INORGANICA CHIMICA ACTA
·
2024
·
IF 2.7
Jie Cao,Gang Xiong,Zhixiong Luo,Qiuyan Huang,Wenyan Zhou,Ileana Dragutan,Valerian Dragutan,Yaguang Sun,Fu Ding
An amide functionlized bidentate NHC-Pd complex was successfully prepared by a facile solvothermal methodology from a bridged bis-benzimidazolium chloride and K 2 PdCl 4. The new bidentate NHC-Pd complex has been effectively applied as catalyst in Suzuki-Miyaura cross-coupling reactions of aryl halides with arylboronic acids in distilled water (yields up to 99.0%). The bridged bis-benzimidazolium ligand from the Pd complex, bearing the amide functional groups on the nitrogen atom, showed to distinctly influence the electronic and steric effects on the catalytic process. The potential of application of the new NHC-Pd catalyst in diverse C C bond forming processes, working under environmentally friendly conditions, is further outlined.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Weizhen Xie,Chenting Yang,Quanwei Deng,Shigang Su,Lu Lin,Xing Tang
The selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) under mild conditions holds great significance for sustainable chemical production. However, this process remains hindered by challenges such as the instability of HMF in aqueous media and the insufficient efficiency of H 2 activation. Herein, a Pd catalyst supported on oxygen-vacancy–enriched MnO x -VC (Pd/MnO x -VC) is developed, featuring highly dispersed Pd/PdO heterostructures with abundant Pd–O–Mn interfacial active sites. Notably, Pd/MnO x -VC offered a high BHMTHF formation rates of 366.5 mol BHMTHF ·mol Pd −1 ·h −1 in water under mild conditions. Moreover, the catalyst was able to efficiently convert both purified and crude HMF at high concentrations (≥ 10 wt%), achieving BHMTHF yields exceeding 90 % in either batch or continuous-flow reactor under low temperatures (30–60 °C), underscoring its potential for industrial application. Mechanistic studies revealed that the relay activation of H 2 over Pd nanoparticles and adjacent Pd–O–Mn sites generates polarized H δ⁺ –H δ⁻ pairs, which primarily contributed to the outstanding activity of Pd/MnO x -VC. This work highlights the importance of interfacial site engineering in designing high-performance catalysts for HMF hydrogenation.
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LANGMUIR
·
2026
·
IF 3.9
Shisong Yang,Mingyang Lin,Zili Wang,E Yang,Yangyang Luo,Ran Zhu,Zheng Chen,Qian Lin,Hongyan Pan
Selective oxidation of methane to methanol by in situ-generated hydrogen peroxide (H2O2) from H2 and O2 is a promising alternative to the current industrial methods. However, it still faces the dilemma that the slow formation of the hydroxyl radical (•OH) leads to a low efficiency of partial oxidation of methane to methanol. In order to solve this problem, we constructed an Fe–Pd/SIL–NH2 composite catalyst synergistically modified by amino and [BMIM]PF6. Comprehensive characterization and experimental results show that the electron transfer path between Pd and Fe is regulated. Fe2+ and Pd2+ species are mainly distributed in Fe–Pd alloy catalysts. The Fe–Pd/SIL–NH2 catalyst not only successfully coupled the in situ synthesis and efficient decomposition of H2O2 to produce •OH radicals but also changed the local hydrophobic microenvironment of the active sites, thereby promoting the rapid desorption of hydrophilic products. These factors work together to weaken the adsorption energy of HOOH* (from 0.78 to 0.49 eV) and greatly promote the dissociation of HOOH*, thereby greatly improving the efficiency of generation of •OH radicals, which lays a foundation for the efficient synthesis of methanol. The final CH3OH yield and selectivity were as high as 73.42 mmol gFePd–1 h–1 and 87.4%, respectively, which were 2.52 and 1.67 times those of of Fe–Pd/SBA-15–NH2 and 4.87 and 2.11 times those of Fe–Pd/SIL, respectively. This study highlights the surface modification of Fe–Pd alloy catalysts for bimetallic catalysis.
