Antioxidants
·
2026
·Vol. 15
·期 9
·1064
·
IF 8.2
Yuri P. Tsentalovich,Nataliya A. Osik,Maxim V. Fomenko,Nikita A. Dmitriev,Vadim V. Yanshole
Ergothioneine (ESH) is one of the most abundant antioxidants in the human body, but its biological functions remain unclear. In this work, we elucidated the detailed mechanism of the deactivation of divalent copper ions Cu(II) by ESH using optical spectroscopy, NMR, and LC-MS. We found that the reduction of Cu(II) ions to Cu(I) by ESH occurs in a bimolecular reaction of CuII(ES−)2complexes, leading to the formation of the disulfide ESSE. Cu(I) ions remain bound in stable complexes with ESH, preventing their reactions with molecular oxygen. Over longer timescales, ESSE decomposes, regenerating reduced ESH and forming the final reaction product, hercynine (EH). The conversion of one ESH molecule to EH causes the reduction of four Cu(II) ions. We determined the rate constants of the bimolecular reaction between CuII(ES−)2complexes to be k3= (8 ± 4) × 104M−1s−1and of ESSE hydrolysis to be k4= (1.7 ± 0.4) × 10−5s−1and also estimated the formation constant K12≈ 1.2 × 1017M−2for the CuII(ES−)2complex. The high efficiency of Cu(II) reduction and the chelation of the resulting Cu(I) ions in a stable complex supports the hypothesis that protecting cells from oxidation by metal ions is likely one of the main functions of ESH.
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MOLECULES
·
2026
·Vol. 31
·期 13
·2304
·
IF 5.1
Haopeng Cui,Zhiying Li,Siyu Huang,Tianyi Zhang,Xiaodong Zhang,Zhongxiao Zhang,Jianqiu Lei,Ning Liu
Photocatalytic CO2reduction into CH4is a promising route for solar fuel production, but its efficiency is still limited by poor charge separation, insufficient CO2activation, and sluggish multi-electron transfer kinetics. Herein, Cu-modified TiO2(Cu/TiO2) was prepared by calcining a Cu-modified defective MIL-125(Ti) precursor, denoted as Cu-MIL-125, through a temperature-controlled calcination strategy. The effects of calcination temperature on the structural evolution, surface chemical states, interfacial charge transport, and CO2photoreduction performance were examined. These results indicated that the Cu/TiO2was successfully prepared, while the crystallinity, porous structure, and interfacial electronic properties of Cu/TiO2were strongly dependent on the calcination temperature. Among the obtained samples, the Cu/TiO2sample obtained by calcining Cu-MIL-125 at 450 °C (450 Cu/TiO2) exhibited the highest CH4formation rate, reaching 15.90 μmol g−1h−1, corresponding to an approximately 9.8-fold enhancement over TiO2calcined from defective MIL-125(Ti) at 450 °C, together with a high CH4selectivity of 93.05%. Control experiments and13CO2isotope-labeling tests confirmed that the detected carbon-containing products were generated from CO2under photocatalytic conditions. In situ diffuse reflectance infrared Fourier transform spectroscopy measurements further revealed the formation of carbonate, bicarbonate and hydrogenated carbon-containing intermediates during the reaction. This work offers a practical route for constructing metal–organic framework-derived Cu/TiO2photocatalysts for selective CH4production from CO2.
