JOURNAL OF ALLOYS AND COMPOUNDS
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2025
·
IF 6.3
Yakai Chen,Xinya Feng,Xiaohan Yu,Xingliang Xu,Jing Xu
Catalytic transfer hydrogenation of nitro compounds to amines under mild conditions offers an alternative strategy to traditional hydrogenation processes involving pressurized molecular hydrogen, which necessitate the rational design and integration of multifunctional catalyst. Herein, a ternary composite catalyst (Pd/CeO 2 -C 3 N 4 ) was designed and synthesized for the transfer hydrogenation of nitro compounds to corresponding amines compounds using formic acid as hydrogen donor. The Pd/CeO 2 -C 3 N 4 catalyst shows remarkably high performance for the catalytic transfer hydrogenation of nitrobenzene (NB) to aniline (BA), achieving > 98 % conversion and exceedingly high selectivity (>99 %). The catalyst exhibits a high turnover frequency (TOF) of up to 2868 h - , significantly surpassing both the reference catalyst (Pd/C 3 N 4 and Pd/CeO 2 ) and the conventional Pd/C catalyst. The multi-functional Pd/CeO 2 -C 3 N 4 catalyst features enhanced electron transfer properties,well-exposed Pd active sites, and abundant acid-base sites, enabling effective enhancement of formic acid dehydrogenation and nitro group activation. Moreover, Pd/CeO 2 -C 3 N 4 demonstrates excellent recyclability and a broad substrate scope for the catalytic transfer hydrogenation of various nitro compounds. The rational design of Pd/CeO 2 -C 3 N 4 will broaden the application range of Pd-based catalysts and provide a sustainable and effective approach for the catalytic transfer hydrogenation of other industrially relevant organic compounds.
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高影响因子
Translational Cancer Research
·
2025
·Vol. 14
·期 10
·6454
·
IF 1.7
Jiaxuan Zhao,Han Wu,Zhe Sun,Yeting Cui,Nan Liu,Yixuan Wang,Youyong Wang,Jiangzhou Shi,Tongcun Zhang
Background Chimeric antigen receptor T cell (CAR-T) therapy targeting cluster of differentiation 19 (CD19) has shown promise in treating B-cell acute lymphoblastic leukemia (B-ALL), but the long-term efficacy of CD19-targeted CAR-T therapy remains limited. Programmed cell death protein 1 (PD-1), an inhibitory receptor on activated T cells, engages programmed death ligand 1 (PD-L1) in the tumor microenvironment, suppressing CAR-T cell function by impairing key signaling pathways. To address this limitation, we investigated the effect of short hairpin RNA (shRNA)-mediated PD-1 knockdown on alleviating CAR-T cell exhaustion, preserving memory phenotype, and enhancing the long-term efficacy of CD19-targeted CAR-T cells. Methods To overcome this limitation, we employed shRNA to achieve PD-1 knockdown in CD19-targeting CAR-T cells. Following screening multiple shRNA candidates, we assessed the cytotoxicity, cytokine secretion, and proliferation of PD-1 knockdown CAR-T cells. Their memory phenotype, exhaustion marker, and cytolytic function were further evaluated after repeated antigen stimulation. Therapeutic efficacy and safety were validated in NOD.Cg-PrkdC scid Il2rg tm1 /Vst (NPG) mice. Results PD-1 knockdown significantly enhanced CAR-T cell cytotoxicity and persistence against PD-L1+ RAJI (human Burkitt’s lymphoma cell line) cells. After three rounds of antigen stimulation, PD-1 knockdown CAR-T cells sustained cytotoxic activity, retained a memory-like phenotype, and displayed attenuated exhaustion markers. In vivo , they prolonged survival without inducing cytokine release syndrome (CRS), indicating improved efficacy and safety. Conclusions PD-1 knockdown mitigates tumor-induced T-cell exhaustion and represents a promising strategy to enhance the durability and potency of CAR-T cell therapy in cancer treatment.
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DOI
PubMed
高影响因子
Ecological Frontiers
·
2025
·
IF 0
Xinyi Wu,Yan Li,Linghan Li,Hongwei Liu,Yongguang Yin,Shixiang Gao,Maoyong Song,Zhiqiang Tan,Yan Ma
Monitoring nanoplastic (NP) aggregation in bidisperse systems under environmentally relevant ionic conditions remains a significant challenge. Conventional techniques such as dynamic light scattering and transmission electron microscopy are hindered by matrix interference, low sensitivity, and difficulties in resolving polydispersity. Here, we addressed this gap by using a coupled system including hollow fiber flow field-flow fractionation (HF5), ultraviolet-visible detector (UV), and point-discharge optical emission spectroscopy (PD-OES) to investigate aggregation behavior of bidisperse polystyrene NPs (PSNPs, 50 nm and 100 nm) at ionic conditions below 1 mM, representative of freshwater ecosystems. We demonstrated that bidisperse PSNPs exhibit enhanced aggregation compared to monodisperse counterparts by using the HF5-UV/PD-OES platform for purification, separation, and carbon-specific quantification. This platform elucidated the critical roles of cation valence (Na + vs. Ca 2+ ) and low concentration ion gradients (0.01–1 mM) in modulating aggregation over extended scales (i.e., 24 h). Finally, toxicity assessments on Microcystis aeruginosa revealed that aggregation reduces PSNP ecotoxicity depending on cation valence, thereby alleviating growth inhibition, oxidative stress, and impairment of chlorophyll biosynthesis. These findings elucidate how environmentally relevant ionic conditions govern NP fate and effects in freshwater ecosystems, providing a critical link between physicochemical transformations and biological responses for ecological risk evaluation.
