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MICROCHIMICA ACTA · 2017 ·Vol. 184 ·期 7 ·2325-2331 · IF 4.58

Synthesis of silica nanoparticles doped with [Ru(bpy)3]2+ and decorated with silver nanoclusters for the ratiometric photoluminescent determination and intracellular imaging of Cu(II) ions

Huang Xinan,Jiang Hong,Li Yongxin,Sang Lijia,Zhou Huipeng,Shahzad Sohail Anjum,Ibupoto Zafar Hussain,Yu Cong

A sensitive and selective luminescent nanoprobe (referred to as DEPN) is designed for the determination of Cu(II) ions. DEPN shows two emission peaks, one at 602 nm and caused by [Ru(bpy) 3 ] 2+ , the other (peaking at 500 nm) caused by silver nanoclusters (AgNCs). The luminescence of the ruthenium complex is inert and acts as the internal reference signal, while that of the AgNCs is quenched by Cu(II) ions. Under 350 nm photoexcitation, a linear relationship is found between the ratio of emission intensity (I 500 /I 602 ) and the concentration of Cu(II) ions in the 0.1–16 μM range. The detection limit of Cu(II) ions is estimated to be 50 nM. The DEPN was applied to the determination of Cu(II) ions in (spiked) water samples, and to intracellular imaging of Cu(II) in HeLa cells using confocal fluorescence microscopy. Schematic presentation of a dual-emission photoluminescence nanoprobe for selective Cu 2+ sensing. The emission of the Ag nanoclusters (at 500 nm) is quenched by Cu 2+ , while that of the Ru(bpy) 3 2+ -doped silica nanoparticles (at 602 nm) remains unchanged and serves as a reference.

CAS / MDL: 9002-98-6 78-10-4
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ANALYTICAL LETTERS · 2024 · IF 1.6

Ultrasensitive Label-Free Electrochemical Immunosensor for Carbohydrate Antigen-125 (CA125) Employing Cu(II)-Polyethyleneimine (PEI)/Silica Nanoparticle@Overoxidized Polypyrrole (OPPy)/Multi-Walled Carbon Nanotubes (MWNTs) Hybrid Nanomaterial

Zheng Chang,Qiqi Zhao,Binghua Yao,Lei Han

Novel electroactive nanotags of Cu(II) functionalized polyethylenimine (PEI)/SiO2 nanoparticles (abbreviated as Cu2+/PEI/SiO2 NPs) were conveniently synthesized using a strong coordination reaction between Cu(II) and the multi-amino groups of PEI. These electroactive nanotags were easily coated on the overoxidized polypyrrole (OPPy) modified Nafion/multi-walled carbon nanotubes (abbreviated as Nafion/MWNTs) electrode surface through Cu-N bonds and strong electrostatic interactions. The Cu2+/PEI/SiO2 NPs@OPPy/MWNTs hybrid nanomaterial was formed without the addition of extra membrane-forming substances. The experimental results demonstrate that the OPPy/MWNTs composite membrane coupled with electrocatalytic Cu(Tris)42+ complexes in tris(hydroxymethyl)aminomethane (Tris)-HCl buffer medium amplified the electrochemical signals of nanotags based on the mutual synergistic effects. As an application, a label-free electrochemical immunosensor for epithelial ovarian cancer biomarker-carbohydrate antigen-125 (CA125) was constructed by covalently immobilizing CA125 antibody onto the hybrid nanomaterial modified electrode. With the increasing concentrations of CA125 antigen, different decreases in the electrochemical signals of the nanotags were observed due to the formation of antigen-antibody immune complexes. The electrochemical immunosensor showed a linear relationship from 0.001 to 500 U·mL−1 for CA125 with a detection limit of 3.4 × 10−4 U·mL−1. In addition, the proposed immunosensor was applied to the determination of CA125 in human serum with satisfactory results.

