oxidation resistance at 1473–1773 K through the oxidation depth quantitative analysis obtained by machine learning, which is attributed to the reason that the moderate WO 3 can effectively inhibit the volatilization of B 2 O 3 . Furthermore, a four-layered structure is found in the generated product layers at 1773 K, which is due to the preferential oxidation of Hf and Zr elements at low oxygen partial pressure and the different diffusion activation energies of oxide products. The preferential oxidation of Hf and Zr elements is further demonstrated by the computational phase stability diagrams, and oxygen adsorption energies and charge transfer between oxygen atoms and different metal adsorption sites via first-principles calculations. Such superior performance endows (Hf 0.28 Zr 0.28 Ta 0.28 W 0.15 )B 2 with potential applications as ultrahigh-temperature structural materials.

CAS / MDL: 7440-42-8
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CATALYSIS LETTERS · 2023 · IF 2.8

N-doped Metallocene Catalysts for Synthesis of High Quality Lubricant Base Oils from Fishcher–Tropsch Synthesized α-Olefin

Shi Bingyu,Liu Man,Chen Jiangang

Derivatives of 2,4-dimethyldihydrocyclopentadiene were prepared, characterized by NMR spectroscopy, which was applied to 1-decene oligomerization. A two-step activation method in which both triisobutylaluminium (TIBA) and methyl aluminoxane (MAO) were co-used in sequence particularly been developed for N-doped ligand catalyst. N-doped catalyst had a very high polymerization conversion at 60–110 °C by varying the reaction temperature at 20 eq. of TIBA and 100 eq. of MAO, reaching 89.95% at 80 °C. In addition, oligomers with different viscosity grades could be obtained by adjusting the temperature. At optimized reaction conditions 75 °C, 10 eq. of TIBA and 50 eq. of MAO activation, the single pass conversion of 91.33% was achieved. The obtained oligomers had a high viscosity index above 170 at KV 100  = 6. In addition, the two-step activation method was used to compare with the conventional one-step activation method on catalysts with three different ligands of zirconium chloride. A high catalytic productivity was achieved by the two-step activation process. Depending on the nature of the ligands used, β-hydride elimination, 2,1 insertion and 1,2 rearrangement were detected as main chain release mechanisms. Meanwhile, the pathways of oligomer formation were also summarized. In brief, N-doped complex is promising catalysts for the production of high quality lubricant base oils due to their high catalytic activity and high thermal stability. Graphical Abstract

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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-10 · IF 16.6

Light-driven flow synthesis of acetic acid from methane with chemical looping

Zhang Wenqing,Xi Dawei,Chen Yihong,Chen Aobo,Jiang Yawen,Liu Hengjie,Zhou Zeyu,Zhang Hui,Liu Zhi,Long Ran,Xiong Yujie

Oxidative carbonylation of methane is an appealing approach to the synthesis of acetic acid but is limited by the demand for additional reagents. Here, we report a direct synthesis of CH 3 COOH solely from CH 4 via photochemical conversion without additional reagents. This is made possible through the construction of the PdO/Pd–WO 3 heterointerface nanocomposite containing active sites for CH 4 activation and C–C coupling. In situ characterizations reveal that CH 4 is dissociated into methyl groups on Pd sites while oxygen from PdO is the responsible for carbonyl formation. The cascade reaction between the methyl and carbonyl groups generates an acetyl precursor which is subsequently converted to CH 3 COOH. Remarkably, a production rate of 1.5 mmol g Pd –1 h –1 and selectivity of 91.6% toward CH 3 COOH is achieved in a photochemical flow reactor. This work provides insights into intermediate control via material design, and opens an avenue to conversion of CH 4 to oxygenates.

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EUROPEAN JOURNAL OF NUTRITION · 2023 ·Vol. 62 ·期 6 ·2687-2703 · IF 5

Fecal metabonomics combined with 16S rDNA sequencing to analyze the changes of gut microbiota in rats fed with different protein source diets