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Green Energy & Environment
·
2025
·
IF 14.6
Wen Zhao,Qun Yu,Bingqing Wei,Lei Nie,Fabio Souza Toniolo,Zhenglong Li
Although current methods enable lignin extraction and depolymerization, the selective hydrogenolysis of lignin into alkene-functionalized monomers remains a significant scientific challenge. These monomers can be further functionalized into diverse natural products or pharmaceutical intermediates, thereby enabling higher-value utilization of biomass resources. Here, we report a catalyst with low Pd loading (0.4 wt%) supported on ZnO-modified carbon nanotubes (Pd/ZnNC) for the selective catalytic hydrogenolysis of the dimer β-O-4 lignin model compound (veratrylglycerol-β-guaiacyl ether, VG) via distinct reaction pathways. The Pd/ZnNC catalyst achieves a selectivity of 37.5% toward alkene-functionalized monomers (1,2-dimethoxy-4-allylbenzene and 1,2-dimethoxy-4-propenylbenzene), approaching 75% of the theoretical maximum selectivity (50%). In contrast, the Pd/CNT catalyst predominantly produces 3-(3,4-dimethoxyphenyl)-1-propanol, and excessive side-chain saturation of monomers are not conducive to subsequent utilization processes. Moreover, the Pd/ZnNC catalyst achieves a conversion rate seven-fold higher than that of commercial catalysts Pd/C (5 wt%). Experimental characterization results demonstrate that the ZnO sites on carbon nanotubes facilitate the dispersion of Pd nanoparticles, resulting in a reduction in particle size. Furthermore, the synergistic effect between ZnO and Pd active sites promotes the selective catalytic formation of monomers containing unsaturated C=C bonds. The DFT calculations reveal that the Cγ-OH elimination is facilitated by Pd nanoparticles supported on ZnO, which reduces the reaction energy barrier and promotes the generation of propenyl-substituted monomers. The pathway enabled by Pd/ZnNC catalyst offers a great potential for lignin depolymerization into high-value products.
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高影响因子
Frontiers in Bioengineering and Biotechnology
·
2023
·
IF 5.7
Wei Min,Shen Xiao,Fan Xueqi,Li Jiwei,Bai Jingwen
Immune checkpoint blockade is now recognized as a paradigm-shifting cancer therapeutic strategy, whereas there remains difficulty in accurately predicting immunotherapy efficacy by PD-L1 expression. In addition, radiotherapy for cancer patients faces the problem of insufficient dose of radiotherapy at the tumor site while which have been not tolerated by normal tissues. In this study, we created PD-L1 aptamer-anchored spherical nucleic acids (SNAs) with a shell made of PD-L1 aptamer and indocyanine green (ICG) embedded in a mesoporous hafnium oxide nanoparticle core (Hf@ICG-Apt). Upon low pH irradiation in the tumor sites, the nano-system enabled the release of ICG in the high PD-L1 expression tumor to develop a high tumor-to-background ratio of 7.97 ± 0.76 and enhanced the ICG tumor retention to more than 48 h. Moreover, Hf@ICG-Apt improved radiation therapy (RT) when combined with radiation. Notably, Hf@ICG-Apt showed scarcely any systemic toxicity in vivo. Overall, this research offered a novel approach for applying reliable monitoring of PD-L1 expression and localization and robust RT sensitization against cancer with good biosafety.
