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JOURNAL OF STRUCTURAL CHEMISTRY · 2018 ·Vol. 59 ·期 3 ·744-747 · IF 0.521

Structural Characterization of a Cu(I)/Br Complex with Bis(4-(1H-Imidazol-1-Yl)Phenyl)Methanone Ligands

Sun S.-W.,Wang G.-F.

The synthesis of a novel Cu(I) complex with V-shaped bidentate ligands {[Cu(BIPMO)]×[CuBr 2 ]} n where BIPMO = bis(4-(1 H -imidazol-1-yl)phenyl)methanone is reported. It is characterized by IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. Copper(I) ions in the complex are in a distorted environment in which donor atoms are provided by the bromide anion and nitrogen atoms of BIPMO ligands, respectively. Infinite anion chains formed by CuX 4 (X = Br or N) polyhedra are linked by BIPMO ligands to give rise to layers. Furthermore, the layers are linked into 3D networks through weak intermolecular interactions.

研究领域: 无机化学 · 材料科学 · 晶体学
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INORGANIC CHEMISTRY · 2024 · IF 4.3

In Situ Formed 3,3′,5,5′-Tetramethylbenzidine-Cu(I/II) Charge-Transfer Complex Intermediates Promoting Colorimetric Assay of Cr6+

Jiahui Zhao,Yixuan Zhao,Xuefeng Shao,Ying Sun,Huang Wen,Jian Liu

Developing a synthesis-free, multifunctional, and effective colorimetric assay system based on 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation is attractive yet challenging. Herein, we established a synergetic Cu2+/Cr6+-promoting strategy for TMB-based colorimetric detection of Cr6+. By introducing Cu2+, critical TMB·+···Cu(I/II)···TMB charge transfer complex (TMC) intermediates were in situ formed to reduce the activation energy of TMB oxidation, thereby accelerating Cr6+-mediated TMB oxidation. TMC intermediates also played a pivotal role in H2O2-participated TMB oxidation, clarifying the secondary responsibility of reactive oxygen species frequently caused by Fenton-like reactions. Leveraging the synergetic capacity between Cu2+ and Cr6+ for TMB oxidation, we demonstrated sensitive and specific colorimetric detections for Cr6+ with a limit of detection of 0.006 μM. With its convenient operation and rapid responsiveness, this strategy successfully enabled the practical detection of Cr6+ in real water samples. This work not only enhances the understanding of the internal acceleration mechanism in colorimetric sensing but also provides valuable opportunities to advance synthesis-free detection platforms.

研究领域: 分析化学 · 环境科学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Journal of Cleaner Production · 2021 · IF 9.297

Crednerite CuMnO2 as highly efficient Fenton-like catalysts for p-nitrophenol removal:Synergism between Cu(I) and Mn (III)

Chuankun Yin,Siji Zhou,Keyi Zhang,Jiale Bai,Yangyang Lv,Xuewen Zhang,Xiaoxia Li,Aihua Xu

p-Nitrophenol (PNP) is one of the highly toxic and mutagenic pollutants existed in aquatic environment. In this work, the crednerite CuMnO 2 nanoflake was prepared and used to degrade PNP with peroxymonosulfate (PMS) as the oxidant. It was found that CuMnO 2 exhibited much higher activity than other Cu-based catalysts such as CuO, Cu 2 O, CuFe 2 O 4 and CuFeO 2 , with 90% of PNP degraded after 10 min under mild reaction conditions. The catalyst was also stable during five successive runs. Sulfate and hydroxyl radicals produced from PMS reduction by Cu(I) species, as well as superoxide ions and single oxygen, contribute to the degradation of PNP. More importantly, the interactions between Mn and Cu species in CuMnO 2 were identified by X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FT-IR) and linear sweep voltammetry (LSV), and were further confirmed by the control experiment with the mixture of Cu 2 O + Mn 2 O 3 . The results implied that the high valent Mn(III) species acted as Lewis acids to withdraw electron from PMS, resulting that the Cu(I) species can be easier oxidized to Cu(II) by PMS with the formation of radicals. These findings provide an ideal bimetallic heterogeneous catalyst and a new mechanism for PMS-mediated reaction.