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APPLIED SURFACE SCIENCE
·
2026
·
IF 6.6
Shuo Han,Xu-bin Wang,Qian-cheng Sun,Wen-feng Yang,Fei Xiao
Simple immersion surface Pd alloying modification yields high-strength Cu-Cu bonding. • Disorder-to-order transformation offers extra driving force unlike inert Pd layer. • Lattice distortion & atomic pinning give 160 MPa shear strength at 76% bonding ratio. • Glycerol reduces oxide to nanocrystals and prevents oxidation during bonding in air. Low-temperature Cu-Cu thermal-compression bonding is essential for three-dimensional integrated circuits (3D ICs) to achieve high-density vertical interconnects. The key scientific challenge lies in achieving sufficient atomic interdiffusion at temperatures below 250 °C, where volume diffusion is sluggish and native oxides impede metal‑to‑metal contact. Here, this challenge is overcome by a simple galvanic displacement reaction that forms a disordered Cu-Pd surface alloy, followed by glycerol‑assisted bonding. This surface engineering simultaneously reduces roughness, raises surface energy, refines grains, and introduces micro-strain, while glycerol removes residual oxides in-situ and protects the interface from re-oxidation. These modifications accelerate atomic diffusion, and the exothermic defect annihilation and disorder-to-order transformation further lowers the diffusion barrier. Consequently, Pd‑displaced samples exhibit high shear strength and bonding ratio, and Kirkendall voids shrink under bonding conditions, potentially mitigating electrical concerns. The measured strength exceeds predictions from the bonding area alone due to solid‑solution hardening and lattice distortion. This work provides a simple, selective, and industrially viable route for low‑temperature Cu-Cu and hybrid bonding, offering a new surface‑alloying strategy with potential applicability to advanced packaging. Simple immersion surface alloying with glycerol reduction and protection achieves high‑strength Cu‑Cu bonding in air via abundant grain boundaries, disorder‑to‑order transformation and lattice distortion (exceeding estimated bulk Cu shear strength), while Kirkendall voids shrink with bonding durations to reduce potential electrical concerns. Download: Download high-res image (408KB) Download: Download full-size image
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Materials
·
2022
·Vol. 15
·期 5
·1846
·
IF 3.748
Haiyao Cao,Zaiji Zhan,Xiangzhe Lv
Ti3AlC2presents a hexagonal layered crystal structure and bridges the gap between metallic and ceramic properties, and Gadolinia (Gd2O3) has excellent thermodynamic stability, which make them potentially attractive as dispersive phases for Cu matrix composites. In this paper, Cu@Ti3AlC2-Gd2O3/Cu composites, Ti3AlC2-Gd2O3/Cu composites, and Gd2O3/Cu composites were prepared by electroless Cu plating, internal oxidation, and vacuum hot press sintering. The microstructure and the effect of the Cu plating on the properties of the Cu@Ti3AlC2-Gd2O3/Cu composites were discussed. The results showed that a Cu plating with a thickness of about 0.67 μm was successfully plated onto the surface of Ti3AlC2particles. The ex situ Ti3AlC2particles were distributed at the Cu grain boundary, while the in situ Gd2O3particles with a grain size of 20 nm were dispersed in the Cu grains. The electroless Cu plating onto the surface of the Ti3AlC2particles effectively reduces their surfactivity and improves the surface contacting state between the Cu@Ti3AlC2particles and the Cu matrix, and reduces electron scattering, so that the tensile strength reached 378.9 MPa, meanwhile, the electrical conductivity and elongation of the Cu matrix composites was maintained at 93.6 IACS% and 17.6%.Keywords:Cu@Ti3AlC2-Gd2O3/Cu composites;electroless Cu plating;microstructure;electrical conductivity;mechanical properties
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ACS Applied Electronic Materials
·
2022
·
IF 4.494
Longjun Guo,Wei Liu,Xiaoliang Ji,Ying Zhong,Chunjin Hang,Chunqing Wang
In this work, a multiscale coralloid nano-Cu3Sn composed of a bimodal structure (∼55 and ∼120 nm) has been successfully synthesized to meet low-cost and Pb-free packaging demands for high-power electronic application. Owing to the excellent oxidation resistance of the Cu3Sn intermetallic compounds (IMCs) and the protection of solvent poly(ethylene glycol)-400 (PEG-400) at high temperature, the full-Cu3Sn joints sintered in air have a comparative shear strength with the joints acquired in vacuum when the sintering temperature is no more than 300 °C. The full-Cu3Sn joints acquired at 300 °C in air achieve a high bonding strength of 40.4 MPa, which is superior to those of traditional Sn-based solder joints (19 MPa) and full-Cu6Sn5 joints (17.7 MPa). The electrical resistivity of the sintered Cu3Sn films reaches 29.1 μΩ·cm in air. Cu3.02Sn0.98 is formed at the interface between the Cu substrate and sintered Cu3Sn layer, contributing to the exceptional bonding strength of the full-Cu3Sn joints. The bonding strength of the joints after high-temperature storage (HTS) tests reveals that the prepared full-Cu3Sn joints possess outstanding long-term thermal stability with a shear strength of 47.9 MPa after 800 h of storage at 250 °C. Our work breaks through the synthesis bottleneck of nano-Cu3Sn IMCs and provides the underlying insights needed to guide the design of highly stable full-IMC joints for high-temperature electronic packaging.
