Science China-Materials
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2024
·Vol. 67
·期 7
·2285-2292
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IF 6.8
An Ran,Xu Xiangdong,Li Bingxuan,Han Jun,Sun Ruiliang,Zhang Mingang,Jiang Yadong
Nonlinear optical (NLO) organic materials with large optical nonlinearity and high stability are highly attractive for wide applications. Herein, a new organic NLO chalcone derivative, 1-(4-methoxy phenyl)-3-(4-ethoxy phenyl)-2-propenyl-1-ketone (DMPO), with an ultra-strong second-order nonlinear response was designed and systematically investigated. The as-designed DMPO was synthesized, and DMPO single crystals with a size of 10 × 5 × 4 mm 3 were grown rapidly in only 5 days. The as-grown DMPO crystals formed by neutral organic molecules exhibit high transparency over a wide range of 600–1800 nm, a moderate optical band gap of 2.51 eV, and excellent anti-deliquescence. In particular, the second-harmonic generation response of DMPO reaches 1.86 times that of the benchmark material 4- N,N -dimethylamino-4′- N′ -methyl-stilbazolium tosylate, revealing the outstanding macroscopic optical nonlinearity of DMPO, as designed. Therefore, DMPO combines several advantages, holding great potential for applications in nonlinear optics.
研究领域:
材料科学
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光学
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DOI
高影响因子
TALANTA
·
2025
·
IF 6.1
Chen Zeng,Jianxiong Chen,Chengbiao Zhu,Zhenwei Wei
Capturing and analyzing low-abundance, short-lived, and unstable radical intermediates during electrochemical (EC) reactions is important for understanding EC reaction mechanisms. Herein, we developed a chemical labeling strategy for rapid screening and highly sensitive analysis of EC radical intermediates by mass spectrometry (MS). Taking 5,5-dimethyl-1-pyrroline N-oxide (DMPO) labeling reagent as an example, DMPO can react with radical intermediates to form stable labeling products with characteristic fragmentation daughter ions or neutral loss in tandem MS, so the labeled intermediates can be screened by precursor ions scan or neutral loss scan. Further combined with our recently established floating electrochemical electrospray mass spectrometry platform (FE-ESI-MS), we realized online confirmation and in-depth analysis of radical intermediates, and accelerated the study of EC reaction mechanisms. We established the strategy based on the labeling analysis of radical intermediates produced by EC oxidation of acetaminophen and a mixed EC reaction system containing 10 substrates, and further studied the radical-radical cross coupling mechanism of sodium p -toluenesulfinate and 2-methyl-2H-indazole. The labeled products not only improved the MS response by more than 10 times, but also exhibited typical fragmentation behavior, which contributed to the rapid screening of radical intermediates. This chemical labeling strategy will increase the capability of MS for finding important EC intermediates in untargeted analysis and further investigating low abundant and short-lived EC intermediates in the future.
研究领域:
分析化学
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电化学
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质谱学
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DOI
PubMed
高影响因子
Environmental Science & Technology Letters
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2024
·
IF 8.9
Jing-Hang Wu,Han-Qing Yu
Limited by the detection techniques, the reactive species involved in catalytic water purification processes are difficult to be clarified. Spin-trapping electron paramagnetic resonance (EPR) analysis is recognized as a reliable tool for radical identification, in which 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) is usually used as the radical trapper. However, it is questioned that the detection of adducts of DMPO definitively indicates the generation of radicals. In this work, the DMPO transformation caused by transition metal oxides is monitored by EPR, and abundant spin signals are observed. MnO2, Mn2O3, and NiO could oxidize DMPO into DMPOX through direct oxygen transfer. Besides, the dissolved transition metal ions could transform DMPO into misleading DMPO–OH and DMPO–R. The findings in this work, e.g., the interactions between DMPO and different metal oxides and the quenching behavior of the different pathways, would help with reliable identifications of reactive species in both engineered systems and natural environments.