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PubMed
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JOURNAL OF CATALYSIS
·
2026
·
IF 6
Long-Gen Hu,Guo-Sheng Zhang,Chen Chen,Pei-Ying Peng,Yong Lu,Xiao-Li Zhao,Ying-Xi Hua,Ye Liu
Hydrocarboxylation of alkynes using formic acid (FA) as carboxyl-source is highly challenging due to the competing decomposition of FA to H 2 /CO 2 and to CO/H 2 O to sacrifice the utilization efficiency of FA as well as to induce the side-reactions. Herein, a series of flexible and steric-bulky bis-P,O-ligands ( L1-L4 ) were synthesized and characterized on purpose to promote this reaction by avoiding unwanted FA-decomposition. It was found that L2 , characteristic with the most electron-rich nature, the bulkiest steric-hindrance, and the convenient P,P-chelation effect, enabled Pd(TFA) 2 highly active and selective for hydrocarboxylation of alkynes with FA under additive-free condition, affording the target α,β -unsaturated branched-carboxylic acids in the yield of 37–85 %. The in situ FT-IR analysis verified that the competing decomposition of FA like dehydrogenation to H 2 /CO 2 and dehydration to CO/H 2 O were completely inhibited, and the labile FA-based hybrid anhydride was the real product generated upon the catalysis of L2 -modifed Pd(TFA) 2 system.
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DIAMOND AND RELATED MATERIALS
·
2026
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IF 5.1
Bairui Tao,Chengyu Tao,Fengjuan Miao,Peng Zhang
In this study, a series of Pd Co bimetallic catalysts (Pd1Co1/C, Pd1Co2/C, Pd1Co5/C) were designed and prepared using multi-walled carbon nanotubes (MWCNTs) as supports, leveraging the strong reducing effect of sodium borohydride (NaBH 4 ) and bimetallic synergistic interactions. The objective was to optimize the electrocatalytic ethanol oxidation performance by tuning the Pd/Co ratio, with a target metal loading of approximately 0.3 mg/cm 2 . Experimental results show that the introduction of Co modulates the d-band center of Pd through electronic effects, weakening the strong adsorption of intermediates (such as Co-like species and acetaldehyde), while the high electrical conductivity and specific surface area of MWCNTs significantly enhance the dispersion of active sites and electron transfer efficiency. Electrochemical tests indicate that Pd1Co2/C exhibits the optimal catalytic activity, with a Tafel slope as low as 24.15 mV dec −1 , an exchange current density of 4430 mA/g, a specific capacitance (Cs) of 4.3 mF/cm 2 , and an electrochemical active surface area of 6.58m 2 /g. This is attributed to the synergistic promotion of reaction kinetics by the Pd Co alloy structure and the stabilizing effect of the support on nanoparticles. XRD and TEM characterizations further confirm the interatomic interactions of the bimetallic system and uniform loading characteristics. This work investigates the influence of Pd/Co ratio adjustment on the electrocatalytic ethanol oxidation performance of bimetallic catalysts, revealing the critical role of the bimetallic ratio in optimizing reaction kinetics and intermediate adsorption behavior. The findings provide experimental insights for the design of efficient anode catalysts for direct ethanol fuel cells (DEFCs).