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NANOTECHNOLOGY
·
2020
·Vol. 31
·期 19
·195710
·
IF 3.551
Songtan Yang,Zhixin Kang,Tao Guo
A facile, low-cost and environmentally-friendly technique has been developed to prepare highly conductive copper-graphene nanosheet (Cu-GNS) composite coatings on ABS (Acrylonitrile-Butadiene-Styrene) substrate. The surface activation of ABS substrate was obtained by a chrome-free and palladium-free pretreatment consisting of molecular bonding. Before electroplating Cu, the homogeneous single Ag film on ABS surface was achieved by the electroless spray-plating process. In addition, the deposition of Cu and GNS increased in the coatings along with the current density increasing. Four-point-probe test confirmed that the resistivity of Cu coatings (0.08 mΩ mm) and Cu-GNS composite coatings (0.05 mΩ mm) was in the same order of magnitude as pure copper (0.0175 mΩ mm) at high current density. Meanwhile, comparing with the Cu coatings, the resistivity of Cu-GNS composite coatings was reduced by nearly 40% at the same current density. The conductive property was significantly improved owing to the deposition of GNS. Therefore, this work was expected to expand the method of polymer materials surface metallization.
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LANGMUIR
·
2022
·
IF 4.331
Yibo Ao,Jinqing Ao,Ling Zhao,Liwei Hu,Fengsheng Qu,Biao Guo,Xue Liu
Cu(OH)2 nanomaterials are widely investigated for non-enzymatic glucose sensors due to their low-cost and excellent performance. Cu(OH)2 nanomaterials usually grow on substrates to form sensor electrodes. Reported works mainly focus on structure adjusting of the Cu(OH)2 nanostructures, while the optimization of substrates is still lacking. In the present work, directional porous Cu (DPC) was applied as the substrate for the growth of Cu(OH)2 nanograss (NG), and hierarchical structures of Cu(OH)2@DPC were prepared by alkaline oxidation. The morphology and microstructure evolution of the prepared hierarchical structures was investigated, and the non-enzymatic glucose sensing performance was evaluated. Cu(OH)2@DPC exhibits enhanced comprehensive non-enzymatic glucose sensing performance compared to the reported ones, which may benefit from both the effective adsorption of the Cu(OH)2 NG with a relatively high surface area and the high solute exchange of the DPC by a channel effect. This work provides new insights into the further improvement of the non-enzymatic glucose sensing performance of Cu(OH)2 nanostructures by optimizing the substrate structure.
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Journal of Energy Chemistry
·
2023
·
IF 13.1
Yonghai Feng,Min Yu,Minjia Meng,Lei Liu,Dewei Rao
In the selective oxidation of biomass-based 1,2-propanediol (PDO) with oxygen as the terminal oxidant, it is challenging to improve the lactic acid (LA) selectivity for nonnoble metal nanoparticles (NPs) due to their limited oxygen reduction rate and easy C–C cleavage. Given the high economic feasibility of nonnoble metals, i.e., Cu, in this work, copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles (Cu@Cu-N-C) were developed to realize highly selective of PDO oxidation to LA. The carbon-encapsulated ultrasmall Cu 0 NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu (Cu-N) sites are responsible for the high oxygen reduction efficacy. Therefore, the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO → hydroxylacetone → lactaldehyde → LA. Specifically, the enhanced LA selectivity is 88.5%, and the PDO conversion is up to 75.1% in an O 2 -pressurized reaction system (1.0 MPa O 2 ), superior to other Cu-based catalysts, while in a milder nonpressurized system (O 2 flow rate of 100 mL min −1 ), a remarkable LA selectivity (94.2%) is obtained with 39.8% PDO conversion, 2.2 times higher than that of supported Au nanoparticles (1% Au/C). Moreover, carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.
