CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Kui Jin,Meiyun Zhang,Penghua Che,Dongru Sun,Yong Wang,Hong Ma,Qiaohong Zhang,Chen Chen,Jie Xu
ABSTRACT Hydrogen bonding is a fascinating interaction that controls the outcomes of chemical reactions. However, overcoming the strong deactivation arising from alterations in the polarity and electronic properties of the reactants and intermediates remains a challenge. Herein, we proposed a “solvent-scissors” strategy for overcoming the inert hydrogen bonding, enabling the efficient aerobic oxidation of methyl aromatics into aromatic acids under atmospheric oxygen at 25–45 °C. The hydrogen bonds between the key intermediate, benzaldehyde (PhCHO), and hexafluoroisopropanol (HFIP) were reconstructed using solvent-scissors (acetic acid (HOAc), ethyl acetate, ethyl chloroacetate , and methyl chloroacetate), which promoted the release of free PhCHO from its inert hydrogen-bonded state and enabled the one-step oxidation of toluene to benzoic acid under mild conditions. The standard Gibbs free energy changes (Δ G 0 ) representing the proton acceptance capability of the solvent were of the same order of magnitude as the turnover number (TON) (capacity for promoting benzaldehyde oxidation). This approach affords remarkable benzoic acid selectivity (98.7%) with high toluene conversion (96.8%) at 45 °C within 4 h under 0.1 MPa O 2 using NHPI/metal acetate/HFIP-HOAc. This strategy opens up a new avenue for regulating hydrogen bonding in a wider range of applications for the planning and development of synthesis protocols.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Xiao Chen,Yunmei Du,Yu Yang,Kang Liu,Jinling Zhao,Xiaodan Xia,Lei Wang
ABSTRACT Directional construction of crystalline/amorphous (c/a)-phosphosulfide heterostructures with exceptional intrinsic activity through a facile strategy is challenging. In this study, we synthesized q-CoPS nanorods with a unique c/a-CoPS core-shell heterostructure through the ‘gas-phase phosphorus vulcanization-quenching' treatment. This work also innovatively masters the regulation of the initial quenching temperature to alter the c/a ratio of the CoPS nanorods . Surprisingly, with increasing initial quenching temperature, the area of the amorphous CoPS shell gradually increases. Density functional theory calculations reveal that the Co sites at the c/a-heterointerface, as the difunctional c/a-interface active site, effectively optimize the kinetics of the hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). As anticipated, q-CoPS/CF requires an overpotential of only 90 mV at a current density of 1000 mA cm –2 for the alkaline HER, which is much lower than that required using the state-of-the-art Pt/C catalyst. Additionally, q-CoPS/CF achieves a current density of 1000 mA cm –2 at only 0.06 V in the HzOR. Overall, this work proposes an efficient strategy for developing a bifunctional electrocatalyst with a unique c/a-heterostructure to address future energy needs.
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CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Mengzhen Ren,Tianfu Liu,Yuanyuan Dong,Zheng Li,Jiaxin Yang,Zhenheng Diao,Hongjin Lv,Guo-Yu Yang
ABSTRACT Simultaneously harnessing the photogenerated electrons and holes to convert thiols into the value-added disulfides with the concomitant formation of H 2 represents a highly promising strategy for maximizing the conversion of solar energy into chemical energy. Herein, we report an effective catalytic system comprising CdS nanorods (NRs) and Ni-containing polyoxometalate (Na 6 K 4 [Ni 4 (H 2 O) 2 (PW 9 O 34 ) 2 ] (Ni 4 P 2 )) (Ni 4 P 2 /CdS), which exhibited efficient photocatalytic activities towards the near-unity dehydrocoupling of 4-methoxythiophenol (4-MTP) into disulfide and H 2 evolution. The photooxidative dehydrocoupling of 4-MTP can be finished after 4 h photocatalysis , leading to 98.39% conversion of 4-MTP with the yield of disulfide and H 2 reaching 24.45 and 25.96 μmol, respectively. The Ni 4 P 2 /CdS catalytic system also showed good photocatalytic recycling stability. Comprehensive experimental and characterization results indicated that the synergistic cooperation between CdS NRs and Ni 4 P 2 facilitated the separation and migration of the photogenerated electron-hole pairs, thereby improving the photocatalytic dehydrocoupling of 4-MTP to disulfide coupling with hydrogen production .