Zhuang Kejin,Meng Weihong,Shu Xin,Liang Defu,Wang Lidong,Zhang Dongjie

Purpose When blended, animal and plant proteins can complement each other in terms of amino acid composition and release time. In this study, we investigated whether the blended protein diet has a better feeding effect than the single protein diet, and to reveal the differences in growth and intestinal microbiota composition caused by the blended protein diet. Methods Forty Sprague Dawley (SD) rats received diets with different protein sources, including casein (C), whey protein (WP), black soybean protein (BSP), and black soybean-whey blended protein (BS-WP), for eight weeks. To investigate the effects of blended protein supplement on gut microbiota and metabolites, we performed a high throughput 16S rDNA sequencing and fecal metabolomics profiling. In addition, we determined growth and serum biochemical indices, and conducted intestinal morphology analyses. Results Compared to those in the BSP and WP groups, the daily body weight gain and feed conversion efficiency increased in the BS-WP group. Serum biochemical indices indicated that the protein utilization efficiency of the WP and BS-WP groups was relatively high, and the BS-WP blended protein diet improved the protein adoption rate. The BS-WP blended protein diet also improved intestinal tissue morphology and promoted intestinal villi development compared to the single protein diets. Furthermore, dietary protein altered the composition of gut microbiota, the gut microbial diversity of rats fed with the BS-WP diet was significantly ( P  < 0.05) higher than that of the other groups. The difference in dietary protein corresponded with an alteration of fecal amino acids and their metabolites, and tryptophan and tyrosine metabolism were the key mechanisms leading to the changes in fecal microbial composition. Conclusion Dietary protein sources played an important role in the growth and development of rats by influencing intestinal metabolism and microbial composition. The BS-WP blended protein diet was more conducive to nutrient absorption than the single protein diet. Furthermore, blended protein increased the diversity of intestinal microbes and aided the establishment of intestinal barrier function.

CAS / MDL: 30525-89-4 26675-46-7
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JOURNAL OF SOLID STATE ELECTROCHEMISTRY · 2023 ·Vol. 27 ·期 10 ·2593-2606 · IF 2.5

Inhibiting effect of tin additives on the solid-phase conversion of PbSO4 to PbO2

Li Er-Mei,Zhu Li,Li Chao-Xiong,Shi Ling-Jun,Li Bing,Li Fang,Deng Ning,He Jian-Bo

Stannous sulfate is commonly used as an additive in the positive lead pastes of lead-acid batteries, but its real function and mechanism are still vague and need further study. The present work investigates the intrinsic effects of tin additives on the positive electrode performance under well-controlled experimental conditions. The tin additives are added in three ways: the SnSO 4 dissolved in 4.5 M H 2 SO 4 electrolyte, the metal Sn melted in metal Pb substrate, and the SnSO 4 mixed in homemade industrial lead pastes. A series of evolutions are clearly revealed in structure, composition, and redox activity of the positive active materials with the content of Sn. Both the SnSO 4 in the electrolyte and in the positive lead pastes have a significant inhibiting effect on the transformation between PbSO 4 and PbO 2 , leading to a decrease in the charge/discharge capacities with increasing content of SnSO 4 . A similar but weaker inhibiting effect was also found for the Sn melted in the Pb-Sn alloys. The SnSO 4 has a significant enhancement effect on the grain size of PbSO 4 /PbO 2 , which increases the resistance of the solid-phase transformation deep inside the grains during the charge/discharge. All these results do not support the use of SnSO 4 in the positive pastes of lead-acid batteries. Graphical abstract

CAS / MDL: 7439-92-1 7440-31-5
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CHEMICAL PAPERS · 2023 ·Vol. 77 ·期 10 ·5999-6006 · IF 2.2

Kinetic analysis of wet process phosphoric acid hydrolysis of corncob

Yuan Yifan,He Fuduo,Li Xue,Xu Dehua,Yan Zhengjuan,Wang Xinlong

Corncob has a high yield and contains a large number of cellulose substances. Wet phosphoric acid hydrolysis of corncob is of great significance to the utilization of organic waste, and provides theoretical support for the development of sugar-containing synergistic phosphorus fertilizers. In this study, the kinetics of hydrolysis of corncob by wet process phosphoric acid was investigated. The time evolution of total sugar, xylose and furfural formation during a 12-h hydrolysis was simulated by Saeman and biphasic models within differential acid concentrations and temperatures. The formations of both total sugar and furfural coincide a first-order irreversible reaction, which was not applicable to the Saeman model nor the biphasic model. Meanwhile, xylose formation was more suitable for the Saeman model. The optimal conditions for xylose are: a temperature of 100 °C, a reaction time of 720 min, an acid concentration of 55.6% (w/w). The xylose yield of corncobs was 0.15 g/g in the optimal conditions. Graphical abstract

CAS / MDL: 98-01-1 25990-60-7
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WATER AIR AND SOIL POLLUTION · 2023 ·Vol. 234 ·期 7 ·1-9 · IF 2.9