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ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Xiaoqiang Dou,Haoran Wang,Zihan Liu,Bowen Zheng,Zijian Zheng,Xuqing Liu,Ruisheng Guo
Flexible copper conductors have been extensively utilized in flexible and wearable electronics. They can be fabricated by using a variety of patterning techniques such as vacuum deposition, photolithography, and various printing techniques. However, vacuum deposition and photolithography are costly and result in material wastage. Moreover, traditional printing inks require posttreatment, which can damage flexible substrates, or grafting polymers, which involve complex processes to adhere to flexible substrates. Therefore, this study proposes a facile method of fabricating flexible metal patterns with high electrical conductivities and remarkable bonding forces on a diverse range of flexible substrates. Catalytic ink was prepared by using a mixture of epoxy resin, copper nanopowder, and nanosilica. The ink was applied to a variety of flexible substrates, including a poly(ethylene terephthalate) (PET) film, polyimide film, and filter paper, using screen printing to establish a bridge layer for subsequent electroless deposition (ELD). The catalytic efficiency was significantly improved by treating the cured ink patterns with air plasma. The fabricated flexible metals exhibited excellent adhesion and desirable electrical conductivity. The sheet resistance of the copper layer on the PET substrate decreased to 9.2 mΩ/□ after 150 min of ELD. The resistance of the flexible metal on the PET substrate increased by only 3.125% after 5000 bending cycles. The flexible metals prepared in this study demonstrated good foldability, and the samples with filter paper and PET substrates failed after 40 and 70 folds, respectively. A pressure sensor with a bottom electrode consisting of a copper interdigital electrode on a PET substrate displayed favorable sensing performance.
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JOURNAL OF SOLID STATE CHEMISTRY
·
2023
·
IF 3.3
Abid Hussain Shah,Zain Ul Abideen,Sumaira Maqsood,Farzana Rashid,Rafi Ullah,Attiq Ur Rehman,Muhammad Dildar,Manzoor Ahmad,Kifayat Ullah,Muhammad Numan Rafi,Fei Teng
In this study, copper based metal organic frame work (Cu-MOF) was synthesized by using different solvents i. e. H 2 O, Dimethylformamide (DMF) and DMF + C 2 H 5 OH + H 2 O solutions at various temperatures. Cu-MOF synthesized in different solvents exhibited a large number of properties and advantages including easy synthesis procedure, high porosity, good crystallinity , high surface area, massive pore volume , controllable pore surface properties (zeta potential), rigid and chemical stability. The as-synthesized Cu- MOF was analysed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area, zeta potential , electrostatic attraction and Thermal gravimetric analysis (TGA). A higher BET surface area of 121.1 m 2 g −1 was obtained for Cu-MOF synthesized in DMF + C 2 H 5 OH + H 2 O compared with H 2 O (109.3 m 2 g −1 ) and DMF (115.1 m 2 g −1 ) solvents. The as-obtained Cu-MOF was used to investigate adsorption kinetic performances of methylene blue (MB) and methyl orange (MO) dye molecules. Compared with other samples, Cu-MOF synthesized in (DMF + C 2 H 5 OH + H 2 O) has a significantly enhanced adsorption ability for MB but a lower for MO dyes. After 4 min, the adsorption co-efficient ( k) values were calculated to be 0.506, 0.846 and 1.1915 min −1 for MB and 0.029, 0.024 and 0.005 min −1 for MO dyes for Cu-MOF (H 2 O), Cu-MOF (DMF) and Cu-MOF (DMF + C 2 H 5 OH + H 2 O), respectively. It was found that Cu-MOF has a higher adsorption for MB dye but a poor adsorption capacity for MO, which was attributed to the electrostatic attraction/repulsion phenomena. Moreover, compared with Cu-MOF (DMF) and Cu-MOF (H 2 O), Cu-MOF (DMF + C 2 H 5 OH + H 2 O) shows an improved stability at 370, 417 and 423 °C temperatures. The result obtained through experiment suggested that porous Cu-MOF microstructures synthesized in DMF + C 2 H 5 OH + H 2 O have potential application for the treatment wastewaters having MB and MO dyes.