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Journal of Environmental Chemical Engineering · 2022 · IF 7.968

Highly efficient removal of As(III), Zn(II), Cu(II) and Cd(II) in aqueous solution using thermal desorption residue from oil sludge contaminated soil: Performance and mechanism

Ge Zhang,Huifen Yang,Tong Zhao,Xuan Li,Yichen Zhou,Song Guo

The thermal adsorption residue (TDR) from oil sludge co-contaminated soil was employed to remove As(III), Zn(II), Cu(II), Cd(II) in aqueous solution. The results showed that the TDR could efficiently neutralize the acid and adapt to the extensive pH. The adsorption of four heavy metals on TDR could be divided into three stages. The maximum adsorption capacity were 86.59, 249.07, 339.88, 322.86 mg·g −1 for As(III), Zn(II), Cu(II), Cd(II), respectively. The coexistence of Zn(II)/Cu(II)/Cd(II) could promote As(III) removal but As(III) led to decreasing of Zn(II)/Cu(II)/Cd(II) adsorption capacity in binary system. There was a significant competitive adsorption on TDR among the three cations which followed the selectivity sequence of Cu(II)>Zn(II)>Cd(II). The SEM-EDS, XRD, FTIR and XPS analyses demonstrated that the As(III) was removed via formation of Ca-As precipitation, and the Zn(II), Cu(II), Cd(II) were removed through precipitating as hydroxides/carbonates/silicates combining with ion exchange. Specially, the Cu(II) mainly precipitated in the form of Cu 4 (SO 4 )(OH) 6 ⋅2H 2 O and Cu 4 (OH) 6 SO 4 under sulfuric acid solution environment. Overall, this study indicates the potential of TDR as a cost-effective adsorbent in acid heavy metals contaminated wastewater treatment .

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Catalysis Science & Technology · 2020 ·Vol. 10 ·期 23 ·8094-8107 · IF 5.721

Spinel copper–iron-oxide magnetic nanoparticles with cooperative Cu(I) and Cu(II) sites for enhancing the catalytic transformation of 1,2-propanediol to lactic acid under anaerobic conditions

Yonghai Feng,Congming Lu,Huijie Wang,Minjia Meng,Yunlei Zhang,Dewei Rao,Lei Liu,Hengbo Yin

The aerobic catalytic oxidation of 1,2-propanediol (PDO) over non-noble metal (e.g. Cu) based catalysts usually suffers serious C3 product dissociation at high temperature, thus showing low lactic acid (LA) selectivity. Here, an alternative anaerobic catalysis strategy over spinel copper–iron-oxide magnetic nanoparticles (CuFeOx MNs) with the coexistence of Cu(I) and Cu(II) dual sites is developed for the catalytic transformation of PDO to LA with a quantitative yield of co-product H2 in basic aqueous solution. The absence of O2 is beneficial for enhancing LA production in comparison with the presence of O2. The synergy between Cu(I) and Cu(II) sites in CuFeOx MNs is vital for improving the catalytic performance as compared to Cu2O or CuO catalysts with Cu(I) or Cu(II) sites alone. Cu1Fe1Ox MNs with a Cu/Fe mole ratio of 1/1 exhibit 94.5% LA selectivity and 72.6% PDO conversion at 160 °C for 8 h. Experimental results and DFT calculations suggest that the spinel CuFeOx MN based catalytic PDO transformation follows a favorable pathway of PDO → hydroxyacetone → lactaldehyde → lactic acid for LA production. In addition to the catalytic PDO transformation, the use of CuFeOx MNs can be extended to favor high activity and selectivity in the catalytic transformation of glycerol to LA (98.5% selectivity) and ethylene glycol to glyceric acid (97.8% selectivity). This work highlights the design of an alternative non-noble metal-based CuFeOx MN catalyst for efficiently catalyzing the transformation of bio-based polyols into value-added carboxylic acids.

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JOURNAL OF INORGANIC BIOCHEMISTRY · 2019 · IF 3.224

Urease inhibition studies of six Ni(II), Co(II) and Cu(II) complexes with two sexidentate N2O4-donor bis-Schiff base ligands: An experimental and DFT computational study