Ecotoxicity of Choline Ionic Liquids with Different Anions

Shi Zhimeng,Liu Yuchen,Wang Xiaowen,Du Kehui,Tian Hongzhe

Five choline ionic liquids were selected to evaluate their toxicity to green alga ( Chlorella vulgaris ) and Daphnia magna . Their influence on chlorophyll content, respiration rate, antioxidase activity, and malondialdehyde content of Chlorella vulgaris and the acute and chronic toxicity of Daphnia magna were investigated. The studied ionic liquids slightly inhibited the algal growth with the median effective concentrations (EC 50 ) > 1900 mg/L. Chlorophyll contents, respiration rate, and protein contents of the alga after 96 h of exposure decreased with the higher concentrations of the ionic liquids, while superoxide dismutase and catalase activity and malondialdehyde content increased firstly and then decreased. The acute toxicity of Daphnia magna after 48 h of exposure (indicated by the median effective concentrations, EC 50 ) was 200.44 and 184.50 mg/L for choline acetate and choline D-lactate, respectively, which was above the toxicity of other ionic liquids. The studied ionic liquids presented low toxicity to Chlorella vulgaris and Daphnia magna .

CAS / MDL: 143314-16-3
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JOURNAL OF APPLIED ELECTROCHEMISTRY · 2023 ·Vol. 53 ·期 12 ·2331-2346 · IF 2.9

Effect of additives on microstructure and properties of the coarsened layer of very low profile (HVLP) copper foil

Xiao Yan,Sun Wan-chang,Bai Zhong-bo,Liu Er-yong,Du Liang-liang,Cai Hui,Wang Li-ping,Liu Jing-pei,Jia Ya-peng,Zhang Jie

Additives are a cost-effective method to improve the performance of the very low profile (HVLP) copper foil coarsened layer. In this paper, the effects of 3,3’-Dithiobis-1-propanesulfonic acid disodium salt (SPS), gelatin, and sodium thiazoline dithiopropane sulfonate (SH110) concentration on the morphology, roughness, and peel strength of HVLP copper foil was reported. The results show that SH110 contributes significantly to the reduction of copper foil roughness, improvement of peel strength, and refinement of coarsened layer grains. In addition, the linear scanning voltammetry and AC impedance spectroscopy of the solution were carried out to understand the action mechanism of additives on the copper foil surface. The results demonstrate that SPS promotes the copper deposition process due to the presence of sulfonic acid groups(–SO 3 ). The amino group(–NH 2 ) of gelatin inhibits copper deposition. SH110 has both promoter (Sodium 3-Mercapto-1-Propane Sulfonate, MPS) and inhibitor (Tetrahydrothiazolidinone, H1) fragments, which achieve synergistic or competitive effects consistent with the composite additive. Graphical abstract

CAS / MDL: 9000-70-8
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Carbon Letters · 2023 ·Vol. 33 ·期 6 ·1839-1846 · IF 4.5

Soft-template-assisted synthesis of N-doping layered CoS2 nanoparticles as an advanced anode for sodium-ion batteries

Han Danyang,Yu Guo,Liu An,Li Gangyong,Wang Wei,He Binhong,Hou Zhaohui,Yin Hong

As a promising anode for sodium-ion batteries (SIBs), cobalt sulfide (CoS 2 ) has attracted extensive attention due to its high theoretical capacity, easy preparation, and superior electrochemical activity. However, its intrinsic low conductivity and large volume expansion result in poor cycling ability. Herein, nitrogen-doped carbon-coated CoS 2 nanoparticles (N–C@CoS 2 ) were prepared by a C 3 N 4 soft-template-assisted method. Carbon coating improves the conductivity and prevents the aggregation of CoS 2 nanoparticles. In addition, the C 3 N 4 template provides a porous graphene-like structure as a conductive framework, affording a fast and constant transport path for electrons and void space for buffering the volume change of CoS 2 nanoparticles. Benefitting from the superiorities, the Na-storage properties of the N–C@CoS 2 electrode are remarkably boosted. The advanced anode delivers a long-term capacity of 376.27 mAh g −1 at 0.1 A g −1 after 500 cycles. This method can also apply to preparing other metal sulfide materials for SIBs and provides the relevant experimental basis for the further development of energy storage materials.

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JOURNAL OF POLYMER RESEARCH · 2023 ·Vol. 30 ·期 6 ·1-12 · IF 2.8

Design of a bio-based flame retardant for polyvinyl alcohol with superior flame retardant, mechanical and UV-blocking properties