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APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Menglin Li,Xinpeng Wang,Jian Zhang,Yonghao Gao,Wen Zhang
The capture of toxic radioiodine is an increasingly important priority for the safe development of nuclear energy. Copper is a promising alternative for expensive silver to capture iodine. To develop novel copper-based adsorbents and determine the effect of copper species on iodine adsorption, the metal–organic framework with dual-pyrazole ligands (MOF-303) is employed as the scaffold to bind Cu 2+ species. Cu 0 nanoparticles were formed after the reduction by NaBH 4 . The obtained Cu 2+ -MOF-303 and Cu 0 -MOF-303 show high iodine uptake capacities at 353 K, 747 mg·g −1 and 837 mg·g −1 , respectively. They also show high iodine uptake capacities of more than 300 mg·g −1 at a high temperature (423 K), which are better than other Cu-based adsorbents. Besides, the loading of Cu can enhance the iodine selectivity under humid vapor, and iodine adsorption rate in iodine-cyclohexane solutions. The Cu 0 on Cu 0 -MOF-303 can react with iodine directly via the redox mechanism. For Cu 2+ -MOF-303, the adjacent pyrazole ligands can chelate with Cu 2+ ions strongly and transfer charges to trapped iodine to form polyiodide anions, and thus stable CuI species could also be generated. The strategy of anchoring Cu species using MOF-303 provides large channels for iodine diffusion, and highly-dispersed Cu and N sites for iodine capture.
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ANALYTICAL CHEMISTRY
·
2019
·
IF 6.35
Li Fu,Bin Zhang,Xiaoyan Long,Kena Fu,Xuwen Gao,Guizheng Zou
Screening a novel electrochemiluminescence (ECL) system is crucial to ECL evolution. Herein, an efficient ECL system with less interference and environmental concern under physiological condition is developed via a unique internal Cu(I)/Cu(II) couple cycling amplified strategy by employing the glutathione- and citrate-capped copper indium sulfide (CIS)/ZnS nanocrystals (NCs) as electrochemiluminophore and N2H4·H2O as co-reactant. CIS/ZnS NCs can be electrochemically injected with valence band (VB) hole at 0.46 and 0.87 V (vs Ag/AgCl), and then achieve the same hole-injected states by relocalizing VB holes with the Cu(I) species inside of CIS/ZnS NCs to form internal Cu(II) defects, while each N2H4·H2O molecule can be successively oxidized to two more reducing species N2H3• and N2H2 around 0.10 V, and inject conduction band (CB) electron onto CIS/ZnS NCs for triple times. The internal Cu(I)/Cu(II) couple cycling involved radiative-charge recombination between these VB hole and CB electron eventually enables two efficient near-infrared ECL processes (around 731 nm) at 0.55 and 0.87 V, in which each single nanocrystal may participate in multiple ECL reaction cycles to produce multiple photons for amplified ECL, similar to the tris(bipyridyl)ruthenium(III) based ECL system. The low-triggering-potential ECL process at 0.55 V can be utilized to selectively determine Cu(II) with a wide linear range from 10 and 1500 nM and a limit of detection of 5 nM (S/N = 3). This work presents a NCs engineering and co-reactant selecting combined strategy for further ECL evolution.
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