研究领域: 环境科学 · 催化化学
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JOURNAL OF POLYMER RESEARCH · 2013 ·Vol. 21 ·期 1 ·1-13 · IF 2.019

The Cu(I)-mediated azide–alkyne cycloadditions as a facile and efficient route for functionalization of waterborne polyurethane

Li Xing-Jian,Sun Dao-Xing,Zhang Yi-Heng

The Cu(I)-mediated azide–alkyne cycloaddition reaction, “click” chemistry, has been used to functionalize the waterborne polyurethane, by which a novel fluorinated waterborne polyurethane (FWPU) was synthesized. FWPU was confirmed by FT-IR and 1 H NMR. The structure and properties of FWPU were characterized by water contact angle, water absorption, surface energy, scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometry (EDS), thermogravimetric analysis (TGA) and X-ray diffraction (XRD), etc. From the research of the surface properties, it was found that the modified materials were endowed with a remarkable hydrophobicity and stain resistance. SEM results showed that the micro-phase separation of FWPU became increasingly apparent with the rise of fluorinated side chains in polyurethane backbone. XRD measurements reflected that the crystallinity of FWPU tended to decrease firstly and then increase with the change of fluorine content. TGA results demonstrated that FWPU possessed flame retardant performance to a certain extent due to the incorporated alkyne groups in the FWPU to improve the final char strongly.

研究领域: 高分子化学 · 材料科学 · 表面工程 · 有机化学 · 应用化学
✓ 已验证 DOI 高影响因子
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CHEMISTRY OF MATERIALS · 2021 · IF 9.811

Ultra-Broad-Band-Excitable Cu(I)-Based Organometallic Halide with Near-Unity Emission for Light-Emitting Diode Applications

Jinglong Huang,Binbin Su,Enhai Song,Maxim S. Molokeev,Zhiguo Xia

Low-dimensional hybrid metal halides demonstrate broad-band emission and high photoluminescence quantum yield (PLQY) acting as excellent candidates for a new generation of luminescent materials in lighting fields. However, most luminescent metal halides can only be excited by ultraviolet radiation, and the discovery of high-efficient emitters with broad-band excitation characteristics, especially upon efficient blue light irradiation, is a challenge. Herein, a zero-dimensional (0D) Cu(I)-based organometallic halide (18-crown-6)2Na2(H2O)3Cu4I6 (CNCI) was prepared with a green emission band centered at 536 nm and a near-unity PLQY (91.8%) upon excitation of 450 nm. Importantly, the ultrabroad excitation band covering a 300–500 nm range was observed in CNCI, and the luminescence mechanism has been discussed in detail. A white light-emitting diode (WLED) was fabricated with high luminous efficiency of 156 lm/W and a high color rendering index of 89.6. This work provides guidance for designing high-performance luminescent metal halides with suitable excitation characteristics and also promotes the application prospects of such materials in WLED fields.

研究领域: 材料科学 · 光学工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Enhanced activation of H2O2 by bimetallic Cu2SnS3: A new insight for Cu (II)/Cu (I) redox cycle promotion