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Chinese Journal of Natural Medicines
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2024
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IF 4
Mengru WANG,Qi WANG,Yanzi MA,Muhammad Aurang ZEB,Xiaoli LI,Feng SHEN,Weilie XIAO
Two new nor-ent-halimane diterpenes and three previously unreported nor -clerodane diterpenes, designated callicaintides A−E ( 1−5 ), were isolated from Callicarpa integerrima . Compounds 1 and 2 feature a distinctive 5/6-membered ring system, while compounds 3−5 are characterized by progressively truncated carbon skeletons, containing 18, 17, and 16 carbons, respectively. In addition, four known compounds 6−9 were also identified. Their structures were elucidated using advanced spectroscopic techniques, including nuclear magnetic resonance (NMR), high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), ultraviolet (UV), infrared radiation (IR), optical rotatory dispersion (ORD), DP4 + analysis and electronic circular dichroism (ECD), supported by quantum chemical calculations. Compounds 1−9 were evaluated for their anti-MRSA activity. Among them, compound 6 demonstrated significant anti-MRSA activity, with a minimum inhibitory concentration (MIC) of 16 μg·mL −1 .
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Ziwen Mei,Kejun Chen,Yao Tan,Qiuwen Liu,Qin Chen,Qiyou Wang,Xiqing Wang,Chao Cai,Kang Liu,Junwei Fu,Min Liu
ABSTRACT Electrocatalytic CO 2 reduction reaction (CO 2 RR) holds significant promise for sustainable energy conversion, with cobalt phthalocyanine (CoPc) emerging as a notable catalyst due to its high CO selectivity . However, CoPc's efficacy is hindered by its limited ability to provide sufficient proton for the protonation process, particularly at industrial current densities . Herein, we introduce defect-engineered carbon nanotubes (d-CNT) to augment proton feeding for CO 2 RR over CoPc, achieved by expediting water dissociation. Our kinetic measurements and in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy reveal d-CNT significantly enhances proton feeding, thereby facilitating CO 2 activation to *COOH in CoPc. Density functional theory calculations corroborate these findings, illustrating that d-CNT decreases the barrier to water dissociation. Consequently, the CoPc/d-CNT mixture demonstrates robust performance, achieving 500 mA cm –2 for CO 2 RR with CO selectivity exceeding 96%. Notably, CoPc/d-CNT remains stability for a duration of 20 h under a substantial current density of 150 mA cm –2 . The study broadens the scope of practical applications for molecular catalysts in CO 2 RR, marking a significant step towards sustainable energy conversion.
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CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Zhounan Yu,Leilei Zhang,Yuanlong Tan,Rizheng Jing,Hongchen Cao,Caiyi Lou,Rile Ge,Junhu Wang,Aiqin Wang,Tao Zhang
Rh-P complexes have been widely used as catalysts for hydroformylation reactions. The extremely high price of Rh and its scarce reserves have prompted the exploration of the alternatives. In this study, we reported that Pt/PS-PPh 2 single-atom catalysts promoted by SnCl 2 were highly efficient and selective for the hydroformylation of higher α-alkenes. A broad scope of substrates (i.e., C 6 –C 12 ) were smoothly converted to the corresponding linear aldehydes with high yields under reaction conditions of 90–120 °C and 4–6 MPa syngas . The turnover frequency (TOF) was comparable to homogeneous Pt-Sn catalysts, and the linear/branched ratio reached as high as > 20. In addition, the catalyst could be reused with the extra addition of SnCl 2 . The promotional role of SnCl 2 was elucidated by quasi- in situ X-ray adsorption fine structure, Fourier transform infrared, and Mössbauer spectroscopy . It was discovered that SnCl 2 was transformed into Sn(dioxane)Cl 3 − species coordinated to Pt as a moderately electron-donating ligand, which, together with the phosphine group, stabilized mononuclear Pt (I) species against reduction and aggregation.