Hu Wang,Cungang Xu,Xia Zhang,Dongmei Zhang,Fan Jin,Yuhua Fan

Six novel complexes, [Ni(C 36 H 34 N 2 O 10 )]·2.25CH 3 OH·0.5C 4 H 10 O ( 1 ), [Co(C 36 H 34 N 2 O 10 )] ( 2 ), [Cu(C 36 H 34 N 2 O 10 )]·2CH 3 OH ( 3 ), [Ni(C 36 H 32 N 2 O 8 Cl 2 )]·2CH 3 OH ( 4 ), [Co(C 36 H 32 N 2 O 8 Cl 2 )]·4CH 3 OH ( 5 ) and [Cu(C 36 H 32 N 2 O 8 Cl 2 )]·2CH 3 OH ( 6 ) with two sexidentate N 2 O 4 -donor bis-Schiff base ligands (C 36 H 34 N 2 O 10  = 1,2-bis(2-methoxy-6-formylphenoxy)ethane- l -tyrosine; C 36 H 32 N 2 O 8 Cl 2  = 1,2-bis(2-methoxy-6-formylphenoxy)ethane- l -4-chlorophenylalanine) have been synthesized and structurally characterized. Theoretical calculation of the six complexes was carried out by density functional theory (DFT) Becke's three-parameter hybrid (B3LYP) method employing the 6-3lG basis set, indicating that the calculation results are in accordance with experimental results. Moreover, the inhibitory activities of complexes 1 – 6 were tested in vitro against jack bean urease . At the same time, molecular docking was investigated to determine the probable binding mode. The experimental values and docking simulation exhibited that complexes 3 and 6 showed strong inhibitory activity (IC 50  = 10.36 ± 1.13, 15.63 ± 3.04 μM) compared with the positive reference acetohydroxamic acid (IC 50  = 26.99 ± 1.43 μM). Their structure-inhibitory activity relationship was further discussed from the perspective of molecular docking and theoretical calculation.

CAS / MDL: 60-18-4
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BIOSENSORS & BIOELECTRONICS · 2023 · IF 12.6

A cost-effective, “mix & act” G-quadruplex/Cu (II) metal-nanozyme-based ratiometric fluorescent platform for highly sensitive and selective cysteine/bleomycin detection and multilevel contrary logic computing

Jun Wang,Jiawen Han,Juan Wang,Xujuan Lv,Daoqing Fan,Shaojun Dong

Versatile nanozymes with fascinating catalytic properties provide inspiring and effective options for biosensing and pharmaceutical analysis. Herein, we report the first nanozyme-based ratiometric fluorescent platform for cysteine (Cys) and bleomycin (BLM) detection by harnessing the cost-effective and “mix & act” G-quadruplex/Cu(II) (G4/Cu) metal-nanozyme with satisfactory peroxidase-like activity, which was fully proven by circular dichroism (CD), electron paramagnetic resonance (EPR) spectra and reactive oxygen species (ROS) scavenging experiments. Based on the catalytic oxidation of G4/Cu metal-nanozyme toward two fluorescent substrates (Amplex Ultrared, AU; Scopoletin , Sc) with opposite responses in the presence of H 2 O 2 , and the specific interaction between Cu 2+ and targets, we achieved the highly sensitive detection of Cys and BLM. Through recording the fluorescence changes of AU (emission at 590 nm, F590) and Sc (emission at 465 nm, F465), we obtained good linear relationships between ratiometric fluorescence values (F590/F465) and variable contents of targets, resulting in the competitive LODs of Cys (6.7 nM) and BLM (10 nM), respectively. Moreover, this platform presented high selectivity (without the need for masking agent) and acceptable performance in human serum samples. Furthermore, a library of DNA contrary logic pairs (CLPs) and multilevel concatenated circuits were fabricated based on the reverse dual-output of the above platform, enriching the building blocks of biocomputing. This work not only enlightened the design of affordable, “mix & act” type nanozyme-based ratiometric biosensors with high reliability, but also facilitated the pluralistic application of nucleic acid-templated nanozymes to innovative biocomputing.

CAS / MDL: 7440-57-5
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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

Editable Au NCs@ZIF-8 nanomaterial-modified paper in situ as well as portable smartphone-assisted sensing assay for the highly sensitive Cu (II) detection in Wilson’s disease

Wenhai Wang,Jiaxuan Li,Bin Hong,Yi Ma,Fei Chen,Keren Kang,Jufang Wang

High levels of Cu (II) in the human body can cause kidney dysfunction, liver cirrhosis, and many neurological diseases, such as Wilson’s disease (WD). Therefore, rapid and efficient detection of Cu (II) in urine is highly essential. First, by a simple multiple seeded growth method, the gold nanoclusters (Au NCs) embedded metal-organic framework (ZIF-8) is decorated on cellulose paper to generate a fluorescent Au NCs@ZIF-8 paper. Then the Au NCs@ZIF-8 paper is loaded on the fluidic cartridge integrated with the syringe for ultra-sensitive urine copper detection. The fluorescence paper is intercalated in a reusable fluidic cartridge and attached to a syringe, allowing the fluidic cartridge to flow a amount of samples through the paper. The interaction of Cu (II) with in situ growth of Au NCs@ZIF-8 on the paper induced fluorescence quenching , which fluorescence images can be recorded and analyzed by the portable smartphone-assisted device. Furthermore, a large amount of sample solution was flowed through the Au NCs@ZIF-8 paper, enabling more Cu (II) to react with the Au NCs@ZIF-8 paper on the novel paper-based analytical device (nPAD). Cu (II) detection can be completed by nPAD in 20 mins, and the limit of detection was as low as 9.2 nM. We show the value of the paper device for on-site detection of copper (II) and indicate that it has excellent potential for clinical applications and environmental monitoring.