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Catalysts
·
2023
·Vol. 13
·期 2
·435
·
IF 3.9
Yiran Liu,Yao Chen,Wen Guan,Yu Cao,Fang Wang,Yunlei Zhang
Aerobic oxidation of bio-sourced 2,5-bis(hydroxymethyl)furan (BHMF) to 2, 5-furandicarboxylic acid (FDCA), a renewable and green alternative to petroleum-derived terephthalic acid (TPA), is of great significance in green chemicals production. Herein, hierarchical porous bowl-like nitrogen-rich (nitrated) carbon-supported bimetallic Au-Pd nanocatalysts (AumPdn/ N-BNxC) with different nitrogen content and bimetal nanoparticle sizes were developed and employed for the highly efficient aerobic oxidation of BHMF to FDCA in sodium carbonate aqueous solution. The reaction pathway for catalytic oxidation of BHMF went through the steps of BHMF→HMF→HMFCA→FFCA→FDCA. Kinetics studies showed that the activation energies of BHMF, HMF, HMFCA, and FFCA were 58.1 kJ·moL−1, 39.1 kJ·moL−1, 129.2 kJ·moL−1, and 56.3 kJ·moL−1, respectively, indicating that the oxidation of intermediate HMFCA to FFCA was the rate-determining step. ESR tests proved that the active species was a superoxide radical. Owing to the synergy between the nitrogen-rich carbon support and bimetallic Au-Pd nanoparticles, the Au1Pd1/N-BN2C nanocatalysts exhibited BHMF conversion of 100% and FDCA yield of 95.8% under optimal reaction conditions. Furthermore, the nanocatalysts showed good stability and reusability. This work provides a versatile strategy for the design of heterogeneous catalysts for the highly efficient production of FDCA from BHMF.Keywords:2,5-bis(hydroxymethyl)furan;2,5-furandicarboxylic acid;aerobic oxidation;nitrogen-doped carbon;bimetallic Au-Pd nanoparticles
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Cancer Communications
·
2023
·Vol. 43
·期 5
·562-581
·
IF 16.2
Zhaowei Wen,Huiying Sun,Zhihua Zhang,Yannan Zheng,Siting Zheng,Jianping Bin,Yulin Liao,Min Shi,Rui Zhou,Wangjun Liao
Background Several clinical studies have uncovered a negative correlation between baseline tumor burden and the efficacy of immune checkpoint inhibitor (ICI) treatment. This study aimed to uncover the specific mechanisms underlying the difference in sensitivity to ICI treatment between tumors with high (HTB) and low (LTB) tumor burden. Methods For in vivo studies, several mouse models of subcutaneous tumors were established, and transcriptome sequencing, immunohistochemistry, and flow cytometry assays were used to detect the immune status in these subcutaneous tumors. For in vitro experiments, co-culture models, cytokine antibody arrays, western blotting, flow cytometry, and enzyme-linked immunosorbent assays were used to explore the underlying molecular mechanisms Results We found that MC38 or B16 subcutaneous tumors from the HTB group did not show any response to anti-programmed cell death protein-1 (PD-1) therapy. Through flow cytometry assays, we found that the infiltration with CD8 + T cells was significantly decreased whereas M2-like macrophages were enriched in subcutaneous tumors of HTB groups compared with those of LTB group. These changes were not affected by the initial number of injected tumor cells or tumor age, nor could they be reversed by surgical tumor reduction. Intraperitoneal colony-stimulating factor 1 receptor (CSF-1R) inhibitor PLX3397 injection at different time points of tumor growth only had an effect when administered in the early tumor stage to maintain the “heat” of the tumor microenvironment during the process of tumor growth, thereby achieving a response to ICI treatment when the tumor grew to a large size. Mechanistically, we found that insulin-like growth factor binding protein 2 (IGFBP2) expression levels were significantly elevated in HTB tumor tissues. IGFBP2 promoted the programmed death-ligand 1 (PD-L1) expression in M2-like macrophages by activating signal transducer and activator of transcription 3 (STAT3), and PD-L1 + M2-like macrophages exerted an immunosuppressive effect by inhibiting the proliferation and activation of CD8 + T cells in a PD-L1-dependent fashion. Conclusions This study suggested that the low efficacy of ICI treatment in HTB tumors is mainly attributed to the intratumoral accumulation of PD-L1 + M2-like macrophages via the IGFBP2-STAT3-PD-L1 signaling pathway and their substantial inhibitory effects on T cell proliferation and activation.