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TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA
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2024
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IF 4.7
Li-guo ZHU,Chong-lin BAI,Ling-xin KONG,Bin YANG,Bao-qiang XU
To reduce the production cost of titanium, a new method for direct preparation of low-oxygen titanium powder by the magnesiothermic reduction of TiO 2 with the assistance of a MgCl 2 -HoCl 3 molten salt was proposed. Thermodynamic calculations showed that the magnesiothermic reduction of TiO 2 was feasible. However, hindrance of the reduction reaction by the reduction by-product of MgO resulted in a considerably high O concentration in the titanium powder. The addition of HoCl 3 to the system significantly reduces the activity of MgO to produce low-oxygen titanium powder. Thermochemical deoxidation and reduction experiments were conducted with MgCl 2 -HoCl 3 molten salt in the temperature range of 1023-1273 K. The results showed that titanium powder with oxygen concentration (mass fraction) below 5.00×10 -4 can be prepared at the Mg-MgCl 2 -HoOCl-HoCl 3 equilibrium.
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Chinese Journal of Natural Medicines
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2024
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IF 4
Qiaobei YE,Yu ZHU,Meng SHI,Linxi LV,Yuyan GONG,Luyao ZHANG,Lehe YANG,Haiyang ZHAO,Chengguang ZHAO,Huanhai XU
ABSTRACT Double cortin-like kinase 1 (DCLK1) exhibits high expression levels across various cancers, notably in human colorectal cancer (CRC). Diacerein, a clinically approved interleukin (IL)-1β inhibitor for osteoarthritis treatment, was evaluated for its impact on CRC proliferation and migration, alongside its underlying mechanisms, through both in vitro and in vivo analyses. The study employed MTT assay, colony formation, wound healing, transwell assays, flow cytometry, and Hoechst 33342 staining to assess cell proliferation, migration, and apoptosis. Additionally, proteome microarray assay and western blotting analyses were conducted to elucidate diacerein’s specific mechanism of action. Our findings indicate that diacerein significantly inhibits DCLK1-dependent CRC growth in vitro and in vivo . Through high-throughput proteomics microarray and molecular docking studies, we identified that diacerein directly interacts with DCLK1. Mechanistically, the suppression of p-STAT3 expression following DCLK1 inhibition by diacerein or specific DCLK1 siRNA was observed. Furthermore, diacerein effectively disrupted the DCLK1/STAT3 signaling pathway and its downstream targets, including MCL-1, VEGF, and survivin, thereby inhibiting CRC progression in a mouse model, thereby inhibiting CRC progression in a mouse model.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Xuemeng Sun,Jianan Liu,Qi Li,Cheng Wang,Baojiang Jiang
Nitrate pollution poses a significant environmental challenge, and photocatalytic nitrate reduction has garnered considerable attention due to its efficiency and environmental advantages. Among these, the development of Schottky junctions shows considerable potential for practical applications. However, the impact of metal nanoparticle size within Schottky junctions on photocatalytic nitrate reduction remains largely unexplored. In this study, we propose a novel method to modulate metal nanoparticle size within Schottky junctions by controlling light intensity during the photodeposition process. Smaller Au nanoparticles were found to enhance electron accumulation at active sites by promoting charge transfer from COF to Au, thereby improving internal electron transport. Additionally, the Schottky barrier effectively suppressed reverse electron transfer while enhancing NO 3 – adsorption and activation. The Au 2 -COF exhibited remarkable nitrate reduction performance, achieving an ammonia yield of 382.48 μmol g –1 h –1 , 5.7 times higher than that of pure COF. This work provides novel theoretical and practical insights into using controlled light intensity to regulate metal nanoparticle size within Schottky junctions, thereby enhancing photocatalytic nitrate reduction.