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高影响因子
ANALYTICAL CHEMISTRY
·
2019
·
IF 6.35
Shuzhen Lv,Kangyao Zhang,Ling Zhu,Dianping Tang,Reinhard Niessner,Dietmar Knopp
With the introduction of gas-based contactless electrochemical biosensors lies the prospects of separating the sensing interface from the bioassembly platform, enhancing stability, and exploring signal transduction mechanism, all intimately linking to development of immunoassay. Herein, we report on a H2-based electrochemical biosensor whose signals derived from the chemical signal transduction between a H2 and Pd nanowires@ZIF-67 (ZIF: Zeolitic Imidazolate Frameworks) bilayered sensing interface for immunoassay. Dendritic Pt nanoparticles (DPNs) conjugated on the detection antibody were introduced on the interface of a magnetic microsphere according to an immune sandwich assembly between the antigen and antibody. H2 as a bridge originates from DPNs catalyzing NH3BH3 and links biological signals to electrical signals by reacting with Pd nanowires. Nevertheless, the response of Pd nanowires being extremely effected by O2 in air due to the competitive adsorption on the surface of Pd nanostructures as well as the reaction between chemisorbed O (Pd–O) and adsorbed dihydrogen lead to a decrease in H absorption into PdHx and poor sensing responses under low target concentration. Porous ZIF-67 (window aperture 0.331 nm) as a molecular sieve self-assembling on the surface of the Pd nanowires film could easily permeate H2 (kinetic diameter of 0.289 nm), while interferential O2 (kinetic diameter of 0.346 nm) has difficultly passing through the ZIF-67 layer to contact Pd nanowires and achieves a response of a lower concentration target as well as faster response rate. Under optimal conditions, H2-based electrochemical biosensors exhibit great response toward target alpha-fetoprotein (AFP) within a dynamic working range of 0.1–50 ng mL–1 at a detection limit of 0.04 ng mL–1. Our strategy provides a reusable sensing interface, high specificity, and acceptable accuracy for the immunoassay. In addition, it also expands a promising platform for application as a molecular sieve in electrochemical biosensors.
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高影响因子
JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY
·
2017
·Vol. 314
·期 1
·59-67
·
IF 1.282
Liu Zhanxiang,Dong Yang,Liao Jiali,Li Xingliang,Yang Jijun,Yang Yuanyou,Luo Shunzhong,Liu Ning
A novel extractant, 5-octyloxymethyl-7-bromo-8-quinolinol (HBrO 8 Q), was employed to extract Pd(II) from low-acidity aqueous solution. The extraction behaviors indicated that HBrO 8 Q had high extraction efficiency and selectivity for Pd(II) under the experimental conditions, and the stoichiometry of Pd(II) with HBrO 8 Q was found to be 1:1 by means of mole ratio method and Job’s method. The thermodynamic study indicated that the extraction process was endothermic and spontaneous. Additionally, complete back extraction of palladium could be achieved by using acidic thiourea solution.
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Yifan Yang,Lu Jin,Guoxiang Chen,Jiabao Ye,Yongfeng Mei
A transparent nanoporous Pd-WO 3 -Nafion film is developed for gasochromic H 2 leak detection. • The Nafion overlayer significantly boosts the transmittance variation and response kinetics. • A semi-enclosed attachable H 2 leak detector with a top vent ensures the safe upward release of H 2 . • The reusable and detachable detector allows precise visual localization of leaks in H 2 systems. Hydrogen (H 2 ) is a promising clean energy carrier, but its high leakage risk and explosive nature demand safe and reliable detection technology. Here, we present a reusable and attachable H 2 leak detector based on a transparent gasochromic Pd-WO 3 -Nafion film. The film consists of a nanoporous WO 3 layer decorated with an ultrathin Pd (2 nm) catalyst and a Nafion overlayer. It exhibits a transmittance variation of approximately 59% (from 75% to 16%) upon exposure to 4% H 2 , with a coloring time of 69 s and a bleaching time of 117 s. Notably, the Nafion coating significantly enhances the transmittance variation and response kinetics compared to Nafion-free films. Building on this material, we design a semi-enclosed detector with a top vent for safe upward H 2 release and clear visual detection. Its detachable configuration enables repeated use and precise leak localization across complex systems, providing a cost-effective, visually intuitive solution for H 2 infrastructure. Download: Download high-res image (214KB) Download: Download full-size image
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ACS Omega
·
2021
·
IF 3.512
Lin-Xi Wan,Yong-Qi Zhen,Zhen-Xiang He,Yang Zhang,Lan Zhang,Xiaohuan Li,Feng Gao,Xian-Li Zhou
A new series of N-aryltacrine derivatives were designed and synthesized as cholinesterase inhibitors by the late-stage modification of tacrine, using the palladium-catalyzed Buchwald–Hartwig cross-coupling reaction. In vitro inhibition assay against acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) demonstrated that most of the synthesized compounds had potent AChE inhibitory activity with negative inhibition of BuChE. Among them, N-(4-(trifluoromethyl)phenyl)-tacrine (3g) and N-(4-methoxypyridin-2-yl)-tacrine (3o) showed the most potent activity against AChE (IC50 values of 1.77 and 1.48 μM, respectively). The anti-AChE activity of 3g and 3o was 3.5 times more than that of tacrine (IC50 value of 5.16 μM). Compound 3o also displayed anti-BuChE activity with an IC50 value of 19.00 μM. Cell-based assays against HepG2 and SH-SY5Y cell lines revealed that 3o had significantly lower hepatotoxicity compared to tacrine, with additional neuroprotective activity against H2O2-induced damage in SH-SY5Y cells. The advantages including synthetic accessibility, high potency, low toxicity, and adjunctive neuroprotective activity make compound 3o a new promising multifunctional candidate for the treatment of Alzheimer’s disease.