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PubMed
高影响因子
Catalysts
·
2023
·Vol. 13
·期 3
·637
·
IF 3.9
Yuling Wang,Yun Chen,Xinlei Ding,Jianwei Song,Gaixia Wei,Hengwei Dai,Hanyang Wang,Yadong Liu,Guangmei Bai,Wenge Qiu
In order to reduce the noble metal palladium dosage in the preparation of CL-20 so as to reduce its production cost, several carbon supports were prepared successfully using the hydrothermal carbonization method in the absence or presence of urea using microcrystalline cellulose (MC) as the carbon source, and the corresponding Pd(OH)2/C catalysts were fabricated using the deposition–precipitation method, which showed high activity in the debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) and tetraacetyldibenzylhexaazaisowurtzitane (TADB). It was found that all the catalysts showed a high efficiency in the debenzylation of HBIW, indicating that the structure of the used carbon supports had a limited impact on the catalyst performance in this reaction. On the contrary, the activities of the catalysts in the debenzylation of TADB were quite different. The results of the nitrogen sorption isotherm measurement (BET), scanning electron microscope (SEM), scanning transmission electron microscopy (STEM), powder X-ray diffraction (XRD), element analysis and temperature programmed desorption (TPD), as well as X-ray photoelectron spectra (XPS) characterizations of the supports and catalysts, showed that the relatively high activity of Pd/HTC in the debenzylation of TADB was related to the high Pd dispersion and novel mesoporous structure, while the further higher activity and stability of Pd/HTC-N1:1in the same reaction were related with its high Pd dispersion, high total oxidized Pd species, and high surface pyridinic N contents as well as the eggshell distribution of Pd species on the support.Keywords:nitrogen doping carbon support;Pd(OH)2/C catalyst;hydrogenolytic debenzylation
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CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Yan Du,Chunlei Shan,Yuchan You,Minjiang Chen,Luwen Zhu,Gaofeng Shu,Gang Han,Liming Wu,Jiansong Ji,Hong Yu,Yongzhong Du
Lenvatinib (LEN) combined with immune checkpoint PD-1 blockade is among the most effective treatment strategies for advanced hepatocellular carcinoma (HCC) and has been deemed a breakthrough therapy by the Food and Drug Administration. However, this combined strategy is associated with disadvantages such as non-tumor targeted aggregation and low oral bioavailability after long-term administration of LEN, and some patients show poor responses to immunotherapy as well. To overcome these drawbacks, SP94 peptide-modified thermal-sensitive micelles (SP94-poly(ethylene glycol)-poly(acrylamide- co -acrylonitrile, SP94-PEG-p(AAm- co -AN)) with an upper critical solution temperature (UCST) of 43 °C were designed. The micelles were further co-loaded with LEN and IR-1061-Acridine (IR-1061-AcD) to simultaneously achieve small molecule targeted drug, photothermal and photodynamic therapy for HCC under the guidance of near-infrared second-region (NIR-II) fluorescence imaging. After intravenous injection, the co-loaded micelles (SP94-PEG-p(AAm- co -AN)/LEN/IR-1061-AcD, SPLI) showed greater accumulation at tumor sites because SP94 has a high affinity for glucoregulatory protein 78 (GRP78), which is overexpressed on HCC cells. Given these HCC-targeted effects, SPLI appeared useful for NIR-II fluorescence imaging, enabling real-time tumor monitoring and surgical resection. In addition, SPLI could extensively induce immunogenic cell death in tumors, resulting in beneficial systemic immune responses. When further combined with anti-PD-1 immunotherapy, SPLI displayed a superior potential in suppressing tumor growth and metastasis while avoiding immune inhibition. Taken together, our study suggests that the aforementioned combinational strategy could serve as a desired multifunctional approach for HCC management.