Qiao Yang,Chuanhai Xia,Shuai Chen,Xuezhi Cao,Jingcheng Hao

Hypothesis Despite that the development of Cu 2 SnS 3 (CTS) catalyst has attracted increasing interests, few study has reported to investigate its heterogeneous catalytic degradation of organic pollutants in a Fenton-like process. Furthermore, the influence of Sn components towards Cu (II)/Cu (I) redox cycling in CTS catalytic systems remains a fascinating research. Experiments In this work, a series of CTS catalysts with controlled crystalline phases were prepared via a microwave-assisted pathway and applied in the H 2 O 2 activation for phenol degradation. The efficiency of phenol degradation in CTS-1/H 2 O 2 system (CTS-1: the molar ratio of Sn (copper acetate) and Cu (tin dichloride) is determined to be Sn:Cu = 1:1) was systematically investigated by controlling various reaction parameters including H 2 O 2 dosage, initial pH and reaction temperature. We discovered that Cu 2 SnS 3 exhibited superior catalytic activity to the contrast monometallic Cu or Sn sulfides and Cu (I) acted as the dominant active sites. The higher Cu (I) proportions conduce to the higher catalytic activities of CTS catalysts. Quenching experiments and electron paramagnetic resonance (EPR) further proved that the activation of H 2 O 2 by CTS catalyst produces reactive oxygen species (ROS) and subsequently leads to degradation of the contaminants. A reasonable mechanism of enhanced H 2 O 2 activation in Fenton-like reaction of CTS/H 2 O 2 system was proposed for phenol degradation by investigating the roles of copper, tin and sulfur species. Findings The developed CTS acted as a promising catalyst in Fenton-like oxidation progress for phenol degradation. Importantly, the copper and tin species contribute to a synergetic effect for the promotion of Cu (II)/Cu (I) redox cycle, which thus enhanced the activation of H 2 O 2 . Our work may offer new insight on the facilitation of Cu (II)/Cu (I) redox cycle in Cu-based Fenton-like catalytic systems.

研究领域: 环境科学 · 催化化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2023 · IF 5.8

DDTC-Cu(I) based metal-organic framework (MOF) for targeted melanoma therapy by inducing SLC7A11/GPX4-mediated ferroptosis

Chan Li,Sheng Zhou,Chuncheng Chen,Lijun Zhu,Shijie Li,Zhuoyue Song,Jian Liang,Chunzhi Tang,Nenggui Xu,Tao Liu,Shihui Liu

Disulfiram (DSF), a drug for alcohol withdrawal , has attracted extensive scientific attention due to its potential to treat cancer. The metabolite of DSF, diethyl dithiocarbamate (DDTC), forms a Cu-DDTC complex in vivo with copper ions , which has been shown to be a proteasome inhibitor with high antitumor activity . However, the in vivo stability of Cu-DDTC complexes remains a challenge. In this study, the nanomedicine [email protected] with high antitumor activity was prepared by using the nanoscale metal-organic framework (MOF) Cu-BTC as a carrier and loading diethyldithiocarbamate (DDTC) through coordination interaction. The results showed that [email protected] had high drug loading and adequate stability, and exhibited DDTC-Cu(I) chemical valence characteristics and polycrystalline structure features. In vitro cytocompatibility investigation and animal xenograft tumor model evaluation demonstrated the anti-cancer potential of [email protected] , especially the combination of [email protected] with low-dose cisplatin showed significant antitumor effect and biosafety. This study provides a feasible protocol for developing antitumor drugs based on the drug repurposing strategy.

CAS / MDL: 20427-59-2 554-95-0
研究领域: 药学 · 纳米技术 · 肿瘤学 · 材料科学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Journal of Materials Chemistry C · 2023 ·Vol. 11 ·期 38 ·13030-13038 · IF 6.4

Phase transition and rapid temperature response of lead-free perovskite Cs–Cu–I nanocrystals enabled by their size