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CANCER RESEARCH
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2025
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IF 16.6
Zhang Jie,Chen Weiwu,Zhang Chen,He Qian,Wang Xudong,Han Jiayu,Gao Peng,Wang Kunyu,Xie Haoze,Gao Feng,Guo Yining,Guo Wenhao,Jiang Haofei,Le Jing,Zang Ruichen,Mo Sisi,Fan Haobo,Zhu Xiaoxiao,Jiang Xinrong,Gao Fengbin,Yu Yanlan,Ding Guoqing,Chen Yicheng
PD-1 restrains effective killing of cancer cells by the immune system and is predominantly located on the surface of T cells or other immune cells. However, cancer cells also express PD-1 to varying degrees, which is commonly associated with a poor prognosis. Here, we investigated the regulation and function of PD-1 expression in prostate cancer (PCa) and revealed the impact on the tumor microenvironment. PD-1 expression in cancer cells positively correlated with Gleason grade and metastasis but negatively correlated with CD8+ T cell infiltration in PCa patients. PCa cells secreted PD-1 in exosomes that enhanced the activity of myeloid-derived suppressor cells (MDSCs) by activating JAK/STAT3 signaling. The activated MDSCs in turn reduced the infiltration of CD8+ T cells within the tumor, promoting tumor immune evasion. The ubiquitin-specific protease USP7 induced deubiquitination and elevated the abundance of PD-1 in PCa, and USP7 inhibition sensitized PCa tumors to anti-PD-1 antibody treatment. Given the modest efficacy of current immunotherapeutic approaches for PCa, strategies to inhibit the secretion of PD-1-bearing exosomes or USP7 function may emerge as promising immunostimulatory interventions for treating PCa.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Adel Al-Salihy,Ce Liang,Abdulwahab Salah,Abdel-Basit Al-Odayni,Ziang Lu,Mengxin Chen,Qianqian Liu,Ping Xu
The potential of sustainable hydrogen production technology through water splitting necessitates the rational design of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) bi-functional electrocatalysts . In this context, we initially synthesized and empirically evaluated ultralow Ru-doped NiMoO 4 @Ni 3 (PO 4 ) 2 core-shell nanostructures on nickel foam (Ru-NiMoO 4 @Ni 3 (PO 4 ) 2 /NF). The hydrous NiMoO 4 nanopillars were hydrothermally grown on NF, followed by successive RuCl 3 etching and subsequent phosphorylation processes, leading to the final Ru-NiMoO 4 @Ni 3 (PO 4 ) 2 /NF. The catalyst demonstrated impressive HER overpotential values of −14.8 and −57.1 mV at 10 and 100 mA cm −2 , respectively, with a Tafel slope of 35.8 mV dec −1 . For OER at 100 mA cm −2 , an overpotential of 259.7 mV was observed, with a Tafel slope of 21.6 mV dec −1 . The cell voltage required for overall water splitting was 1.43 V at 10 mA cm −2 and 1.68 V at 100 mA cm −2 . Moreover, the catalyst exhibited superior stability for 150 h, emphasizing its practical utility for long-term applications. Subsequent density functional theory calculations aligned with these empirical findings, indicating a low water dissociation energy barrier (Δ G b = 0.46 eV), near-zero free adsorption energy for HER (Δ G *H = 0.02 eV), and suitable free adsorption energy for OER (Δ G *OOH − Δ G *OH = 2.74 eV), alongside a high density of states near the Fermi level . These results, informed by both experimental evaluation and theoretical validation, highlight the potential of Ru-NiMoO 4 @Ni 3 (PO 4 ) 2 /NF as a high-performance catalyst for water splitting, setting a solid foundation for advancements in sustainable energy technologies.
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CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Shuhao Wei,Ye Chen,Yiyang Qiu,Wei Kong,Di Lin,Jiarong Li,Guojun Lan,Yi Jia,Xiucheng Sun,Zaizhe Cheng,Jian Liu,P. Hu,Ying Li
Metal-free carbon catalysts have garnered significant attention since their inception. Despite substantial advancements, including widely adopted strategies such as heteroatom doping and defect engineering, their catalytic performance remains inferior to that of metal-based catalysts. In this study, we have predicted and demonstrated that the curvature of carbon plays a pivotal role in the adsorption of acetylene and the overall catalytic performance. First-principles calculations suggest that a tip-enhanced local electric field at the defect site on the curved carbon catalyst enhances the reaction kinetics for acetylene hydrochlorination. The experimental results highlight the structural advantages of the curved defect site, revealing that high-curvature defective carbon (HCDC) demonstrates an adsorption capacity for acetylene that is almost two orders of magnitude higher than that of defective carbon. Notably, HCDC achieves an acetylene conversion of up to 90% at 220 °C under a gas hourly space velocity of 300 h –1 , significantly surpassing the performance of the benchmark 0.25% Au/AC catalyst. This proof-of-concept study reveals the fundamental mechanisms driving the superior performance of carbon catalysts with curved nanostructures and presents a straightforward, environmentally friendly method for large-scale production of carbon materials with precisely controlled nanostructures. It highlights the potential for commercializing metal-free carbon catalysts in acetylene hydrochlorination and related heterogenous catalytic reactions.
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