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SENSORS AND ACTUATORS B-CHEMICAL
·
2022
·
IF 9.221
Minghui Wang,Yuxin Lin,Shuai Wu,Ying Deng,Yuanyuan Zhang,Jie Yang,Genxi Li
Programmed death-ligand 1 protein positive (PD-L1 + ) exosome is one of the most prospective biomarkers for the diagnosis of cancer. However, the current methods for the detection of PD-L1 + exosomes are usually laborious, time-consuming and require numerous samples. Herein, we report in this paper an electrochemical biosensor for PD-L1 + exosomes detection based on ultra-thin two-dimensional covalent organic framework nanosheets (2D COF NSs) coupled with clustered regularly interspaced short palindromic repeats (CRISPR) Cas 12a for signal amplification . Firstly, COF-367 NSs functionalized with gold nanoparticles (AuNPs) have been synthesized for the modification of the working electrode , thus the proposed sensor can show highly improved electrochemical performance. Secondly, by utilizing the trans-cleavage activity of Cas12a, this sensor can achieve very high sensitivity for the detection of PD-L1 + exosomes. With such design, the biosensor can have a linear range from 1.2 × 10 2 to 1.2 × 10 7 particles/μL with a detection limit of 38 particles/μL. Moreover, this sensor can be employed to analyze non-small cell lung cancer (NSCLC) patient serum samples, and successfully identify NSCLC patients, demonstrating the great potential in clinical applications.
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ACS Applied Nano Materials
·
2022
·
IF 6.14
Lijing Zhang,Jiaqi Han,Yuchao Wang,Wenbo Yang,Shengyang Tao
Achieving a room-temperature Suzuki–Miyaura coupling (SMC) with high efficiency is of great significance to the development of low-carbon organic synthesis. Nevertheless, it is still a great challenge to construct a promising nanocatalyst with high activity for room-temperature SMC reaction. In this paper, a strong alkaline-supported nanocatalyst Pd/Mg(OH)2/MgO–ZrO2 was rationally developed based on MgO–ZrO2 hybrid nanofibers. Physicochemical characterizations present that the in situ conversion of MgO to Mg(OH)2 on the surface of the nanofibers results in a great increase in surface alkalinity of the carrier. The strong alkalinity can greatly accelerate the oxidation addition and transmetalation of the SMC process, resulting in the obvious reduction of activation energy of the reaction (Ea = 9.0 kJmol–1 for Ph–Br). The coupling conversion can reach up to 100% at room temperature within 8 min with a maximum TOF > 6516 h–1. It also shows an excellent performance in substrate applicability and chlorobenzene activation. The rational design of a high-basicity catalyst for room-temperature SMC will be a rewarding attempt for the development of low-carbon green organic synthesis.
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高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2023
·Vol. 58
·期 36
·14299-14314
·
IF 4.5
Xu Chenzhe,Qiu Yue,Wang Zheng,Gao Zifei,Liu Cai,Sun Yanran,Zhang Haitao,Ma Juanjuan,Liu Lin,Liu Chao,Tong Zhiwei
A facile one-step hydrothermal approach was proposed to fabricate Pd nanoparticles decorated Mg–Al layered double hydroxide nanosheets (denoted as Pd NPs/Mg–Al LDH composite), wherein polyvinylpyrrolidone (PVP) functioned as both a reductant and stabilizer. The resulting samples were characterized by XRD, SEM, TEM, XPS and BET techniques. The effect of synthetic parameters during the hydrothermal reaction including PVP dosage and temperature on the size and distribution of Pd NPs was investigated in details. Pd nanoparticles with an average particle size of 3.6 nm were uniformly supported onto Mg–Al LDH nanosheets under the optimal conditions. The obtained Pd NPs/Mg–Al LDH composite could serve as an efficient heterogeneous catalyst for the Heck reaction between iodobenzene and methyl acrylate, achieving a high yield of 95.8% within 60 min at 100 °C. Furthermore, Pd NPs/Mg–Al LDH was highly stable and reused 6 times without significant loss of its catalytic activity.
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