Jie Chen,Yu Li,Zhe Yin,Shuaibing Wang,Ouyang Lin,Wentao Niu,Feng Teng,Aiwei Tang

Cu-based halide perovskites have attracted extensive attention in the optoelectronic field owing to their non-toxic nature and excellent stability. Nevertheless, the growth mechanism of Cu-based halide perovskite nanocrystals (NCs) remains unclear, and the size and uniformity of NCs are difficult to control, which seriously hinders the development of these materials. Herein, a facile hot-injection method was applied to control the size and uniformity of blue-emitting (450 nm) Cs3Cu2I5 NCs. The dimensions of Cu-based perovskites were tuned from zero-dimensional NCs to one-dimensional nanorods. Additionally, the sizes of Cs3Cu2I5 NCs could be tuned from 22.1 ± 1.5 to 8.9 ± 1.1 nm by varying the reaction temperature and the dosage of cesium oleate, which is also extended to tune the size of Cs3Cu2X5 (X = Br and Cl) NCs. Interestingly, the photoluminescence (PL) maximum at 450 nm was almost unchanged with the size tuning, indicating that PL is from the radiation recombination of self-trap exciton emission. Moreover, the phase transition temperature of Cs3Cu2X5 NCs was regulated by varying the size, where a small size is beneficial to the decrease of the phase transition temperature. As a demonstration, the different-sized Cs3Cu2X5 NCs exhibited a size-dependent temperature response, and the response time became shorter as the size decreased. The temperature response of the small-sized Cs3Cu2X5 NCs could be decreased to only 15 s, which is better than that of their counterparts reported previously. This work may deepen the understanding of the size-dependent phase transition process in Cu-based perovskite NCs.

研究领域: 材料科学 · 光学
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JOURNAL OF HAZARDOUS MATERIALS · 2023 · IF 13.6

Novel strategy for copper precipitation from cupric complexes wastewater: Catalytic oxidation or reduction self-decomplexation?

Yingpeng Gu,Yue Sun,Weisheng Zheng

Cupric (Cu(II)) complexes in industrial wastewater are responsible for the failure of conventional alkaline precipitation, but the properties of cuprous (Cu(I)) complexes at alkaline circumstance have not been focused. This report proposed a novel strategy for the remediation of Cu(II)-complexed wastewater by coupling alkaline precipitation with green benign reductant, namely, hydroxylamine hydrochloride (HA). This remediation process (HA-OH) exhibits superior Cu removal efficiency that cannot be achieved with the same dosage of oxidants (3 mM). The possibility of Cu(I) activated O 2 catalysis and self-decomplexation precipitation were investigated, and the results identified that 1 O 2 was generated from Cu(II)/Cu(I) cycle, but it was insufficient to annihilate organic ligands. Cu(I) self-decomplexation was the dominate mechanism of Cu removal. For real industrial wastewater, HA-OH process can realize the efficient Cu 2 O precipitation and Cu recovery. This novel strategy utilized intrinsic pollutant in wastewater without introducing other metals, complicated materials, and expensive equipment, broadening the insight for the remediation of Cu(II)-complexed wastewater.

研究领域: 环境工程 · 废水处理 · 化学工程
✓ 已验证 产品关联 DOI PubMed 高影响因子
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2026 · IF 19.7

Engineering CObridge adsorption in Cu(II)/Cu(I) interfaces modulated by ionic liquid for enhanced CO2 electroreduction to ethylene

Ruirui Wang,Hasnain Nawaz,Linbo Huang,Sheng Zhong,Shuang Wei,Bin He,Ruixia Liu,Suojiang Zhang

Electrochemical CO 2 reduction to highly selective ethylene is particularly desirable yet challenging. The competition between methane and ethylene in the CO 2 RR process underscores the critical necessity of designing the catalyst for ethylene by suppressing the methane pathway. Herein, we introduced controllable Cu(II)/Cu(I) interfaces by regulating the ratio of ionic liquids (ILs) and H 2 O. The Cu x O-IL4 catalyst with main CuO/Cu 2 O structure, exhibits a high Faraday efficiency toward C 2 H 4 (∼54 %) and less CH 4 (∼1 %) under 250 mA·cm −2 current density at −1.18 V (vs RHE). Experimental and theoretical analyses demonstrate that Cu(I) sites favor CO bridge formation, while Cu(II) sites preferentially generate CO atop on Cu x O-IL4 catalysts. The Cu(II)/Cu(I) interface in Cu x O-IL4 facilitates the generation of CO bridge intermediates, thereby lowering the energy barrier for *CO dimerization and also preventing *CO hydrogenation to CH 4 formation, thus enhancing the selectivity of CO 2 -to-ethylene conversion. The study provides a novel approach for precisely controlling CO adsorption configurations to enhance CO 2 RR selectivity toward high-value multicarbon products formation.