研究领域:
环境科学
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化学
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DOI
高影响因子
FREE RADICAL RESEARCH
·
2020
·
IF 2.839
Bo Yin,Rui Rui Liu,Ya Jie Meng,Hong Lin Zhai,Sha Sha Li,Jules Muhire
Found in various natural food products, many in vitro evidence indicated that resveratrol (RES) has been linked to neuroprotective and cardioprotective effects and prevent cancer development. However, human clinical trials have been conducted with varying results, making the usage of RES controversial. In this paper, we demonstrated that the drug RES could be conjugated with the high levels of endogenous GSin cancer cells. 5,5-Dimethyl-1-Pyrroline-N-Oxide (DMPO) was employed to capture the GS•. The molecular mechanism of the reaction between RES and GSwas further studied by UV-Vis spectrometry, mass spectrometry and Density Functional Theory (DFT) calculations. Besides, the formation of the adduct GS-RES in cancer cell was obtained when RES was added during incubation. Further study indicated that over 77.6% of the RES was consumed in cancer cells. This study suggested that endogenous GSmay be one of the important factors to cause the depletion of anti-tumour drugs during chemotherapy, which should be paid special attention in clinical therapeutics and drug development.
研究领域:
药理学
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肿瘤学
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生物化学
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化学生物学
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DOI
PubMed
高影响因子
Journal of Cleaner Production
·
2023
·
IF 11.1
Shicheng Yuan,Hui Hu,Hao Huang,Zhongming Chen,Jiaxin Chen,Mi Zhang,Kunpeng Li,Ting Zhou,Ruibin Lv
Chlorobenzene (CB) is an important organic chemical material that is volatile and difficult to degrade, and has received much attention because of its strong ozone generation potential. An electrochemical-sodium peroxydisulfate (PDS) system was constructed and the oxidation reaction path of chlorobenzene in this system was analyzed. The effects of current density, PDS concentration, initial pH, CB blow-off gas ratio and temperature on the oxidation and mineralization rate of chlorobenzene in the system were investigated respectively. At a current density of 168 A/m 2 , a PDS concentration of 0.5 mol/L, an initial pH of 10, a CB blow-off gas ratio of 20% and a reaction temperature of 60 °C, the CB conversion and mineralization rates were able to reach more than 90%. The results of electron paramagnetic resonance (EPR) experiments using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) and 2,2,6,6-tetramethyl-4-piperidone hydrochloride (TEMP) as spin trapping agents indicate the presence of ⦁OH, · S O 4 − and 1 O 2 in the system. The signal of · O 2 − was also captured after the quenching of ⦁OH, which further indicates the presence of 1 O 2 . And the results of active substance quenching experiments showed that the active species that mainly contributed to the oxidation of chlorobenzene included ⦁OH, · S O 4 − and 1 O 2 , and their contributions to the oxidation of chlorobenzene were 25.0%, 31.7% and 22.2%, respectively. The Liquid Chromatograph Mass Spectrometer (LC-MS) characterization results showed that the formation of chlorophenol and hydroquinone and their ring-opening reactions were the most critical processes in the oxidative decomposition of chlorobenzene, and the reaction pathways for the oxidation of chlorobenzene by ⦁OH, · S O 4 − and 1 O 2 were proposed by these characterization results.
研究领域:
环境科学
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化工工程
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分析化学
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DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Jing Li,Yu-Jing Gao,Lu-Lu Hao,Tian Wang,Yi-Ming Zhao,Qiang Liu,Zhiguang Sun,Jiyun Hu,Yin-Shan Meng,Tao Liu
Developing highly efficient photocatalysts for purifying polluted water and degrading organic contaminants has attracted increasing attention. The generation of singlet oxygen (1O2) and superoxide radicals (O2•–) remains a key challenge for achieving high catalytic performance. Herein, a range of metal–organic frameworks (MOFs), denoted as {[MBPDC)]·H2O}n (M = Fe2+ (MOF 1), Co2+ (MOF 2), and Ni2+ (MOF 3); H2BPDC = 2,2′-bipyridine-5,5′-dicarboxylic acid), served as an efficient peroxymonosulfate (PMS) activator for the regioselective oxidation of organic pollutants. Photocatalytic experiments revealed that MOF 2 exhibited superior degradation efficiency toward Rhodamine B (RhB), achieving 99.4% removal within 12 min, significantly faster than MOF 1 (4.5%) and MOF 3 (10.0%). Notably, MOF 2 demonstrated excellent reusability and structural robustness over five consecutive cycles. Through integrated radical scavenging tests and electron paramagnetic resonance (EPR) spectroscopy, 1O2 and O2•– were determined to be the key reactive oxygen species driving the degradation process. The outstanding durability and anti-interference capacity of MOF 2 underscore its practical potential for cost-effective and robust environmental remediation applications.