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JOURNAL OF CHROMATOGRAPHY A · 2016 · IF 3.926

Development of a high speed counter-current chromatography system with Cu(II)-chiral ionic liquid complexes and hydroxypropyl-β-cyclodextrin as dual chiral selectors for enantioseparation of naringenin

Shanshan Wang,Chao Han,Sisi Wang,Lijuan Bai,Shanshan Li,Jianguang Luo,Lingyi Kong

Cu(II) complexed amino acid ionic liquid , Cu(II)-[1-butyl-3-methylimidazolium][L-Pro] (Cu(II)-[BMIm][L-Pro]), was successfully adopted as chiral ligand to improve the enantioseparation efficiency in high speed counter-current chromatography (HSCCC). For the enantioseparation of intractable naringenin (NRG) racemic mixtures, Cu(II)-[BMIm][L-Pro] coupled with hydroxypropyl-β-cyclodextrin (HP-β-CD) was successfully applied as dual chiral selectors in HSCCC. The influence of important parameters, including the concentration of the chiral selectors, the pH value, and the temperature were investigated. Under optimal conditions, 4.5   mg of (+)-NRG and 4.1   mg of (−)-NRG were successfully separated from 10   mg NRG racemic mixtures with the purity of 98%. The chiral recognition mechanism of dual chiral selectors was illuminated by the UV–vis and NMR spectra, suggesting that the enantioseparation was upon the difference of the thermodynamic stability of the quaternary complexes of Cu(II), [BMIm][L-Pro], HP-β-CD, and NRG. The results illustrated that the developed HSCCC system, based on the synergistic mechanism of Cu(II)-[BMIm][L-Pro] and HP-β-CD, exhibited better performance on enantioseparation and had great application potential in preparative chiral separation of natural products.

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RSC Advances · 2015 ·Vol. 5 ·期 65 ·52369-52381 · IF 3.84

Monodisperse magnetic ion imprinted polymeric microparticles prepared by RAFT polymerization based on γ-Fe2O3@meso-SiO2 nanospheres for selective solid-phase extraction of Cu(II) in water samples

Zhanchao Liu,Zhaoyong Hu,Yan Liu,Minjia Meng,Liang Ni,Xiangguo Meng,Guoxing Zhong,Fangfang Liu,Yanmin Gao

Utilising a general protocol for making surface-imprinted core–shell microparticles via a RAFT-mediated approach, we developed a Cu(II) imprinted polymer with a novel magnetic nanosphere, γ-Fe2O3@meso-SiO2, as support. Attributed to the controlled/living polymerization mechanism of the RAFT polymerization process, the Cu(II) imprinted polymer prepared by RAFT polymerization (IIP-RAFT) presented a more well-defined morphology, more mono-dispersed properties, and much higher magnetic responsiveness, compared to the Cu(II) imprinted polymer prepared by traditional free-radical polymerization (IIP-TP). Moreover, in the static saturation binding experiments, a higher binding capacity of IIP-RAFT (210 mg g−1) than IIP-TP (145 mg g−1) was also found. Afterwards, a series of adsorption experiments were carried out to systematically evaluate the adsorption performance of the as-prepared IIP-RAFT. And the results showed that IIP-RAFT exhibited excellent selectivity, good reusability and desirable dynamic adsorption behavior, and could be an ideal candidate for SPE sorbents for the removal of Cu(II) in real wastewater.

CAS / MDL: 78-67-1 97-90-5 79-41-4
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JOURNAL OF MOLECULAR STRUCTURE · 2024 · IF 4

Urease inhibition studies of two Cu(II) complexes with an ONO tridentate Schiff base and two different secondary ligands: An experimental, DFT, molecular docking and molecular dynamics study

Hu Wang,Pengxiao Guo,Yadong Zhou,Chaochuang Yin,Yizhu Lei,Renshu Wang,Yinyan Wang,Tingting Wu,Ziao Zong