✓ 已验证 产品关联 DOI 高影响因子
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Biochar loaded with Cu(I) to activate peroxyacetic acid for sulfamethoxazole removal: Effect of electron transfer and free radicals

Chenyu Zeng,Anting Ding,Xi Chen,Yongfei Ma,Hui Lin,Han Ding,Fuyu Xie,Lu Zang,Song Cui,Ping Li,Junwei Ma,Zulin Zhang

Cu/BC-PAA (Peroxyacetic acid) system was established in this study to remove sulfamethoxazole (SMX) from waters. Cu/BC-PAA achieved high elimination efficiency (91.2 %, k = 0.081 min −1 ) for SMX within 30 min. Cu (II) loaded on corn straw biochar was converted into form Cu (I) site. Characterization, electron paramagnetic resonance (EPR), and electrochemical analysis proved that Cu (I) and C O took part in the reaction, which accelerated electron transfer and produced free radicals and non-radicals (R-O· and singlet oxygen ( 1 O 2 )). Fukui index and Liquid Chromatograph Mass Spectrometer (LC–MS) analysis revealed that sulphonamide bond cleavage and isoxazole ring opening were the main detoxification pathway. Density functional theory (DFT) calculation exhibited the adsorption energy of Cu/BC (E ads  = −3.68 eV) enhanced the electron transfer between Cu (I) and PAA. The evaluation of anion effects, diverse water matrices, various sulfonamide antibiotics, and catalyst cycling tests demonstrated the Cu/BC-PAA system's exceptional stability, broad-spectrum applicability, and excellent reusability. This work successfully synthesized a stable environment-friendly catalyst for efficient activating PAA to eliminate antibiotics in waters.

研究领域: 环境科学 · 化学工程 · 水处理 · 高级氧化过程 · 材料科学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2026 · IF 8.7

Functional ETHYLENE RESPONSE 1 (ETR1) from Pichia pastoris: Dimer-dependent coupling of Cu(I)/ethylene sensing to kinase output

Jinying Shi,Zhendong He,Yifan Xu,Wen Chen

Ethylene is a crucial gaseous phytohormone that regulates diverse aspects of plant growth and development. In Arabidopsis thaliana , perception of ethylene is mediated primarily by ETHYLENE RESPONSE 1 (ETR1), a prototypic membrane protein that couples ligand sensing to signal transduction through a transmembrane copper cofactor-dependent ethylene-binding site and a cytoplasmic histidine kinase domain. Previous work established that ETR1 binds copper and forms covalent homodimers, but the functional significance of its dimeric architecture in signal transduction has remained elusive. In this study, we expressed and purified full-length ETR1 from Pichia pastoris, enabling the systematic dissection of its oligomeric state, copper redox chemistry, and ligand binding effects. Using an in vitro luminescent kinase assay, we demonstrate that the Cu(I)-ethylene complex strongly suppresses ETR1 autophosphorylation, but only when the receptor is in its disulfide-linked dimer form. Monomeric ETR1 generated by reductive cleavage retained basal kinase activity yet was insensitive to ethylene. Furthermore, the ethylene antagonists Ag + and 1-MCP reversed the ligand-induced suppression. Mutational analysis revealed that the H353Q variant lacked kinase activity, while the C65S/H69A double mutant retained basal activity but was resistant to ethylene-induced inhibition, implicating both the catalytic histidine residue and the copper-binding site in the regulatory mechanism. Together, these findings establish that ETR1 functions as a dimer-dependent ethylene sensor, in which covalent dimerization is essential for allosteric coupling between the ligand-binding and kinase domains. This work thus provides a definitive biochemical model for ethylene perception and offers a robust platform for future structural and mechanistic studies of plant membrane-receptor signaling.

CAS / MDL: 10016-20-3
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