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高影响因子
Catalysis Science & Technology
·
2021
·Vol. 11
·期 20
·6732-6741
·
IF 6.119
Yafeng Chen,Guimin Jiang,Xiangzhi Cui,Zuotai Zhang,Xinmei Hou
Eliminating indoor formaldehyde (HCHO) pollution at room temperature is highly needed to improve the environment while saving energy. Herein, Pd/CeO2 catalysts with different morphologies of the CeO2 support were employed to investigate their performance for HCHO oxidation. The Pd/CeO2 nanocube (Pd/CeO2-C) catalyst exhibited excellent catalytic activity compared to commercial CeO2 and CeO2 nanorods. HCHO can be completely converted into CO2 and H2O over the Pd/CeO2-C (0.64 wt% Pd) catalyst at a weight hourly space velocity of 36 000 mL g−1 h−1 at room temperature. Multiple characterization results confirmed that the strong interfacial interaction between Pd and the CeO2-C support guarantees a high percentage of metallic Pd on the CeO2-C surface and its high dispersion, which is crucial for the oxidation of formaldehyde at low temperature. The in situ diffuse reflectance infrared Fourier transform results indicated that CO, formate and dioxymethylene species are the main intermediates over the Pd/CeO2-C catalyst, and the active O species is responsible for their decomposition and oxidation. This work may promote the practical application of high performance Pd-based catalysts for indoor HCHO purification and related catalytic processes.
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高影响因子
Nature Communications
·
2020
·Vol. 11
·期 1
·1-8
·
IF 12.121
Xu Hong-Lei,Tkachenko Nikolay V.,Wang Zi-Chuan,Chen Wei-Xing,Qiao Lei,Muñoz-Castro Alvaro,Boldyrev Alexander I.,Sun Zhong-Ming
Sandwich-type clusters with the planar fragment containing a heterometallic sheet have remained elusive. In this work, we introduce the [K(2,2,2-crypt)] 4 {(Ge 9 ) 2 [ η 6 -Ge(PdPPh 3 ) 3 ]} complex that contains a heterometallic sandwich fragment. The title compound is structurally characterized by means of single-crystal X-ray diffraction, which reveals the presence of an unusual heteroatomic metal planar fragment Ge@Pd 3 . The planar fragment contains a rare formal zerovalent germanium core and a peculiar bonding mode of sp 2 -Ge@(PdPPh 3 ) 3 trigonal planar structure, whereas the nonagermanide fragments act as capping ligands. The chemical bonding pattern of the planar fragment consists of three 2c-2e Pd-Ge σ-bonds attaching Pd atoms to the core Ge atom, while the binding between the planar fragment and the aromatic Ge 9 ligands is provided by six 2c-2e Pd-Ge σ-bonds and two delocalized 4c-2e σ-bonds. The synthesized cluster represents a rare example of a sandwich compound with the heteroatomic metal planar fragment and inorganic aromatic capping ligands.
研究领域:
无机化学
·
材料科学
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高影响因子
GREEN CHEMISTRY
·
2018
·Vol. 20
·期 11
·2588-2595
·
IF 8.586
Da Yang,Huan Liu,Dong-Liang Wang,Zhoujie Luo,Yong Lu,Fei Xia,Ye Liu
A bi-functional ligand (L1) containing a diphosphino fragment and sulfonic acid group (–SO3H) enabled PdCl2(MeCN)2 to efficiently catalyze the tandem bis-alkoxycarbonylation of terminal alkynes to produce aryl-/alkyl-substituted succinate (α,ω-diesters). It was found that the –SO3H incorporated in L1 indispensably assisted the Pd-catalyst in accomplishing this tandem reaction via intramolecular synergic effects. Co-catalysis over the L1-based Pd-catalyst was not due to the physical mixture of Xantphos and MeSO3H. In situ FTIR analysis verified that the formation and stability of Pd–H active species were facilitated by the presence of L1. The formation of stabilized diacylpalladium intermediate (F) was the critical driving force for the second-step methoxycarbonylation. DFT calculation was carried out to optimize the geometric structure of F, which indicated that the developed intramolecular O⋯H hydrogen bonds were an important structural feature to stabilize F. In addition, the L1-based Pd-catalyst could be recycled successfully for at least 3 runs in the ionic liquid [Bmim]NTf2 without obvious activity loss and detectable metal leaching.
研究领域:
有机化学
·
催化化学
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高影响因子
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