研究领域:
环境化学
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材料科学
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催化
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水净化
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污染物降解
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产品关联
DOI
PubMed
高影响因子
Catalysis Science & Technology
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2025
·
IF 4.2
Yu-Le Wang,Songhai Wu,Yu-Zhen Xu,Yu-Dong Shan,Yong Liu,Xu Han
The selective oxidation of cyclohexene (Cy) to cyclohexene oxide (Cy-ep) using O2 remains challenging due to low epoxidation selectivity. In this work, a series of Mo-doped TS-1 (Mo-TS-1) catalysts were successfully synthesized for the epoxidation of Cy under solvent- and initiator-free conditions with O2 as the oxidant. Among them, 5Mo-TS-1 exhibited high catalytic performance, achieving 43.5% Cy conversion and 50.6% selectivity toward Cy-ep. Additionally, valuable byproducts such as 2-cyclohexen-1-ol (Cy-ol) and 2-cyclohexen-1-one (Cy-one) were obtained with yields of 28.0% and 21.4%, respectively. Since both Cy-ol and Cy-one are valuable intermediates in fragrance synthesis, over 43.5% of Cy was effectively converted into high-value products. Quenching experiments and Raman spectroscopy revealed that surface oxygen vacancies (Ov) facilitate the activation of O2 to form ≡Ov‑superoxo species, which abstract hydrogen from the allylic C-H bond of Cy to generate 3-cyclohexenyl radicals (Cy•). These radicals subsequently react with O2 to form Cy-OO•, followed by hydrogen abstraction from another Cy molecule to yield 2-cyclohexene-1-hydroperoxide (Cy-OOH). A positive correlation between Cy-OOH and Cy-ep formation underscores the critical role of Cy-OOH in the epoxidation process. Furthermore, Raman spectroscopy confirmed the presence of ≡Mo-(η2-O2) peroxo species on the catalyst surface, which preferentially attack the C=C bond of Cy to form Cy-ep. DFT calculations elucidated two distinct O2 activation pathways: In Pathway I, O2 is activated at Ov sites to form ≡Ov‑superoxo, which subsequently reacts with Cy to generate ≡Ov‑peroxo, Cy-OOH, and Cy•. In Pathway II, Mo(V/VI) sites either directly activate O2 or react with peroxo intermediates (≡Ov‑peroxo or Cy-OOH) to form ≡Mo-(η2-O2). This species selectively epoxidizes the alkene bond in Cy to Cy-ep. Notably, the direct activation of O2 at Mo(V/VI) sites bypasses the allylic oxidation route, thereby enhancing the epoxidation selectivity beyond the theoretical limit of 50.0%. This study provides new insight on the importance of surface superoxo and peroxo mediated by Ov and Mo(V/VI) in the epoxidation processes.
研究领域:
催化化学
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材料化学
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绿色化学
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多相催化
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氧化反应
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产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Jinzhi Cao,Yilin Zhao,Meihui Chen,Zhiyi Zhao,Yuhan Xiong,Dingding Tang,Yan Zhou,Xiong Qin,Nanqi Ren,Hui Wang,Jie Ding
Visible light-driven degradation of chlorophenols using metal-free photocatalysts has attracted significant attention. Two-dimensional covalent organic frameworks (2D COFs) exhibited high levels of visible-light activity. To address the challenges of insufficient redox capacity and recombination of photogenerated carriers of COFs, an S-scheme heterojunction is constructed from COFs with nitrogen vacancies modified graphitic carbon nitride (NVCN) to improve photocatalytic activity. Introducing electron donors (-OH and -C C) into COF could reduce the optical band gap and increase visible-light absorption. Meanwhile, they can form donor-acceptor (D-A) effects with nitrogen vacancies, thereby redistributing charge and enhancing the transfer rate of photogenerated electrons. Formation of S-scheme heterojunction effectively enhances the migration of photogenerated carriers and redox ability, the optimized heterojunction (COF-C C/NVCN) was able to degrade 98 % 4-chlorophenol within 90 min under visible light irradiation ( k = 0.044 min –1 ), which was 10–12 times higher than COF-H/NVCN or NVCN. This study provides the great potential of D-A COF/NVCN-based S-scheme heterojunctions for environmental remediation.