Wang Chenlin,Zhang Zhihao,Ma Zhongying,Zhou Zhenzhu,Wang Yuhua

In present, during preparing flame retardant polyvinyl alcohol (PVA) composites, most flame retardants present inferior fire retardant efficiency and trend to decrease the mechanical performance of PVA owing to bad dispersibility. Besides, they possess possible threat to human and environmental safety. In order to solve these issues, a bio-based flame retardant (PAE) is synthesized by using phytic acid and ethylenediamine to improve PVA flame retardancy, UV shielding properties and mechanical properties. According to thermographic examination, PVA composites retained its well-performed capacity of char production and thermal stability with the addition of PAE. The limiting oxygen index grows from 18.4% of pure PVA to 29.7% of PVA/PAE-15 composite and vertical burning rating reaches UL-94 V-0. The peak heat release rate and total heat release of PVA/PAE-15 sharply decreased by 68.1% and 31.0% comparing with pristine PVA. More importantly, PVA/PAE composites have outstanding mechanical properties and UV shielding, the addition of 5 wt.% PAE increases the tensile strength from 67.6 MPa to 85.1 MPa compared with pure PVA. Therefore, the results imply that the inclusion of PAE can elevate the flame retardant capability, mechanical properties and UV shielding of PVA.

CAS / MDL: 83-86-3
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JOURNAL OF APPLIED ELECTROCHEMISTRY · 2023 ·Vol. 53 ·期 12 ·2443-2455 · IF 2.9

An environmentally friendly, layer-by-layer assembled electrode for ultrafast electrochemical detection of nitrite in water

Du Xinle,Zhang Yuhan,Liu Mengying,Tian Xinyu,Cao Zhenbo

The development of sensors for rapid nitrite detection in water is of great significance to human health and environmental protection. In this study, carboxylated cellulose nanocrystals were prepared by oxidizing microcrystalline cellulose with ammonium persulfate. Subsequently, a composite film was successfully prepared by depositing carboxylated nanocrystalline cellulose and poly(diallyldimethyl ammonium chloride) onto a glass carbon electrode using the layer-by-layer assembly method. After electrodepositing poly(3,4-ethylenedioxythiophene), the resulting electrode was utilized as an electrochemical sensor for nitrite detection. The effect of the number of layers of the composite film on electrocatalytic performance towards nitrite was investigated. Under optimal conditions, the sensor exhibited an ultrafast response to nitrite within 0.5 s, which was better than that of most similar sensors reported. Additionally, it had a wide linear range of 0.5–3000 µM and a low detection limit of 0.26 µM. Furthermore, this sensor showed satisfactory recovery between 98.78 and 103.29% for nitrite in real water samples. Our study presents a significant approach towards the development of an environmentally friendly nitrite sensor with an ultrafast response. Graphical abstract

CAS / MDL: 7727-54-0
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Journal of Orthopaedic Surgery and Research · 2023 ·Vol. 18 ·期 1 ·1-15 · IF 2.6

Tanshinone I alleviates steroid-induced osteonecrosis of femoral heads and promotes angiogenesis: in vivo and in vitro studies

Sun Kai,Xue Yuman,Zhang Xin,Li Xiaodong,Zhao Jun,Xu Xilin,Zhang Xiaofeng,Yang Fubiao

Background The impaired blood supply to the bones is an important pathological feature of steroid-induced osteonecrosis of the femoral head (SIONFH). Danshen is a Chinese herb that shows therapeutic effects on SIONFH, but the effects of one of its major bioactive constituents, Tanshinone I (TsI), on SIONFH remain unknown. Here, we evaluated the effects of TsI on SIONFH, particularly focusing on its effects on angiogenesis, in in vivo and in vitro research. Methods SIONFH was induced in Sprague–Dawley rats by an intramuscular injection of methylprednisolone (40 mg/kg) in combination with an intraperitoneal injection of lipopolysaccharide (20 μg/kg). Morphological alterations of the femoral head were observed by dual-energy X-ray absorptiometry and HE staining. Western blot, qRT-PCR, and immunohistochemical/immunofluorescence staining were used to determine gene expression. Results TsI (10 mg/kg) alleviated bone loss and rescued the expression of angiogenesis-related molecules (CD31, VWF, VEGF, and VEGFR2) in the femoral heads of SIONFH rats. Notably, TsI rescued the down-regulated expression of SRY-box transcription factor 11 (SOX11) in CD31 + endothelial cells in the femoral heads of SIONFH rats. In vitro studies showed that TsI preserved the dexamethasone-harmed angiogenic property (migration and tube formation) of human umbilical vein cells (EA.hy926), suppressed dexamethasone-induced cell apoptosis, reduced pro-apoptotic proteins (cytosolic cytochrome C, Bax, and caspase 3/9) and increased anti-apoptotic protein Bcl-2, whereas silencing of SOX11 reversed these beneficial effects. Conclusions This study demonstrates that TsI alleviates SIONFH and promotes angiogenesis by regulating SOX11 expression. Our work would provide new evidence for the application of TsI to treat SIONFH. Graphical Abstract

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