Two mononuclear Copper(II) complexes, identified as [Cu(C 10 H 8 NO 4 F)(C 6 H 7 N)] ( C1 ) and [Cu(C 10 H 8 NO 4 F)(C 12 H 8 N 2 )]·H 2 O·CH 3 OH ( C2 ), incorporating a tridentate Schiff-base ligand with an ONO coordination (C 10 H 8 NO 4 F = 5-fluoro-2-hydroxybenzylidene-L‑serine) and two unique auxiliary ligands (C 6 H 7 N = 4-methylpyridine and C 12 H 8 N 2 = 1,10-phenanthroline) were developed and detailed structurally. Density functional theory (DFT) evaluations of these complexes employed Becke's three-parameter hybrid (B3LYP) approach within the Gaussian 16 computational package. The outcomes from computational analysis corresponded with experimental data. Additionally, the inhibition capabilities of complexes C1 and C2 were evaluated in vitro targeting jack bean urease. Simultaneously, molecular docking was utilized to determine potential binding interactions. Experimental results and docking analyses showed that C1 had considerable inhibitory strength (IC 50 = 2.44 ± 0.15 μM) relative to the benchmark control, acetohydroxamic acid (IC 50 = 27.73 ± 2.93 μM). Furthermore, a 100-ns molecular dynamics assessment was performed to examine the interaction stability of urease with C1 and C2 , using the Desmond 2021 tool from Schrödinger. The correlation between structural configurations and inhibition efficacy was further explored through molecular docking, density functional theory analysis, and molecular dynamics evaluations.

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MOLECULES · 2020 ·Vol. 26 ·期 1 ·109 · IF 3.267

Self-Assembly by Tridentate or Bidentate Ligand: Synthesis and Vapor Adsorption Properties of Cu(II), Zn(II), Hg(II) and Cd(II) Complexes Derived from a Bis(pyridylhydrazone) Compound

Hong-Juan Liu,Rui Yi,Dong-Mei Chen,Chao Huang,Bi-Xue Zhu

Four complexes, [Cu4L2(OCH3)2(CH3OH)2]·2H2O (1), [Zn2L2Cl4]·2H2O·2CH3OH (2), [Hg2L2Br4]·4CH3OH (3), and {[CdL2Cl2]·4H2O·4CH3OH}n(4), have been synthesized and characterized from a bis(pyridylhydrazone) ligand (L) with copper(II), zinc(II), mercury(II) or cadmium(II), respectively. Complex1exists as a centrosymmetric tetranuclear dimer withLas deprotonated tridentate ligand. Complexes2and3exist as centrosymmetric metallamacrocycles withLas bidentate ligand. Complex4exists as a 1D looped-chain coordination polymer. The thermal stabilities and vapor adsorption properties of the four complexes were investigated as well.Keywords:pyridylhydrazone;complex;crystal structure;vapor adsorption

研究领域: 化学 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Competitive adsorption of Cd(II), Pb(II) and Cu(II) ions from acid mine drainage with zero-valent iron/phosphoric titanium dioxide: XPS qualitative analyses and DFT quantitative calculations

Jingjing Ren,Liuchun Zheng,Yaoming Su,Peipei Meng,Qianya Zhou,Hao Zeng,Tao Zhang,Huajian Yu

In order to treat heavy metal pollutants in acid mine drainage, zero-valent iron/phosphoric titanium dioxide (PTO-3nZVI and PTO-nZVI) was developed with phosphoric acid treatment and loading of zero valent iron and showed excellent adsorption of heavy metals. PTO-3nZVI and PTO-nZVI greatly improved the adsorption capacity for the targeted heavy metal Cd(II) (308 mg·g −1 for PTO-3nZVI and 206 mg·g −1 for PTO-nZVI) through complexation and coprecipitation. Additionally, competitive adsorption occurred between Cd(II) and coexisting heavy metal ions (Pb(II) and Cu(II)), resulting in different adsorption effects for PTO-3nZVI and PTO-nZVI, and their adsorption efficiencies decreased in the order Cu(II) > Pb(II) > Cd(II) for PTO-3nZVI and Pb(II) > Cu(II) > Cd(II) for PTO-nZVI. Based on these two aspects, X-ray photoelectron spectrometer (XPS) analyses and Density Functional Theory (DFT) calculations were used to characterize the adsorption behaviors of PTO-3nZVI and PTO-nZVI. In particular, competitive relationships for different heavy metals were clearly revealed by binding energies, Frontier Molecular Orbitals (FMOs) analyses, electrostatic potentials, and total potential and differential charge analyses of adsorption sites, binding sites and binding strengths.

研究领域: 环境科学 · 材料化学 · 重金属修复 · 计算化学 · 水处理
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