研究领域:
环境科学
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材料化学
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光催化
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有机半导体
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污染物降解
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
·
IF 9
Tingting Jiang,Siyu Huang,Yu Wang,Guanbo Wang,Wei Wang,Haifeng Zhang
Persulft-based advanced oxidation processes (PS-AOPs) are an efficient strategy to degrade refractory pollutants. Fabricating a highly efficient catalyst is the most pivotal factor in PS activation. This study designs a novel CoP 3 -anchored layered Bi 2 O 2 S through an interface engineering strategy, where the unique electronic structure and surface properties of Bi 2 O 2 S lead to dramatically reduced cobalt ion leaching compared with that of CoP 3 . It exhibited outstanding catalytic activity and achieved nearly complete removal (>99%) of 50 mg L −1 2,4-Dichlorophenol (2,4-DCP) within 30 min. Radical quenching experiments, EPR technique, electrochemical tests, and HPLC validated the coexistence of radical (•OH, SO 4 •− ) and non-radical ( 1 O 2 , electron transfer, high-valent metal species) pathways in the Light/Bi 2 O 2 S/CoP 3 /PMS system for 2,4-DCP degradation. Importantly, Bi 2 O 2 S/CoP 3 induced a pronounced photothermal effect that enhanced 2,4-DCP degradation efficiency. Furthermore, the attack sites of 2,4-DCP were precisely identified based on the Fukui index. Based on density functional theory calculation and high-performance liquid chromatography-mass spectrometry, the detailed degradation pathways were proposed. The toxicity of 2,4-DCP and its intermediate products were predicted by using the toxicity assessment software tool. Moreover, excellent reusability, real-water treatment efficacy (verified by 3D-EEM), high-efficiency removal of multiple pollutants, and wide pH adaptability (3−11) confirm practical potential for sewage treatment. This study provides insight into designing a highly efficient and green catalyst for simultaneous pollutant treatment.
研究领域:
环境催化
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材料科学
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水处理技术
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高级氧化过程
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纳米材料
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理论化学
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产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2025
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IF 11.3
Yiming Sun,Chenying Zhou,Shuang Meng,Shuang Zhong,Yang Liu,Chuanshu He,Peng Zhou,Bo Lai
Heteroatom doping has been applied as an excellent method for mediating the catalytic reactivity of carbon materials. To overcome the inherent defect of slow Fe(III) reduction in Fenton chemistry, this work finds that boron-doped carbon materials demonstrate high cocatalytic activity in boosting Fenton oxidation. During Fenton chain reactions catalyzed by boron-doped reduced graphene oxide (B-rGO, the typical boron-doped carbon material), highly reactive near-free Fe(III) formed on the B-rGO surface can dramatically promote H2O2 mediated Fe(III) reduction, which strongly accelerates the rate-determining reaction in Fenton chain reactions to generate hydroxyl radicals. The results of DFT calculations, electrochemical analysis, characterizations (XAFS, in situ Raman, and HAADF-STEM), and pH-dependent performance reveal that doped boron atoms can modulate the electron-deficient iron atom of FeOH2+ by stretching the Fe–O bond (from 163.6 to 179.2 pm), which forms near-free Fe(III) on the B-rGO surface with higher oxidation capability than free Fe(III), and the Fe(III) oxidation potential is positively and linearly related to the boron content of B-rGO (R2 = 0.96). Moreover, near-free Fe(III) can dramatically oxidize H2O2 (a green electron donor) to accelerate Fe(II) regeneration, thereby promoting Fenton chain reactions for long-lasting Fenton oxidation. These discoveries afford a strategy for designing green and sustainable cocatalysts to overcome the intrinsic weaknesses of classical Fenton chemistry.
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DOI
PubMed
高影响因子
ACS Nano
·
2025
·
IF 16
Xuyu Li,Qingfu Zhao,Xiaolin Feng,Pinyuan Cui,Jingjing Yu,Binyong Liang,Chao Liu,Ye Wang,Yiting Wu,Ruiqi Wang,Bo Hu,Yihan Lin,Lichong Zhu,Xuan Zhu,Ban Luo,Xiangliang Yang,Jun Hu
Immunoradiotherapy (iRT) has emerged as a promising strategy for liver hepatocellular carcinoma (LIHC) treatment to synergistically activate both localized antitumor immunity and systemic immune responses. However, radiation will aggravate LIHC hypoxia, resulting in an adenosine metabolism level elevation, which promotes the differentiation of T cells into terminally exhausted phenotypes and weakens the efficacy of immunotherapy. To overcome this challenge, we engineered a nanocatalytic probiotic-based radiation-metabolic modulator, in which Escherichia coli Nissle 1917 (EcN) was programmed to in situ synthesize gold–palladium bimetallic nanocatalysts (EcNcGP) via biodirected mineralization. Guided by lattice mismatch and interfacial strain engineering, engineered EcN orchestrates the epitaxial assembly of Au atoms on Pd nanoclusters, yielding a precisely strain-tuned heterostructure with a modulated d-band electronic structure. This architectural design optimizes oxygen intermediate adsorption–desorption kinetics and significantly enhances the catalytic efficiency. This design enables EcNcGP to exhibit robust catalase- and peroxidase-like activities, which effectively catalyze intratumoral H2O2 into O2 and hydroxyl radicals, intensifying radiation damage and alleviating tumor hypoxia to inhibit adenosine metabolism by downregulating the expression of ectonucleoside triphosphate diphosphate hydrolase 1 (CD39) and ecto-5′-nucleotidase (CD73). By blocking the binding of adenosine (ADO)–adenosine receptor A2A (ADORA2A) to inhibit the following cyclic adenosine monophosphate (cAMP)–protein kinase A (PKA)–phosphorylation of cAMP response element binding (pCREB) signaling transduction, radiation-induced T-cell exhaustion could be inhibited. Compared to stereotactic body radiotherapy (SBRT), the combination of EcNcGP with SBRT increased CD8+ T-cell infiltration by 99.8% and reduced PD-1hi-exhausted T cells by 63.9%. Integration with anti-PD-L1 therapy (αPD-L1) achieved complete tumor regression in 60% of the treated mice-bearing orthotopic hepatocellular carcinoma. These findings establish a paradigm-shifting strategy for reprogramming tumor-immune metabolic checkpoints using strain-engineered nanocatalytic probiotics, thereby enhancing iRT and overcoming radioresistance.
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DOI
PubMed
高影响因子
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
·
2025
·
IF 3.8
Yu Su,Bo Zhang,Xiang Cheng,Kun Du,Leqing Feng,Wei Zhao
Herein, a novel sunlight-independent tribocatalytic system with efficient friction energy harvesting capability is proposed. This system demonstrates enhanced tribocatalytic performance of cerium oxide (CeO 2 ) nanoparticles driven by the friction between Cu coated on the glass beaker bottom and a Teflon (PTFE) magnetic disk. An apparent rate constant of 0.045 min −1 was achieved for methylene blue (MB) degradation, representing a 2.7-fold improvement over the CeO 2 @glass/PTFE system (0.01682 min −1 ). Notably, the system achieved > 90% degradation efficiency for high-concentration MB solutions (40 mg/L), surpassing the performance of previously reported tribocatalytic systems. Through multiscale tribo-interface characterization and radical trapping experiments, the synergistic catalytic mechanism was elucidated: Friction-induced charge carriers in CeO 2 are efficiently transferred via the interfacial electronic effects of the Cu/PTFE friction couple and the active surface with Ce 3+ /Ce 4+ redox couples. Electron paramagnetic resonance analysis confirmed that Cu coating modification on the surface of the beaker bottom enhanced hydroxyl radical (·OH) yield by 2.3-fold compared to glass, enabling complete pollutant degradation through hole (h + )-dominated oxidation pathways. This work transcends conventional catalyst modification strategies, establishing a new paradigm for interface engineering in mechano-chemical energy conversion systems.
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高影响因子
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